December 2, 2024
Development of Amino-Functionalized Silica by Co-condensation and Alkylation for Direct Air Capture
Soichi Kikkawa *- ,
Miori Kataoka - , and
Seiji Yamazoe *
This publication is Open Access under the license indicated. Learn More
CO2 chemisorption using amine-based sorbents is one of the most effective techniques for carbon capture and storage. Solid CO2 sorbents with amines immobilized on their surface have been attracting attention due to the easy collection of sorbents and reusability. In this study, we developed a solid CO2 adsorbent by co-condensation of a silanizing reagent having a chloroalkyl group and tetraethyl ethoxysilane, followed by alkylation of the chloroalkyl group with diamine. The fabricated amine-immobilized silica with a high density of amino groups on its surface achieved the chemical adsorption of 400 ppm of CO2 with 4.3 wtCO2 % loading, CO2 release upon heating at 80 °C, and reusability for adsorption and desorption cycles with high amine utilization efficiency (0.20 molCO2/mol–N). This surface modification method is applicable to various amines bearing more than two amino functional groups, enabling the development of solid CO2 sorbents for the selective capture of low-concentration CO2 directly from the air.
Electrochemically Induced Synthesis of N-Allyloxyphthalimides via Cross-Dehydrogenative C–O Coupling of N-Hydroxyphthalimide with Alkenes Bearing the Allylic Hydrogen Atom
Stanislav A. Paveliev - ,
Oleg O. Segida - ,
Andrey Dvoretskiy - , and
Alexander O. Terent’ev *
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The electrochemically induced reaction between alkenes, bearing an allylic hydrogen atom, and N-hydroxyphthalimide was investigated. Cross-dehydrogenative C–O coupling with phthalimide-N-oxyl radical, derived from N-hydroxyphthalimide, occurs instead of oxidation of the allylic site, with the formation of a carbonyl group or functionalization of the double C═C bond. The discovered transformation proceeds in an undivided electrochemical cell equipped with a carbon felt anode and a platinum cathode. Coupling products were obtained with yields up to 79%. The developed process is based on the abstraction of hydrogen atom from the allylic position for functionalization while the C═C bond remains unreacted. The method exploits the ability of the phthalimide-N-oxyl radical to abstract hydrogen atoms with the following interception of the intermediate C-centered radical.
Facile CVD Fabrication of Vertically Aligned MoS2 Nanosheets with Embedded MoO2 on Molybdenum for High-Performance Binder-Free Lithium-Ion Battery Anodes
Navanya Raveendran - ,
Sruthy Subash - ,
Krishna Moorthy Ponnusamy - ,
Jong Bae Park - ,
Keun Heo - ,
K. Kamala Bharathi *- , and
S. Chandramohan *
This publication is Open Access under the license indicated. Learn More
The demand for compact energy storage devices necessitates the development of high-performance anode materials directly integrated with current collectors, minimizing or eliminating the need for binders or additives. With its layered structure and high theoretical capacity, molybdenum disulfide (MoS2) is regarded as a promising anode material for lithium-ion batteries (LIBs). Here, we report chemical vapor deposition (CVD) growth of self-integrated, vertically aligned MoS2 nanosheets with embedded molybdenum dioxide (MoO2) directly on a molybdenum foil and explore its potential as an anode material for LIBs. The results show that the formation of the MoO2/MoS2 hybrid structure occurs through partial conversion of the initially grown MoO2 crystals to MoS2 layers under controlled sulfurization reactions. The self-integrated hybrid material, devoid of additional conductive or binder agents, exhibits remarkably efficient transfer of ions and electrons, facilitated by the high electrical conductivity of MoO2 and exposed active sites of MoS2. Electrochemical studies reveal an impressive areal capacity of 253 μA h cm–2 for the MoO2/MoS2 hybrid material on a molybdenum foil. In addition, the Li-ion diffusion coefficient value is estimated to be 0.798 × 10–10 and 1.14 × 10–10 cm2/s for the delithiation and lithiation processes, respectively. The capacity of LIBs can be significantly enhanced by engineering the MoO2/MoS2 anode material, making it a promising candidate for overcoming the limitations of single-anode materials. Our findings show that CVD can be a potential approach toward the fabrication of binder and conducting agent-free anodes directly on current collectors for advanced LIBs.
Targeting Non-Apoptotic Pathways with the Cell Permeable TAT-Conjugated NOTCH1 RAM Fragment for Leukemia and Lymphoma Cells
Ryota Uchimura - ,
Shinpei Nishimura - ,
Mikako Ozaki - ,
Manami Kurogi - ,
Kohichi Kawahara - ,
Masaki Makise - , and
Akihiko Kuniyasu *
This publication is Open Access under the license indicated. Learn More
Targeting nonapoptotic cell death offers a promising strategy for overcoming apoptosis resistance in cancer. In this study, we developed Tat-Ram13, a 25-mer peptide that fuses the NOTCH1 intracellular domain fragment RAM13 with a cell-penetrating HIV-1 TAT, for the treatment of T-cell acute lymphoblastic leukemia with aberrant NOTCH1 mutation. Tat-Ram13 significantly downregulated NOTCH1-target genes in T-ALL cell lines. Furthermore, the peptide had potent cytotoxic effects on various human leukemia and lymphoma cell lines. However, it did not affect normal lymphocytes and monocytes, some subsets of leukemia cells, or adherent tumor cells. This cell-selective cytotoxic activity was closely correlated with the peptide uptake via macropinocytosis in leukemia cells. In leukemia cells, Tat-Ram13 triggered rapid cell death. This cell death involved mitochondrial membrane depolarization and extracellular release of lactate dehydrogenase and high-mobility group box-1 protein without activation of caspase-3 or cleavage of PARP-1. These results suggest that Tat-Ram13 cell death is nonapoptotic and mediated by rapid plasma membrane rupture. Moreover, alanine scanning analysis identified four critical hydrophobic amino acids in the RAM13 domain essential for its cytotoxicity. Consequently, these results suggest that Tat-Ram13 is a tumor-selective, nonapoptotic cell death-inducing agent for treating refractory leukemia and lymphomas with apoptosis resistance.
December 1, 2024
Theoretical Insights into High-Tc Superconductivity of Structurally Ordered YThH18: A First-Principles Study
Abdul Ghaffar *- ,
Peng Song - ,
Ryo Maezono - , and
Kenta Hongo *
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There has been a marked increase in interest in high-temperature superconductors over the past few years, sparked by their potential to revolutionize multiple fields, including energy generation and transportation. A particularly promising avenue of exploration has emerged in the form of ternary superhydrides, compounds composed of hydrogen along with two other rare-earth elements. Our investigation focuses on the search for Y–Th–H ternary compounds; employing an evolutionary search methodology complemented by electron–phonon calculations reveals a stable superhydride, P6̅m2-YThH18, capable of exhibiting a critical temperature (Tc) as high as 222 K at 200 GPa along a few low-Tc novel hydrides. Our analysis explores the possibility of alloyed structure formation from the disordered condition of Th-doped YH9 and establishes that the P6̅m2-YThH18 is indeed a structurally ordered structure. This opens up an exciting avenue for research on multinary superhydrides, which could facilitate experimental synthesis and provides potential implications for high-temperature superconductivity research.
November 30, 2024
Spider Webs as Passive Monitors of Microplastic and Its Copollutants in Indoor Environments
Kadamparambil Sivasankaran Aradhana - ,
Vishnu S. Moorchilot - ,
Taiha Joo - ,
Charuvila T. Aravindakumar - , and
Usha K. Aravind *
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Indoor environments are particularly vulnerable to microplastics (MPs) and associated copollutants due to limited air circulation and particulate matter accumulation. Continuous monitoring is essential to evaluate exposure levels and health risks. We propose using indoor spider webs as passive monitors for MPs and their copollutants. MPs were found in both web and dust samples with nonuniform distribution (p < 0.05), indicating contamination hotspots. Web samples had significantly higher MP levels (138–33,570 MPs/g) compared to dust samples (59–9324 MPs/g). A strong positive correlation (r = 0.93, p < 0.05) between MPs in dust and webs suggests that spider webs are effective bioindicators of indoor MP contamination. The study also revealed the presence of Bisphenol A and various phthalic acid esters (PAEs). Co-pollutant concentrations ranged from 52.02–1971.78 μg/kg in webs and 43.18–518.42 μg/kg in dust. Diethyl phthalate (DEP) was more common in webs, while Dibutyl phthalate (DBP) predominated in dust. These findings highlight spider webs’ potential as both effective biomonitoring tools and significant sinks for MPs and their cocontaminants in indoor environments.
November 29, 2024
Effect of Mixing Erythritol and Its Fluorine Analogues to Suppress Supercooling
Masaya Ishikawa - ,
Satoru Tsukada - ,
Xudong Tang - ,
Daiju Wada - ,
Katsuyoshi Hoshino - , and
Junichi Ryu *
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Erythritol is a latent heat storage material suitable for the utilization of unused heat in the medium temperature range of 100–250 °C. However, the supercooling characteristic of sugar alcohols reduces the energy utilization efficiency. In this study, erythritol and its fluorine analogues are mixed to suppress supercooling. Erythritol mixed with 2,3-difluorobutane-1,4-diol at a weight ratio of 1% is determined to be effective in suppressing supercooling. This indicates the possibility of utilizing energy more efficiently.
Digital Light Processing (DLP) 3D Printing Fabrication of Hydrophobic Meshes Incorporating Fluorinated and Silicone-Based Acrylates Combined with Surface Engineering: Comparison of Their Oil–Water Separation Efficiency
Wai Hin Lee *- and
David Haddleton *
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Hydrophobic materials have been fabricated by DLP vat photopolymerization of isobornyl acrylate-based resins with chemical modification and/or surface geometry engineering. Fluorinated and polydimethylsiloxane (PDMS)-based acrylic monomers are used for chemical modification and are incorporated into the printed materials. The water wettability was significantly reduced and plateaued with as low as 5% (w/w) of the auxillary hydrophobic monomer. Regarding surface geometry, meshes with different pore sizes are 3D printed, and the surface hydrophobicity increased with the pore size. We compare the oil–water separation efficiency of the 3D-printed meshes hydrophobized by these three approaches. It was found that the isobornyl acrylate-based resin already demonstrated separation at the optimum pore size. Modification with PDMS showed a further improvement in separation efficiency, whereas no significant increase was observed by use of the fluorinated monomer. This highlights that careful design of surface geometry should be considered to avoid the use of environmentally unfriendly and potentially toxic chemicals when making hydrophobic materials.
Evaluating the Anticancer Properties of Novel Piscidinol A Derivatives: Insights from DFT, Molecular Docking, and Molecular Dynamics Studies
Humaera Noor Suha - ,
Syed Ahmed Tasnim - ,
Shofiur Rahman *- ,
Abdullah Alodhayb - ,
Hamad Albrithen - ,
Raymond A. Poirier *- , and
Kabir M. Uddin *
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Cancer is characterized by uncontrolled cell growth and spreading throughout the body. This study employed computational approaches to investigate 18 naturally derived anticancer piscidinol A derivatives (1–18) as potential therapeutics. By examining their interactions with 15 essential target proteins (HIF-1α, RanGAP, FOXM1, PARP2, HER2, ERα, NGF, FAS, GRP78, PRDX2, SCF complex, EGFR, Bcl-xL, ERG, and HSP70) and comparing them with established drugs such as camptothecin, docetaxel, etoposide, irinotecan, paclitaxel, and teniposide, compound 10 emerged as noteworthy. In molecular dynamics simulations, the protein with the strongest binding to the crucial 1A52 protein exceeded druglikeness criteria and displayed extraordinary stability within the enzyme’s pocket over varied temperatures (300–320 K). Additionally, density functional theory was used to calculate dipole moments and molecular orbital characteristics, as well as analyze the thermodynamic stability of the putative anticancer derivatives. This finding reveals a well-defined, potentially therapeutic relationship supported by theoretical analysis, which is in good agreement with subsequent assessments of their potential in vitro cytotoxic effects of piscidinol A derivatives (6–18) against various cancer cell lines. Future in vivo and clinical studies are required to validate these findings further. Compound 10 thus emerges as an intriguing contender in the fight against cancer.
Impact of the Metal–Organic Frameworks Polymorphism on the Electrocatalytic Properties of CeO2 toward Oxygen Evolution
Nicolle Pauline de Araújo Mendes - ,
Antonio Lopes de Souto Neto - ,
Johnnys da Silva Hortêncio - ,
André L. Menezes de Oliveira - ,
Rafael A. Raimundo - ,
Daniel Araújo Macedo - , and
Fausthon Fred da Silva *
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Hydrogen (H2) is a viable alternative as a sustainable energy source, however, new highly efficient electrocatalysts for water splitting are still a research challenge. In this context, metal–organic frameworks (MOFs)-derived nanomaterials are prominent high-performance electrocatalysts for hydrogen production, especially in the oxygen evolution reaction (OER). Here, a new synthesis of two cerium oxide (CeO2) electrocatalysts using Ce-succinates MOFs as templates is proposed. The cerium succinates polymorphs ([Ce2(Succ)3(H2O)2], Succ = succinate ligand) were obtained via hydrothermal reaction and room temperature crystallization, adopting monoclinic (C/2c) and triclinic (P1̅) crystalline structures, respectively, confirmed by X-ray diffraction (XRD). MOFs-Ce were also characterized by infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). CeO2 electrocatalysts were obtained via MOFs-Ce calcination at 350 °C in air, and characterized by XRD with Rietveld refinement, HRTEM, SEM, FT-IR, and Raman spectroscopy, UV–vis spectroscopy, X-ray photoelectron spectroscopy. Electrocatalytic performances were investigated in KOH 1.0 M solution, and overpotentials were η = 326 mV (for CeO2 (H) from monoclinic MOF-Ce) and η = 319 mV (for CeO2 (RT) from the triclinic MOF-Ce) for a current density of 10 mAcm–2. The Tafel slope values show the adsorption of intermediate oxygenated species as the rate-determining step. The high values of double-layer capacitance, the presence of oxygen vacancies, and low charge transfer resistance agree with the high performance in OER. Additionally, the materials were stable for up to 24 h, according to chronopotentiometry results.
November 28, 2024
Improvement of Electrochemical Performance with Cetylpyridinium Chloride for the Al Anode of Alkaline Al-Air Batteries
Lei Guo *- ,
Rui Sun - ,
Xinlei Chen - ,
Ting Shang - ,
Qingbiao Li - ,
Xingwen Zheng - ,
Riadh Marzouki - ,
Jun Chang - , and
Savaş Kaya
This publication is Open Access under the license indicated. Learn More
Aluminum-air batteries (AABs) are considered among high-power battery systems with various potential applications. However, the strong self-corrosion of Al in alkaline electrolytes negatively affects its Coulombic efficiency and significantly limits their large-scale application. This work presents the use of cetylpyridinium chloride (CPC) as an inexpensive and environmentally benign electrolyte additive in alkaline AABs. Hydrogen evolution test, electrochemical measurement, and surface analysis techniques were used to investigate the inhibition effects of CPC additive for the Al anode. The potentiodynamic polarization data indicated that the effectiveness of the CPC in inhibiting corrosion increased proportionally with higher CPC concentration. The maximum inhibition efficiency of 53.6% was achieved at a CPC dosage of 5 mM. The hydrogen evolution experiment revealed that the rate of hydrogen evolution decreased from 0.789 mL cm–2 min–1 for the pristine NaOH solution to 0.415 mL cm–2 min–1. The combination of X-ray photoelectron spectroscopy (XPS) and ab initio molecular dynamics (AIMD) provides conclusive evidence that CPC may adhere to the surface of Al and create a protective film. These findings indicate that CPC is successful in preventing the self-corrosion of the Al anode. Additionally, the Al anode has improved electrochemical characteristics, including a high specific capacity of 2041 mAh g–1 and a high energy density of 2874 Wh kg–1. This work focuses on the inhibition of self-corrosion of Al and provides novel insights for the design and development of effective additives for AABs.
Strained Mechanical and Fracture Analyses of Armchair-Chiral-Zigzag-Based Carbon Nanotubes Using Molecular Dynamics Simulations
Ama tul Zahra - ,
Jamoliddin Razzokov - ,
Muhammad Kashif - ,
Umedjon Khalilov - ,
Haipeng Li - ,
Kun Luo - ,
Aamir Shahzad *- ,
Guogang Ren *- , and
G. Reza Vakili-Nezhaad
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Carbon nanotubes (CNTs) have emerged as one of the most capable and interesting materials in recent decades and have extraordinary mechanical properties (MPs) and resourceful applications in bioengineering and medicine. Equilibrium molecular dynamics simulations have been performed to investigate the structural and MPs of armchair, chiral, and semiconducting and metallic zigzag single-walled CNTs (SWCNTs) under varying temperature T (K) and compressive and tensile strains ±γ (%) with reactive bond-order potential. New results elaborate on the buckling and deformation mechanisms of the SWCNTs through deep analyses of density profiles, radial distribution functions, structural visualizations, and stress–strain interactions. Density profile and structural visualizations of SWCNTs provide the understanding of atomic arrangements and structural changes under varying ±γ (%) strains. The structure of SWCNT configurations is changed at varying ±γ (%) and T (K) and radial distribution functions present the appropriate peaks for buckling and deformation states. It has been shown that the mechanical responses of different chirality of the SWCNTs clarify the variations in tensile strength in terms of T (K) and chirality. Stress–strain analyses reveal that the metallic zigzag and armchair SWCNTs have superior tensile strength as compared to chiral ones, having the lowest tensile strength. Simulation results show that yield strength, ultimate tensile strength, and Young’s modulus are higher for metallic zigzag and armchair SWCNTs at room T (K) and overall decrease with increasing T (K). However, the ultimate strain of semiconducting zigzag and armchair SWCNTs is higher as compared to other configurations, and it reflects the MPs of SWCNTs have to shed light on potential applications in nanotechnology and material sciences.
Design, Characterization, and Evaluation of Textile Systems and Coatings for Sports Use: Applications in the Design of High-Thermal Comfort Wearables
Ian C. Orjuela-Garzón *- ,
Cristian F. Rodríguez - ,
Juan C. Cruz - , and
Juan C. Briceño
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Exposure to high temperatures during indoor and outdoor activities increases the risk of heat-related illness such as cramps, rashes, and heatstroke (HS). Fatal cases of HS are ten times more common than serious cardiac episodes in sporting scenarios, with untreated cases leading to mortality rates as high as 80%. Enhancing thermal comfort can be achieved through heat loss in enclosed spaces and the human body, utilizing heat transfer mechanisms such as radiation, conduction, convection, and evaporation, which do not require initial energy input. Among these, two primary mechanisms are commonly employed in the textile industry to enhance passive cooling: radiation and conduction. The radiation approach encompasses two aspects: (1) reflecting solar spectrum (SS) wavelengths and (2) transmitting and emitting in the atmospheric window (AW). Conduction involves dissipating heat through materials with a high thermal conductivity. Our study focuses on the combined effect of these radiative and conductive approaches to increase thermal energy loss, an area that has not been extensively studied to date. Therefore, the main objective of this project is to develop, characterize, and evaluate a nanocomposite polymeric textile system using electrospinning, incorporating graphene oxide (GO) nanosheets and titanium dioxide nanoparticles (TiO2 NPs) within a recycled polyethylene terephthalate (r-PET) matrix to improve thermal comfort through the dissipation of thermal energy by radiation and conduction. The textile system with a 5:1 molar ratio between TiO2 NPs and GO demonstrates 89.26% reflectance in the SS and 98.40% transmittance/emittance in the AW, correlating to superior cooling performance, with temperatures 20.06 and 1.27 °C lower than skin temperatures outdoors and indoors, respectively. Additionally, the textile exhibits a high thermal conductivity index of 0.66 W/m K, contact angles greater than 120°, and cell viability exceeding 80%. These findings highlight the potential of the engineered textiles in developing high-performance sports cooling fabrics, providing significant advancements in thermal comfort and safety for athletes.
Electrostatic Orientation of Optically Asymmetric Janus Particles
Mohammad Mojtaba Sadafi - ,
Achiles Fontana da Mota - , and
Hossein Mosallaei *
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Janus micro- and nanoparticles, featuring unique dual-interface designs, are at the forefront of rapidly advancing fields such as optics, medicine, and chemistry. Accessible control over the position and orientation of Janus particles within a cluster is crucial for unlocking versatile applications, including targeted drug delivery, self-assembly, micro- and nanomotors, and asymmetric imaging. Nevertheless, precise mechanical manipulation of Janus particles remains a significant practical challenge across these fields. The current predominant methods, based on fluid flow, thermal gradients, or chemical reactions, have their precision and applicability limited by the properties of their background fluids. Therefore, this study proposes electrostatics to deliberately control the local orientation of optically asymmetric Janus particles (spherical and matchstick-like hybrid metal–dielectric objects) within a cluster to overcome the aforementioned restraints. We introduce a sophisticated multiphysics platform and employ it to explore and unveil the infrastructural physics behind the mechanical behavior of the particles when subjected to electrostatic stimuli in an ionic environment. We investigate how different deterministic and stochastic variables affect the particles’ short- and long-term responses. By judicious engineering of amplitude, direction, and polarization of the external excitation, we demonstrate that the particles tend to undergo the desired rotational motion and converge to favorable orientations. The functionality of our approach is showcased in the context of an asymmetric imaging system based on optically asymmetric Janus particles. Our findings suggest a viable platform for adequate mechanical manipulation of Janus particles and pave the way for enabling numerous state-of-the-art applications in various fields.
Comparison of the Performance of ICP-MS, CV-ICP-OES, and TDA AAS in Determining Mercury in Marine Sediment Samples
Carolina S. Provete - ,
Bruna M. Dalfior - ,
Rafael Mantovaneli - ,
Maria Tereza W. D. Carneiro - , and
Geisamanda P. Brandão *
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Mercury (Hg) determination in marine sediment is an analytical challenge due to the toxicity of this element even at low concentrations (up to 130 μg kg–1 in marine sediments) and complex matrices. Therefore, it is necessary to use analytical techniques that have high sensitivity, selectivity, and low limits of quantification (LoQ). In this study, two methods that require sample treatment and one method with direct sampling were studied. The techniques studied were inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma optical emission spectrometry with cold vapor generation (CV-ICP-OES), and atomic absorption spectrometry with thermodecomposition and amalgamation (TDA AAS) for Hg determination in marine sediment samples. Since ICP-MS has more studies in the literature, optimization with design of experiments was developed for CV-ICP-OES and TDA AAS. Although it was found to have low levels of instrumental LoQ for all three techniques, differences were found once the method LoQ was calculated. The calculation for method LoQ considers all analytical procedures executed, including sample treatment, which provides a 100-fold dilution for ICP-MS and CV-ICP-OES. The method LoQ obtained were 1.9, 165, and 0.35 μg kg–1 for ICP-MS, CV-ICP-OES, and TDA AAS, respectively. Comparing marine sediment sample analyses, Hg concentrations had no statistical difference when determined by ICP-MS and TDA AAS. It was not possible to determine Hg in marine sediment samples by CV-ICP-OES due to the high method LoQ obtained (165 μg kg–1). Although ICP-MS has the advantage of being a multielemental technique, it is high-value equipment and needs a large volume of argon, which has a high cost in the market, and it requires sample treatment. On the other hand, TDA AAS-based spectrometer DMA-80 performs direct sampling, avoiding the pretreatment stage, and has a relatively lower cost, both in terms of initial investment and maintenance, while maintaining the high sensitivity, accuracy, and precision required for Hg determination on marine sediment samples.
Fc–FcγRI Complexes: Molecular Dynamics Simulations Shed Light on Ectodomain D3′s Potential Role in IgG Binding
Aslı Kutlu *- ,
Eda Çapkın - ,
Kaan Adacan - , and
Meral Yüce *
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FcγRI plays a crucial role in the effector function of IgG antibodies, interacting with the lower hinge region of IgG1 with nanomolar affinity. Binding occurs specifically in domain 2 (D2) of the FcγRI ectodomain, while domain 3 (D3) is a flexible linker. The D3 domain is positioned away from the IgG binding site on the FcγRI and does not directly contact the Fc region. This study investigates the structural and functional properties of FcγRI D3 using 200 ns classical MD simulations of two models: (1) a full FcγRI ectodomain complex with Fc and (2) a truncated model excluding D3. Our findings suggest that the D3 ectodomain provides additional structural flexibility to the FcγRI–Fc complex without altering the C backbone motion or flexibility of the KHR binding motif in the FG loop. Critical residues involved in binding and contributing to complex stability were evaluated regarding changes in intramolecular interactions and destabilization tendency upon D3 truncation. Truncation did not significantly alter interactions around glycan-interacting residues in Fc chains or FcγRI–Fc binding interfaces. These findings provide valuable insights into the role of FcγRI D3 in modulating the structural dynamics of the FcγRI–Fc complex. While D3 does not directly contact Fc, its mobility and positioning may modulate the receptor’s affinity, accessibility, and ability to bind IgG immune complexes. We suggest that a truncated FcγRI construct lacking the D3 domain may be a promising candidate for biosensor or capturing agents’ development and optimization, offering improved performance in IgG capture assays without compromising critical binding interactions.
Quality and Safety in Asparagus Cultivation: A Three-Year Case Study Comparing Standardized Agricultural Bases and Small-Scale Farmers
Yuhong Liu - ,
Gangjun Wang - ,
Guoguang Yu - ,
Weiran Zheng - , and
Caixia Sun *
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To investigate the quality and safety difference between agricultural standardization bases and small-scale farmers, we carried out a three-year investigation of asparagus from seven production sites of different sizes in Pinghu city, Zhejiang Province, China, from 2021 to 2023. We documented trace elements (Fe, Zn, Mn, and Cu), quality indicators (vitamin B1, vitamin B2, vitamin C, total sugar, and proteins), and pesticide residues. The evaluation indicated that the quality of asparagus in standardization bases 1–4 was higher than that in small farmer sites 5–7. The detection rate of pesticides in asparagus was 23.81% (15/63), with a low concentration range of 0.001–0.130 mg mL–1. Low pesticide levels reflect Pinghu’s effective green pest control measures. Results showed that the quality and safety of asparagus at the standardization bases are superior to those at small-scale farmer sites, and our findings may inform better management practices for both large-scale and small-scale asparagus farmers.
Modeling and Simulation of Micron Particle Agglomeration in a Turbulent Flow: Impact of Cylindrical Disturbance and Particle Properties
Shuang Wang - ,
Lin Mu - ,
Chu Wang - ,
Xue Li - ,
Jun Xie - ,
Yan Shang - ,
Hang Pu - , and
Ming Dong *
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The fly ash generated by coal combustion is one of the main sources of PM2.5, so the particulate matter removal technology of coal-fired boilers is receiving increasing attention. Turbulent agglomeration has emerged as a powerful tool for improving the efficiency of removing fine particulates from environments, sparking interest in its study. Our research meticulously investigated the influence of cylindrical vortex wakes on particle flow, agglomeration patterns, and the dynamics between fluids and particles. By employing a novel hybrid computational approach that integrates the discrete element method (DEM) with large Eddy simulation (LES), we were able to accurately simulate particle–particle interactions. The study focused on understanding how particles with different diameters (2, 5, 10, and 20 μm), densities (2,500, 5,000, 7,500, and 10,000 kg·m–3), and surface energies (0.01, 0.1, and 1 J·m–2) behaved within transitioning shear layer flow conditions. Our findings revealed that particles tended to congregate in areas of lower vorticity, with larger and denser particles demonstrating greater agglomeration efficiency due to their resilience against turbulent forces. Conversely, particles of lower density formed smaller agglomerates as their susceptibility to shear forces increased. Additionally, the study discovered that higher surface energies enhance adhesion, leading to the formation of larger agglomerates.
Influence of Gold Nanoparticles on eNOS Localization in Gill Tissues: Advancements in Immunofluorescence Techniques
Ramla Gary - ,
Manel Ben Salah - ,
Taoufik Soltani - ,
Patrizia Formoso - , and
Souhaira Hbaieb *
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This study optimizes immunofluorescence techniques using gold nanoparticles (AuNPs) to improve visualization of endothelial nitric oxide synthase (eNOS) in gill tissue. Two types of AuNP dispersions, stabilized in phosphate buffered saline (PBS) and citrate buffer (CB), were evaluated for their imaging performance. AuNPs suspended in PBS provided significantly better optical contrast due to uniform distribution and effective tissue attachment, whereas citrate-suspended AuNPs exhibited aggregation, resulting in reduced contrast. These results highlight the influence of suspension media on AuNP performance, particularly in balancing fluorescence signals to improve contrast. The PBS suspension allowed clearer visualization of eNOS, highlighting the role of AuNP compatibility in improving immunofluorescence results. This study highlights the importance of strategic selection of AuNP dispersions in contrast agent design and provides insights for advanced imaging applications where sensitivity and accurate localization of biomolecules are essential. By refining the use of AuNPs as contrast enhancers, this approach offers potential improvements in bioimaging accuracy, facilitating more precise visualization in complex tissue environments.
Exploring the Mechanisms Underlying Cellular Uptake and Activation of Dendritic Cells by the GK-1 Peptide
Jacquelynne Cervantes-Torres - ,
Juan A. Hernández-Aceves - ,
Julián A. Gajón Martínez - ,
Diego Moctezuma-Rocha - ,
Ricardo Vázquez Ramírez - ,
Sergio Sifontes-Rodríguez - ,
Gemma L. Ramírez-Salinas - ,
Luis Mendoza Sierra - ,
Laura Bonifaz Alfonzo - ,
Edda Sciutto *- , and
Gladis Fragoso *
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The use of peptides for cancer immunotherapy is a promising and emerging approach that is being intensively explored worldwide. One such peptide, GK-1, has been shown to delay the growth of triple-negative breast tumors in mice, reduce their metastatic capacity, and reverse the intratumor immunosuppression that characterizes this model. Herein, it is demonstrated that GK-1 is taken up by bone marrow dendritic cells in a dose-dependent manner 15 min after exposure, more efficiently at 37 °C than at 4 °C, implying an entrance into the cells by energy-independent and -dependent processes through clathrin-mediated endocytosis. Theoretical predictions support the binding of GK-1 to the hydrophobic pocket of MD2, preventing it from bridging TLR4, thereby promoting receptor dimerization and cell activation. GK-1 can effectively activate cells via a TLR4-dependent pathway based on in vitro studies using HEK293 and HEK293-TLR4-MD2 cells and in vivo using C3H/HeJ mice (hyporesponsive to LPS). In conclusion, GK-1 enters the cells by passive diffusion and by activation of the transmembrane Toll-like receptor 4 triggering cell activation, which could be involved in the GK-1 antitumor properties.
Geochemical Characteristics and Uranium Mineralization Processes in the Shawan Formation of the Chepaizi Uplift, Junggar Basin, Northwestern China
Niannan Chen - ,
Mangen Li *- ,
Guangzhen Mao - ,
Xiangfei Tang - ,
Shengming Wu - ,
Jianbing Duan - ,
Baowen Guan - ,
Pengfei Fan - ,
Rui Jin - , and
Jin Wang
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The Chepaizi Uplift, situated on the western edge of the Junggar Basin in northwestern China, has recently become a significant target area for in situ leach sandstone-type uranium exploration. The Neogene Shawan Formation, a newly identified uranium-bearing layer, has gained considerable attention for its potential. This study utilizes scanning electron microscopy (SEM), X-ray powder diffraction (XRD), whole-rock geochemistry, and electron probe microanalysis (EPMA) of uranium minerals. Combined with sedimentological and tectonic background analysis, these methods were applied to investigate geochemical characteristics and uranium mineralization processes. The sandstones in the Shawan Formation are primarily lithic sandstone and subarkose, with the provenance dominated by felsic rocks from the upper crust. Coffinite is the predominant uranium mineral, accompanied by titanium–uranium oxides and minor amounts of pitchblende. Coffinite appears as colloidal coatings around framboidal pyrite, in short-prismatic aggregates corroding albite, and as banded structures within calcite cement. Elemental ratios indicate that the Shawan Formation’s paleo-hydrological environment was arid, continental, and brackish, with paleo-redox conditions reflecting a hot, dry climate. Uranium mineralization occurred in two stages: initially, uranium-containing oxygenated waters migrated laterally across slope zones, forming a redox transition zone and resulting in the pre-enrichment of uranium. Subsequently, hydrocarbons migrated along faults and unconformities, leading to secondary reduction of the interlayer oxidation zone and resulting in uranium enrichment and mineralization at the interface of grayish-green and gray sandstone layers.
Assessing Lettuce Exposure to a Multipharmaceutical Mixture under Hydroponic Conditions: Findings through LC-ESI-TQ Analysis and Ecotoxicological Assessments
Ludmila Mravcová - ,
Vojtěch Jašek - ,
Marie Hamplová - ,
Jitka Navrkalová - ,
Anna Amrichová - ,
Helena Zlámalová Gargošová - , and
Jan Fučík *
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The escalating global water scarcity demands innovative solutions, one of which is hydroponic vegetable cultivation systems that increasingly use reclaimed wastewater. Nevertheless, even treated wastewater may still harbor various emerging organic contaminants, including pharmaceuticals. This study aimed to comprehensively assess the impact of pharmaceuticals, focusing on bioconcentration factors (BCFs), translocation factors (TFs), pharmaceutical persistence in aqueous environment, ecotoxicological end points, and associated environmental and health risks. Lettuce (Lactuca sativa) was cultivated hydroponically throughout its entire growth cycle, exposed to seven distinct concentration levels of contaminants ranging from 0 to 500 μg·L–1 over a 35-day period. The findings revealed a diverse range of BCFs (2.3 to 880 L·kg–1) and TFs (0.019–1.48), suggesting a high potential of pharmaceutical uptake and translocation by L. sativa. The degradation of 20 pharmaceuticals within the water-lettuce system followed first-order degradation kinetics. Substantial ecotoxicological effects on L. sativa were observed, including increased mortality, alterations in root morphology and length, and changes in biomass weight (p < 0.05). Furthermore, the estimated daily intake of pharmaceuticals through L. sativa consumption suggested considerable health risks, even if lettuce would be one of the many vegetables consumed. It is hypothetical, as the values were calculated. Moreover, this study assessed the environmental risk associated with the emergence of antimicrobial resistance (AMR) in aquatic environments, revealing a significantly high risk of AMR emergence. In conclusion, these findings emphasize the multifaceted challenges posed by pharmaceutical contamination in aquatic environments and the necessity of proactive measures to mitigate associated risks to both environmental and human health.
Raman Spectra and Excitonic Effects of the Novel Ta2Ni3Te5 Monolayer
Alexandre C. Dias *- ,
Raphael M. Tromer - ,
Humberto R. Gutiérrez - ,
Douglas S. Galvão - , and
Elie A. Moujaes *
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We have investigated the Raman spectrum and excitonic effects of the novel 2D Ta2Ni3Te5 structure. The monolayer is an indirect band gap semiconductor with an electronic band gap value of 0.09 and 0.38 eV, determined using GGA-PBE and HSE06 exchange-correlation functionals, respectively. Since this structure is energetically, dynamically, and mechanically stable, it could be synthesized as a free-standing material. We identify 10 Raman- and 10 infrared-active modes for various laser energies, including those commonly used in Raman spectroscopy experiments. It was also observed that the contribution of Ni atoms is minimal in most Raman vibrational modes. In contrast, most infrared vibrational modes do not involve the vibration of the Ta atoms. As far as the optical properties are concerned, this monolayer shows a robust linear anisotropy, an exciton binding energy of 287 meV, and a high reflectivity in the ultraviolet region, which is more intense for linear light polarization along the x direction.
November 27, 2024
Electromagnetic-Driven Spider-Inspired Soft Robot Using Electroelastic Materials and Conductive Actuators
Yanfang Guan *- ,
Lin Yang - ,
Wei Yang - ,
Qingyuan Zhang - ,
Kasolo Enock - ,
Yansheng Liu - ,
Lin Zhang - ,
Haiyong Chen - ,
Yuhang Jian - ,
Zichen Li - ,
Zhengyang Xi - ,
Yuliang Kang - , and
ShuaiLong Zhang
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Soft robots have developed gradually in the fields of portability, high precision, and low noise level due to their unique advantages of low noise and low energy consumption. This paper proposes an electromagnetically driven elastomer, using gelatin and glycerol (GG) as matrix materials and a mixture of multiwalled carbon nanotubes (MWCNTs) and Ag NWs (MA) as the conductive medium. Inchworm-inspired and spider-inspired soft robots have been developed, demonstrating fast movement speed, flexibility, and loading performance. The GG/MA elastomer with a 1:1.2 ratio shows a low elastic modulus and easy demolding. With a 1:1 mixing ratio of MWCNT and Ag NWs, the elastomer exhibits excellent conductivity, torsional stability, and fatigue resistance. The inchworm-inspired soft robot achieves an average speed of 3 mm/s, while supporting weights of grains and capsule at 2.5 and 2.3 mm/s, respectively. The spider-inspired soft robot demonstrates a maximum carrying capacity of 22 g, showcasing its load-bearing capabilities. Overall, the GG/MA elastomer-based soft robot exhibits exceptional flexibility, adaptability, and reliability, with potential in various fields such as goods transportation, safety monitoring, and disaster relief.
Improvement of Photocatalytic and Photodegradable ZnSe Nanorods by a Vulcanization Strategy
Long Chen *- ,
Kai Ou *- ,
Zhaosen Fan - ,
Lingyu Liu - ,
Fanggong Cai - ,
Yudong Xia - , and
Hongyan Wang
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Photocatalysts composed of ZnSe nanorods were prepared by using a glancing angle deposition technique facilitated by electron beam evaporation equipment. To enhance the photocatalytic efficiency of ZnSe, a vulcanization process was introduced. The impact of various parameters, including curing temperature, duration, and nanorod length, on the photocatalytic performance was systematically examined. Comprehensive analysis using X-ray diffraction, scanning electron microscopy, and photocurrent density–potential curves identified optimal vulcanization conditions at 300 °C for 45 min for 170 nm ZnSe nanorods. Under these conditions, the photocurrent reached 44.53 μA/cm2, approximately 7-fold greater than that of untreated ZnSe nanorods. Furthermore, the degradation efficiency of Rhodamine B increased by 50%. Detailed analysis of the photocatalytic mechanism revealed that sulfurization not only enhances light absorption but also facilitates the separation of photogenerated carriers through the formation of ZnS.
Effect of Gentamicin-Loaded Calcium Phosphate Coating and Polymeric Coating on the Degradation Properties of Biodegradable Iron-Based Biomaterials
Martina Petráková - ,
Radka Gorejová - ,
Jana Shepa - ,
Ján Macko - ,
Miriam Kupková - ,
Ondrej Petruš - ,
Matej Baláž - ,
Tibor Sopčák - ,
Matej Mičušík - ,
Martin Kožár - ,
Vanda Hajdučková - , and
Renáta Oriňaková *
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In the past decades, iron has been one of the intensively studied biodegradable metals due to its suitable mechanical properties, but it suffers from slow degradation in a physiological environment and low bioactivity. In this work, the beneficial properties of ceramic and polymer coatings were merged to enhance the corrosion properties and biological compatibility of Fe-based biomaterials. A new bilayer coating for Fe-based biomaterials that speeds up degradation while offering controlled, localized drug release to prevent infections was prepared. In addition, bioactive coatings with an incorporated antibiotic (gentamicin, Ge) were produced to introduce antibacterial properties into the prepared biomaterials and thus increase their bioactivity. The calcium phosphate (CaP) coating layer as well as a bioactive coating layer of CaP doped with gentamicin was electrochemically deposited onto an iron substrate. A layer of poly(ethylene glycol) was subsequently applied to the selection of prepared specimens to create a bilayer ceramic/polymer coating. Electrochemical and immersion corrosion tests revealed that the application of a bilayer coating allowed achieving the desired acceleration of degradation, while the application of only a ceramic coating led to a reduction in the corrosion rate. A slight increase in the corrosion rate was observed for samples with bioactive drug-containing coatings compared to samples with drug-free coatings. Higher viability of human fibroblastic cells cultured in the extracts of the tested samples was noted for samples with a bilayer coating compared to a ceramic coating. The addition of gentamicin in the bioactive coatings had no significant effect on the viability value. Antibacterial tests proved the antibacterial activity of samples with a gentamicin-loaded coating layer against Escherichia coli and Staphylococcus aureus strains. A detailed study of the release of gentamicin from the prepared coatings revealed a different mechanism of drug release from the ceramic and the ceramic/polymer coating. Furthermore, it was found that the drug was released more slowly and uniformly from the bilayer coating. It is therefore possible to adjust the amount and duration of drug release from the bioactive coating by the thickness of the upper polymer layer. Incorporation of an antibiotic in a combined ceramic/polymer coating enabled the creation of a high-performance bioactive coating for Fe bone implants with the possibility to release a drug in the vicinity of the implant in a controlled manner to address the needs of the patient.
Intermediate-Controlled Synthesis of Quasi-2D (PEA)2MA4Pb5I16 in the 20–30% Relative Humidity Glovebox Environment for Fabricating Perovskite Solar Cells with 1 Month Durability in the Air
Yen-Shuo Chen - ,
Min-Han Hsieh - ,
Ching-Chang Lin - ,
Yi-Cheng Huang - ,
Shang-Yu Tsai - , and
Fu-Hsiang Ko *
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Herein, quasi-two-dimensional (Q-2D) (PEA)2MA4Pb5I16 (prepared by a two-step process) and hole transport layer of a solar cell were fabricated in a high relative humidity (25 ± 5%) environment. The PSC behavior of most Q-2D perovskites is worse than that of three-dimensional perovskites owing to the horizontal alignment of the innate characteristic organic plates on the substrate. Using hybrid immersion solvents (HISs), we have improved vertical alignment in an appropriate ratio to enhance the efficiency of charge transfer and the high coverage of the first priming layer (first step). The grazing incidence X-ray diffraction pattern of the optimized structures revealed a preferential orientation for the vertical alignment of (111), which improved the charge transfer in PSCs and micrometer-level grain size growth. The second step was processed in a high-humidity environment (50 ± 5%) (methylammonium iodide solution embedded), and Q-2D (PEA)2MA4Pb5I16 demonstrated distinct grain boundaries. The power conversion efficiency (PCE, 13.09%) of the champion device of the first priming layer prepared using the HIS system increased by >55% compared to the single-immersion solvent (8.3%). The PCE of the ion-modified ETL PSCs was 16.02% (CsF-3) and 14.58% (CsCl-3) and demonstrated 22 and 11% improvement, respectively. The ion-modified electron transport layer (ETL) was deposited in the air, which reduced the power consumption of preparing perovskite solar cells (PSCs). Finally, all Q-2D PSCs were stored in the air, and three PSCs (DMF/DMSO, CsF-3, and CsCl-3) using HIS exhibited long-term stability for 1 month maintaining 80–88% of PCE, demonstrating the importance of the HIS system to improve the first step of growth orientation, which enhances the stability and photovoltaic properties of PSCs.
Marañon Nutshell Extract as a Carbon Steel “Green” Inhibitor in Marine Environments
David Bonfil - ,
Lucien Veleva *- ,
Diana Rubi Ramos-López - ,
William Santiago González-Gómez - , and
Gloria Ivette Bolio-López
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Natural marañon nutshell extract was obtained by mechanical compression. The extract was combined with ethanol and a nonionic surfactant, and it was labeled as EES. The EES inhibitor effect on S135 carbon steel, exposed to a simulated marine-coastal environment (SME), was deduced by mass loss measurement, adsorption isotherm, electrochemical measurements, and surface analysis. The Langmuir adsorption isotherm suggested that a monolayer of the marañon extract was attached by physical–chemical interaction with the steel surface. The increase in the protective efficiency of the adsorbed EES inhibitor was ascribed to the gain of the surface coverage as a function of the inhibitor concentration. It was considered an antioxidant activity of the inhibitor, attributed mostly to the Fe-ion capture by anacardic acid and the posterior ion chelation. This fact was collaborated by the negative zeta potential of the marañon nutshell extract, added to the SME. Electrochemical impedance spectroscopy (EIS) diagrams revealed that the steel polarization resistance (Rp) increased as a function of the inhibitor concentration, while the thickness (d) of the Fe-oxide layer was reduced to ≈0.50 nm.
Synthesis of N-Heteroaryl C-Glycosides and Polyhydroxylated Alkanes with Diaryl Groups from Unprotected Sugars
Yixuan Liu - ,
Jilai Wu *- ,
Likai Zhou - ,
Chao Wei - , and
Hua Chen *
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HCl-catalyzed C-glycosylation was described herein for the convenient preparation of N-heteroaryl C-glycosides and polyhydroxylated alkanes with diaryl groups using hetereoaryl amines and unprotected sugars as starting materials. The reaction temperature and the amounts of aryl amines and HCl had significant effects on reactions. The method provided a highly efficient and environmentally friendly route for constructing C-glycosides at low cost.
Preanalytical (Mis)Handling of Plasma Investigated by 1H NMR Metabolomics
Daniel Malmodin *- ,
Anders Bay Nord - ,
Huma Zafar - ,
Linda Paulson - ,
B. Göran Karlsson - , and
Åsa Torinsson Naluai
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The preanalytical handling of plasma, how it is drawn, processed, and stored, influences its composition. Samples in biobanks often lack this information and, consequently, important information about their quality. Especially metabolite concentrations are affected by preanalytical handling, making conclusions from metabolomics studies particularly sensitive to misinterpretations. The perturbed metabolite profile, however, also offers an attractive choice for assessing the preanalytical history from the measured data. Here we show that it is possible using Orthogonal Projections to Latent Structures Discriminative Analysis to divide plasma NMR data into a multivariate “original sample space” suitable for further less biased metabolomics analysis and an orthogonal “preanalytical handling space” describing the changes occurring from preanalytical mishandling. Apart from confirming established preanalytical effects on metabolite levels, e.g., the consequent changes in glucose, lactate, ornithine, and pyruvate, the sample preparation protocol involved methanol precipitation which allowed the observation of reversible changes in short-chain fatty acid concentrations as a function of temperature.
Novel Glycyrrhetin Ureas Possessing 2-Hydroxy-3-enone A Ring: Modification, Anti-inflammatory Activity, and Targeted STING for the Remedy of Acute Kidney Injury
Hongbo Wang - ,
Xiaoming Wu - ,
Ziyun Li - ,
Kuanrong Rong - ,
Shan Gao - ,
Wenjian Tang *- , and
Jing Zhang *
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Glycyrrhetin urea has emerged as a privileged scaffold with anti-inflammatory activity for the treatment and prevention of acute kidney injury (AKI). In this study, structural modifications of the A ring of glycyrrhetinic acid yielded a series of urea derivatives, among which compound 7o exhibited the most promising anti-inflammatory activity. 7o was confirmed to interact with STING through a cellular heat shift assay and to inhibit the STING/NF-κB pathway in RAW264.7 cells. It acted on the STING pathway, inhibited NF-κB phosphorylation, and subsequently reduced the level of release of inflammatory factors. Additionally, 7o significantly increased the survival rate of renal tubular epithelial cells, demonstrating a protective effect against cisplatin-induced cell death and mitigating inflammation activation. The in vivo AKI mouse model showed that 7o significantly downregulated serum creatinine (Scr), blood urea nitrogen (BUN), and levels of inflammatory factors (IL-1β, IL-6, and TNF-α), thereby improving renal function. Morphological analysis revealed that 7o attenuated the cisplatin-induced renal tubular injury. Therefore, 7o represents a promising lead for the prevention and treatment of AKI.
Exploring Molecular Descriptors and Acquisition Functions in Bayesian Optimization for Designing Molecules with Low Hole Reorganization Energy
Rinta Kawagoe - ,
Tatsuhito Ando *- ,
Nobuyuki N. Matsuzawa - ,
Hiroyuki Maeshima - , and
Hiromasa Kaneko *
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Organic semiconductors have been widely studied owing to their potential applications in various devices, such as field-effect transistors, light-emitting diodes, solar cells, and image sensors. However, they have a limitation of significantly lower carrier mobility compared to silicon, which is a widely used inorganic semiconductor. Therefore, to address such limitations, these molecules should be further explored. Hole reorganization energy has been known to influence carrier mobility; that is, lower energy results in higher mobility. This study uses Bayesian optimization (BO) to identify molecules with low hole reorganization energies. While several acquisition functions (AFs), including probability of improvement, expected improvement, and mutual information, have been proposed for use in BO, it is well established that the performance of AFs can vary depending on the data set. We evaluate the performance of AFs applied to a data set of organic semiconductor molecules and propose a novel approach that alternates the use of AFs in the BO process. Our findings conclude that alternating AFs in BO enhance the stability of the search for molecules with low reorganization energy.
November 26, 2024
Evaluation of the Combinatory Anticancer Effect of Chemotherapeutic Compounds and Prodigiosin against HCT-116, LoVo, and A549 Cell lines
Fares Elghali - ,
Dhouha Msalbi - ,
Fakher Frikha - ,
Mona Alonazi - ,
Emna Sahli - ,
Bochra Hakim - ,
Sami Mnif - ,
Abir Ben Bacha *- , and
Sami Aifa
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Despite their wide usage in reducing tumors and improving patients’ survival, chemotherapeutic drugs or natural compounds are facing the development of cancer resistance. Many experimental data and clinical trials have shown that combinatorial treatment could be an efficient solution for some resistance problems. In this study, we aimed to evaluate the synergistic effects of combining prodigiosin (PG), a natural compound with known anticancer properties, with the commonly used chemotherapy drugs 5-fluorouracil (5-FU), oxaliplatin, and paclitaxel. The primary objective was to identify the most potent combination that could enhance tumor cytotoxicity while minimizing drug resistance. In vitro experiments using three cancer cell lines (LoVo, HCT-116, and A549) were conducted to assess the impact of these combinations on the cell viability and proliferation. Recorded data demonstrated that the combination of 20 μM PG with 1/2 IC50 of 5-FU showed the most significant decrease in cell viability, with remaining viabilities of 28, 32, and 43% for LoVo, HCT-116, and A549 cells, respectively. This combination resulted in a notable increase in the proportion of cells in the G0/G1 phase and a decrease in the S phase of the cell cycle. These findings indicated that this combination effectively induced cell-cycle arrest. In contrast, other combinations such as PG with paclitaxel or oxaliplatin were less effective. Furthermore, molecular docking studies revealed that PG targets Akt1, a key protein in the PI3K/Akt survival pathway, providing a possible explanation for its proapoptotic effects. These findings suggested that the combination of PG with 5-FU enhanced tumor cell sensitivity to chemotherapy, potentially offering a more effective treatment strategy for overcoming drug resistance. In conclusion, the current study highlighted the promising potential of PG in combination with 5-FU as a therapeutic approach for colorectal and lung cancers, warranting further investigations in preclinical and clinical settings.
Sensing Hachimoji DNA Bases with Janus MoSH Monolayer Nanodevice: Insights from Density Functional Theory (DFT) and Non-Equilibrium Green’s Function Analysis
Vasudeo Babar - ,
Sitansh Sharma *- ,
Abdul Rajjak Shaikh - ,
Romina Oliva - ,
Mohit Chawla - , and
Luigi Cavallo *
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Detection of nucleobases is of great significance in DNA sequencing, which is one of the main goals of the Human Genome Project. The synthesis of Hachimoji DNA, an artificial genetic system with eight nucleotide bases, has induced a transformative shift in genetic research and biosensing. Here, we present a systematic investigation of the adsorption behavior and electronic transport properties of natural and modified DNA bases on a Janus molybdenum sulfur hydride (MoSH) monolayer using density functional theory (DFT) and nonequilibrium Green’s function (NEGF) methods. Our results demonstrate that the S side of the MoSH monolayer is more effective as a sensing platform compared to the H side, which undergoes significant structural distortions due to chemisorption. The S side selectively distinguishes natural bases A and T from G and C, and modified bases S and Z from others. However, the negligible changes in current after base adsorption highlight the limitations of relying solely on current sensitivity for detection. Our findings provide valuable insights into the design of MoSH monolayer-based sensing platforms for selective DNA base detection, with potential applications in next-generation DNA sequencing technologies.
Folic Acid–Intercalated Mg/Al Layered Double Hydroxides─A Multifunctional Nanohybrid Delivery System for Topical Applications
Phumelele Kleyi - ,
Vusani Mandiwana - ,
Marinda de Beer - ,
Sreejarani Kesavan Pillai - , and
Suprakas Sinha Ray *
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The delivery of active functional molecules across the skin is laborious due to its structural intricacy and exceptional barrier characteristics. Developments in nanotechnology yielded innovative transport vehicles derived from nanomaterials to reinforce the skin’s ability to interact with active ingredient molecules and increase its bioavailability. The current study employed crystalline inorganic two-dimensional double hydroxides (LDHs) as an efficient carrier and delivery vehicle for folic acid (FA) in a topical skincare formulation. FA was incorporated into the interlayer region of Mg/Al LDHs utilizing a coprecipitation procedure to produce a nanohybrid. The nanohybrid was characterized by XRD and FTIR. FA intercalation into the interlayer galleries of the nanohybrid was confirmed by an XRD diffractogram, which established a shift of the basal d(003) reflection of LDHs to lower 2θ angles. FTIR of the nanohybrids revealed the characteristic absorption frequencies of FA, indicating the existence of FA within the LDH matrix. The FA-intercalated nanohybrid showed antioxidant activity similar to that of free FA. A topical formulation was prepared by dispersing FA-intercalated LDH nanohybrid in an oil-in-water (o/w) emulsion, and it was used to evaluate its properties further. Rheological property evaluation showed that the presence of the nanohybrid resulted in better flow behavior and higher yield stress of the formulation, implying improved stability and quality. The nanohybrid also enhanced the storage modulus and, thus, the dynamic rigidity of the formulation. The test compounds expressed no cytotoxicity in HaCaT cells, as cell viability significantly increased in monolayer cultures after a 24-h incubation period. Release studies conducted in vitro using the nanohybrid showed a pH-dependent controlled release of FA. Transdermal permeation experiments using Franz diffusion cells demonstrated a direct correlation between the concentration of penetrated FA with time, which signified a gradual and effective transfer of FA from the LDH matrix into the oil/water emulsion, demonstrating its efficacy. Thus, the study revealed excellent prospects for the nanohybrid as a multifunctional active ingredient in topical applications.
Development and Application of a Quantitative Model for Proximate and Ultimate Analysis of Flue-Cured Tobacco Based on Near-Infrared Spectroscopy
Yuhan Peng - ,
Jiaxu Xia - ,
Qingxiang Li - ,
Yiming Bi - ,
Shitou Li - , and
Hui Wang *
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A methodology for predicting proximate and ultimate analysis data was developed by using near-infrared spectroscopy (NIR) combined with chemometric methods. The quantitative model has high accuracy, as evidenced by low root-mean-square-error of prediction (RMSEP) values (e.g., 0.41% for volatile matter and 0.29% for carbon). The model was further applied to tobaccos with distinct aroma profiles, and the predicted ultimate and proximate data lead to aroma classification with 86.6% accuracy. This methodology can be expanded to the aroma discrimination of imported tobaccos from Brazil, the United States, Canada, and Zimbabwe, demonstrating its broad reliability. Compared with traditional analyses, this NIR-based approach offers a fast and accurate method for large-scale tobacco evaluation, highlighting its potential for enhancing tobacco quality characterization through a quantifiable, digital, and high-throughput process.
Effects of Surfactants on Oil Droplet Demulsification in Oil-in-Water Emulsions under an Electric Field: A Molecular Dynamics Study
Shasha Liu *- ,
Heng Zhang - ,
Shideng Yuan - , and
Shiling Yuan *
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The application of an electric field to demulsification of oil-in-water (O/W) emulsions has received extensive attention. However, microcosmic information about the effect of surfactant type on the demulsification of an O/W emulsion under an electric field is still rare. In this work, the effects of cationic surfactant cetyltrimethylammonium bromide (CTAB) and anionic surfactant sodium dodecyl sulfate (SDS) on oil droplet demulsification in an emulsion under a pulsed-DC electric field were studied by molecular dynamics (MD) simulation. The MD simulation results show that oil droplets underwent directional movement under the action of an electric field. The larger the electric field strength, the shorter the time required for the oil droplets to coalesce. However, the movement direction of the oil droplets in the electric field was different depending on the type of surfactant. Compared to oil droplets containing SDS, oil droplets containing CTAB molecules exhibited faster deformation and easier migration coalescence under low electric field strength. It was mainly attributed to the fact that the deformation of oil droplets will be accelerated when oil droplets contain asphaltene molecules and surfactant molecules with different electronegativities under an electric field. During the demulsification of oil droplets containing CTAB molecules, CTAB molecules generated electrostatic attraction with asphaltene molecules in adjacent oil droplets, strengthened the interaction between oil droplets, and promoted the demulsification of oil droplets. In the process of oil droplet demulsification containing SDS molecules, the potential energy of the electrostatic interaction between oil droplets did not change, and the demulsification mainly depended on the van der Waals force between oil droplets.
Unleashing Vanadium-Based Compounds for High-Energy Aqueous Zinc–Ion Batteries
Saad Zafar - and
Bimlesh Lochab *
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Rechargeable aqueous zinc–ion batteries (ZIBs) are poised as a promising solution for large-scale energy storage and portable electronic applications. Their appeal lies in their affordability, abundant materials, high safety standards, acceptable energy density, and eco-friendliness. Vanadium-based compounds stand out as potential cathode materials due to their versatile phases and variable crystal structures, empowering design flexibility to affect the theoretical capacity. However, challenges, such as V dissolution and substantial capacity degradation, have hindered their widespread use. Recent breakthroughs in crafting innovative V-based materials for aqueous ZIBs, by preintercalating guest species, have significantly bolstered structural stability and facilitated faster charge migration, leading to enhanced capacity and stable cycling. This review delves into the latest advancements in vanadium-based cathodes with preintercalated guest species, examining their altered crystal structures and the mechanisms involved in Zn2+ ion storage. It also investigates how different guest materials within these cathodes impact the electrochemical capacity. Additionally, this assessment identifies key obstacles impeding progress and proposes potential solutions while also anticipating the future trajectory of aqueous ZIBs. These insights are invaluable to researchers and manufacturers alike, offering a roadmap for commercialization.
Improving Americium/Curium Separation Factors in the AmSel Process through Symmetry Lowering of the Diglycolamide Extractant
Filip Kolesar - ,
Karen Van Hecke *- ,
Ken Verguts - ,
Cécile Marie - ,
Laurence Berthon - ,
Koen Binnemans - , and
Thomas Cardinaels
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Partitioning and transmutation are important strategies for closing the nuclear fuel cycle. The diglycolamide extractant TODGA has played a major role in the development of solvent extraction processes for nuclear fuel reprocessing due to its good extraction performance, its hydrolytic and radiolytic stability, and its compliance with the CHON principle. However, due to drawbacks such as the tendency to form a third phase during extraction if no phase modifiers are used, continued research on diglycolamide-type extractants has led to the development of diglycolamides with decreased symmetry. In this study, it is shown that the recently developed diglycolamide, N,N-diisopropyl-N′,N′-didodecyldiglycolamide (iPDdDGA), is a potential alternative to TODGA with improved separation between Am and Cm or the Ln. Using the AmSel system as a reference, the extraction kinetics, influence of the acid concentration, influence of the iPDdDGA concentration, and influence of temperature were evaluated. Slope analysis indicates similar average stoichiometries for iPDdDGA and TODGA complexes, but the extraction efficiency of iPDdDGA is orders of magnitude higher. The feasibility of selective americium stripping in combination with the hydrophilic sulfonated bis-triazinyl bipyridine SO3-Ph-BTBP complexant was demonstrated. Selective stripping of americium was found to be possible, and the use of iPDdDGA gave an unexpected improvement in Am/Cm separation, with SFCm/Am values of up to 3.0. This represents a small but significant improvement compared to the 2.5 value typically found for TODGA, and it demonstrates the potential of this solvent extraction system to improve existing processes based on diglycolamide-type extractants.
Controlled Ligand-Free Growth of Free-Standing CsPbBr3 Perovskite Nanowires
Ziyun Huang *- ,
Zhaojun Zhang - ,
Nils Lamers - ,
Dmitry Baranov - , and
Jesper Wallentin
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Metal halide perovskite nanowires are widely studied due to their unique electronic and optical characteristics, making them promising for light emitting and detection applications. We developed a ligand-free method to grow vertically aligned free-standing CsPbBr3 nanowires from anodized aluminum oxide nanopore substrates. Here, we investigate the growth process using in situ microscopy with ultraviolet and visible light excitation, revealing a highly dynamic process with pronounced fluorescence at locations where high-density free-standing nanowires could be found. The yield of the growth is strongly improved by using a growth reactor with controlled N2 flow, increasing from 17 to 60%. We systematically investigated the growth dependence on the temperature and N2 flow rate and identified optimal parameters at 70 °C and 0.8 L/min, respectively. The improved control over the growth of free-standing nanowires expands opportunities for their integration into optoelectronic devices.
Experimental Study and Molecular Dynamics Simulation of Oil Displacement Using Different Microemulsions in the Fang2 Block of Songfangtun Oilfield
Qi Zhang - ,
Zhijun Zhou *- ,
Xi Yi - ,
Shuyang Wang - ,
Aoxue Xing - , and
Chenzhu Wang
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After many years of mining in the Fang2 block of the Songfangtun oilfield, the conventional water drive development method can no longer meet the requirement of greatly improving the recovery rate, and ternary composite drive (TCD) technology is adopted for this purpose. TCD is one of the most important methods to further improve crude oil recovery, and it has entered the industrialization and promotion stage, but there are still problems of fouling in the injection and extraction system and high production and maintenance costs. In order to reduce formation damage and improve recovery in the Songfangtun oilfield, an alkali-free microemulsion system was developed by replacing the weak base sodium carbonate with sodium chloride, but its emulsification capacity was weak and the recovery enhancement value was lower than that of the weak base TCD. In order to improve the emulsification performance of the alkali-free microemulsion and enhance the effect of oil repulsion, an alkali-free microemulsion oil-repellent system was developed on the basis of the alkali-free ternary system by using the compounding of surfactant, alcohol, and sodium chloride. Through indoor physical modeling experiments, it was concluded that the SDBS alkali-free microemulsion system had the best effect on improving crude oil rheology and viscosity reduction, and the lowest interfacial tension of 9.4 × 10–4 mN/m in the solution system when the mass fraction was 4%, with the maximum recovery rate of 47.03%, and the decrease in water content of 9.3%. Through molecular dynamics simulation and microemulsion oil-repellent coefficient, it is concluded that the alkali-free SDBS microemulsion system can greatly reduce the interaction force between crude oil and rock, with the lowest peak value of radial distribution function of 4.21, and the oil-repellent coefficient of Fp of 5.85; CMG reservoir numerical simulation software is adopted to verify the chemical repellent numerical simulation of Fang2 block, which shows that the recovery degree of SDBS alkali-free microemulsion system is 24.8% higher than that of water repellent, with the cumulative increase of 213.6 thousand tons of oil. The developed alkali-free microemulsion system not only realizes the goal of ternary composite alkalinity-free but also achieves the purpose of greatly improving the recovery rate and reducing the cost and increasing efficiency. It has a broad application prospect and can also provide a technical reference for the efficient development of other old oilfields with land-phase sandstone.
Study on the Enhanced Oil Recovery Properties of the Pickering Emulsions for Harsh Reservoirs
Liu Yang - ,
Jijiang Ge - ,
Hao Wu - ,
Xiaqing Li - ,
Jianda Li - , and
Guicai Zhang *
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Pickering emulsions stabilized by surfactant-modified SiO2 nanoparticles demonstrate good stability against droplet coalescence, showing application potential for enhanced oil recovery in high-temperature and high-salinity environments. Adjusting the adsorption ratio of surfactant on the nanoparticles significantly affects the wettability of nanoparticles and therefore regulates the microstructure and properties of Pickering emulsions. In this study, a saturated monolayer adsorption occurs at a surfactant-to-nanoparticles ratio of 0.1:1.0%, where an optimal hydrophilic–hydrophobic balance is achieved. However, below or above this ratio, the SiO2 nanoparticles become more hydrophilic with the decreasing or increasing surfactant concentration. Pickering emulsions stabilized by the intermediate wet nanoparticles exhibit the best stability and highest viscosity. Laser confocal scanning microscopy and cryo-scanning electron microscopy reveal that the SiO2 nanoparticles can form a bridge-structure network among the droplets of these emulsions. Microfluidic experiments and sand pack experiments show that Pickering emulsions provide greater permeation resistance than conventional emulsions stabilized solely by surfactant solely. In addition, microscopic experiments show that Pickering emulsions enhance oil recovery by 20% after second waterflooding, compared to a 12% recovery rate with conventional emulsions. It is found that the Pickering emulsions with bridge-structures may be accumulated in and plug channels much larger than their droplets, which results in higher properties of conformance control.
Thermodynamic Simulation and Laboratory-Scale Experiments of Tin Smelting at Al2O3 Saturation
Afif Nur Iksan - ,
Kopdi Saragih - ,
Imam Santoso - ,
Zulfiadi Zulhan - , and
Taufiq Hidayat *
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A significant issue encountered in smelting operations is the corrosion of refractory materials that come into direct contact with the molten slag. Magnesia-based refractories are commonly used in nonferrous smelting operations. On the other hand, alumina-based refractories emerge as a possible alternative, particularly when dealing with the unpredictable slag compositions, owing to alumina’s amphoteric characteristic. Nevertheless, prolonged interaction with aggressive slag can lead to substantial degradation of the refractory material. The research on the use of alumina-based refractories in tin smelting is not well known. Hence, this paper focuses on slag–refractory interaction in the tin smelting process at Al2O3 saturation. A series of thermodynamic simulations and laboratory-scale experiments were conducted. The software FactSage 8.2 was employed to simulate the solubility of Al2O3 in slag and the ratio of Sn content in slag to Sn content in metal under the conditions relevant to tin concentrate smelting and tin slag reduction stages. The experiments utilized synthetic slag composed of SnO-FeOx-CaO-SiO2-Al2O3, conducted in a vertical tube furnace at a temperature of 1300 °C for 2 h. The experimental parameters that were varied were the Fe/SiO2 ratio in slag (0.3–1.6), CaO/SiO2 ratio in slag (0.3–1.6), and Sn content in slag (3–20%). The simulation results revealed that the solubility of Al2O3 during the tin concentrate smelting and tin slag reduction stages was significantly influenced by temperature, Fe/SiO2, and CaO/SiO2, whereas the ratio of the Sn content in slag to the Sn content in the metal appeared to be independent of these variables, being primarily influenced by the oxidation condition. Experimental results at 1300 °C showed that varying Fe/SiO2 within the range of 0.3–1.6 led to an initial increase in Al2O3 solubility in slag at lower Fe/SiO2 ratios, followed by a decrease in Al2O3 solubility in slag at higher Fe/SiO2 ratios. A similar trend was observed with variations in CaO/SiO2 within the same range, accompanied by the formation of new solid phases, such as hercynite spinel at lower CaO/SiO2 ratios and melilite at higher CaO/SiO2 ratios. Moreover, under constant CaO/SiO2 and Fe/SiO2 ratios of 0.3, reducing the Sn content in the slag was found to increase the solubility of Al2O3 due to the creation of a more aggressive slag toward Al2O3 solid.
Synthesis, Characterization, and BSA Binding Properties of Carboxylated Merocyanine-Based Fluorophores
Rodrigo C. Duarte - ,
Rodrigo Cercená - ,
Bruno B. de Araujo - ,
Otávio A. Chaves - ,
Paulo F. B. Gonçalves - ,
Eduardo Zapp - ,
Fabiano S. Santos - ,
Fabiano S. Rodembusch *- , and
Alexandre G. Dal-Bó *
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This study describes the synthesis of new carboxylated merocyanine dyes by Knoevenagel condensation between 4-carboxybenzaldehyde and indolium/benzoindolium- and benzothiazolium-based coupling compounds. The condensations were performed in the presence of ammonium acetate, and the products were obtained in good yields after simple purification. These merocyanines exhibit UV-A-to-blue absorption and blue-to-green fluorescence emission, characterized by relatively large Stokes shift values (∼5000 cm–1). In addition, quantum chemical calculations were conducted to better explore the electronic and photophysical properties of the merocyanines under study. Thermal analysis via thermogravimetric analysis (TGA) revealed distinct decomposition stages for the merocyanines, with stability up to 200 °C. Cyclic voltammetry revealed irreversible waves for donor oxidation and acceptor reduction. On the basis of the onset potentials, the highest occupied molecular orbital (HOMO) energies were estimated to be between −5.38 and −5.47 eV, and the lowest unoccupied molecular orbital (LUMO) energies were calculated to range from −3.20 to −3.24 eV. These values suggest a narrow electrochemical band gap of 2.07 to 2.13 eV. Finally, fluorescence quenching experiments using the intrinsic fluorescence of the Trp residues in BSA were successfully applied to these compounds, indicating strong interactions with this protein via a static mechanism. The docking simulations corroborated the interaction between the merocyanines and BSA.
NC@Bi2S3 Nanospheres as High-Performance Anode Materials for Lithium-Ion Batteries
Wanda Kang - ,
Sen Li - ,
Xingchen Liu - ,
Kun Yan - ,
Wengao Zhang - ,
Youkang Fan - ,
Yuxiang Pan - , and
Jun Feng *
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Bi2S3 holds immense potential to be promoted as an anode material for lithium-ion batteries (LIBs), owing to the high theoretical gravimetric and volumetric capacities. However, the poor electrical conductivity and volume expansion during cycling hinder the practical applications of Bi2S3. Therefore, through subsequent heat treatment, the nitrogen-doped carbon film was successfully loaded on the nanosphere Bi2S3, which we call nitrogen-rich carbon layer-coated Bi2S3 (NC@Bi2S3). Hence, the nanosphere Bi2S3 uniformly covered by a nitrogen-rich carbon layer was successfully coated on the Bi2S3 surface (NC@Bi2S3) through post-treatment. Due to the effective interaction between glutathione and inorganic materials, dopamine hydrochloride molecules are introduced and polymerized on the surface of the spherical Bi2S3 structure and then converted into a nitrogen-rich carbon layer with an average thickness of 10.0 nm. The electrochemical tests reveal that the discharge specific capacities of Bi2S3 and NC@Bi2S3 reach 340.99 and 645.13 mAh/g after 300 cycles at 100 mA/g, respectively. Kinetic analysis shows that the contribution of pseudocapacitance behavior increases by about 10% after the nitrogen-rich carbon layer is coated. These results suggest the potential of NC@Bi2S3 as a high-performance anode material for LIBs; the stability can be enhanced by core–shell structures.
Synthesis of Lead(II) Carbonate-Containing Nanoparticles Using Ultrasonication or Microwave Irradiation
Madhushika E. Gamage - ,
Kyan D. Ho - ,
Mohammad S. Kader - ,
Katherine Nguyen - ,
Mirudhula Velmurugan - ,
Sara H. McBride-Gagyi - ,
Steven W. Buckner *- , and
Paul A. Jelliss *
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We report on the synthesis of lead(II) carbonate-containing nanoparticles using the polyol process under high-energy ultrasound or microwave irradiation as alternate energization methods. Five carbonate source precursors are used in the reaction, and the precipitation reactions generate four different crystal products, depending on the precursor. More alkaline precursors produce the hydroxy-carbonate structures (abellaite, or its potassium analog, and hydrocerussite), while the less alkaline precursors produce the simple carbonate structure (cerussite). Ultrasonication or microwave irradiation during the arrested precipitation ensures the formation of nanoparticles <100 nm in diameter in a mostly single crystalline phase in all cases, bar one. The products were characterized by powder X-ray diffraction, dynamic light scattering, electron microscopy, infrared spectroscopy, and thermal analysis. These nanoparticles are targeted as X-ray contrast agents for biological imaging, particularly of fine vasculature where small particle size is essential.
Relationships between the Surface Hydrophilicity of a Bismuth Electrode and the Product Selectivity of Electrocatalytic CO2 Reduction
Yujing Ji - ,
Jichuang Wu - ,
Ha Eun Lee - ,
Yongsu An - ,
Duk-Young Jung - ,
Chan Woo Lee - ,
Young Dok Kim *- , and
Hyun Ook Seo *
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Two types of bismuth films (micro-Bi and nano-Bi) were prepared, and their electrocatalytic behavior was studied in terms of reduction current and product selectivity in a potential range of −0.776 to −1.376 V vs RHE. CO2 and H2O molecules competed with each other for reduction on the surfaces of both types of films, and formate and H2 were the respective major products of reductive reactions. Under the same conditions, nano-Bi exhibited lower selectivity for formate and higher selectivity for H2 compared to the respective micro-Bi cases with bismuth films of similar thickness. This can be attributed to the higher hydrophilicity of bismuth film surfaces of nano-Bi due to surface nanoscale roughness and lower surface-carbon content compared with those of micro-Bi. Our results suggest a new strategy for controlling the selectivity of electrocatalytic CO2 reduction under aqueous electrolytes through the use of surface engineering.
November 25, 2024
Computational Study on the Proton Reduction Potential of Co, Rh, and Ir Molecular Electrocatalysts for the Hydrogen Evolution Reaction
Murugesan Panneerselvam - ,
Madhavan Jaccob *- , and
Luciano T. Costa *
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In this study, comprehensive density functional theory calculations were conducted to investigate the molecular mechanism of electrocatalytic proton reduction using group 9 transition metal bpaqH (2-(bis(pyridin-2-ylmethyl)amino)-N-(quinolin-8-yl)acetamide) complexes. The goal was to explore how variations in the structural and electronic properties among the three metal centers might impact the catalytic activity. All three metal complexes were observed to share a similar mechanism, primarily characterized by three key steps: heterolytic cleavage of H2 (HEP), reduction protonation (RPP), and ligand-centered protonation (LCP). Among these steps, the heterolytic cleavage of H2 (HEP) displayed the highest activation barrier for cobalt, rhodium, and iridium catalysts compared to those of the RPP and LCP pathways. In the RPP pathway, hydrogen evolution occurred from the MII–H intermediate using acetic acid as a proton donor at the open site. Conversely, in the LCP pathway, H–H bond formation took place between the hydride and the protonated bpaqH ligand, while the open site acted as the spectator. The enhanced activity of the cobalt complex stemmed from its robust σ-bond donation and higher hydride donor ability within the metal hydride species. Additionally, the cobalt complex demonstrated a necessary negative potential in the first (MIII/II) and second (MII/I) reduction steps in both pathways. Notably, MIII/II–H exhibited a more crucial negative potential for the cobalt complex compared to those of the other two metal complexes. Through an examination of kinetics and thermodynamics in the RPP and LCP processes, it was established that cobalt and rhodium catalysts outperformed the iridium ligand scaffold in producing molecular hydrogen after substituting cobalt metal with rhodium and iridium centers. These findings distinctly highlight the lower-energy activation barrier associated with LCP compared to alternative pathways. Moreover, they offer insights into the potential energy landscape governing hydrogen evolution reactions involving group 9 transition metal-based molecular electrocatalysts.
Petrographic and Molecular Characterization of Organic-Rich Mudstones with Petroleum Generative Potential from The Lower Triassic Montney Formation, Western Canada
Daniela Becerra *- ,
Lavern Stasiuk - ,
Christopher R. Clarkson - ,
Humberto Carvajal-Ortiz - ,
Amin Ghanizadeh - , and
Thomas Moslow
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The Triassic Montney Formation hosts major oil and gas resources in Western Canada. Despite significant historical development of these resources, the origin of its hydrocarbons remains unclear, partly due to limited evidence of primary organic matter within the formation. Most of the hydrocarbons in the Triassic Montney Formation are trapped in low-permeability siltstone facies. For the purposes of this study, however, we investigated the lesser-known and understudied organic- and clay-rich mudstone beds, typically ranging from 2 to 8 cm in thickness, which are interbedded with the siltstone reservoir facies. Petrographic and organic geochemical analyses were conducted on core samples from a well located in west-central Alberta with thermal maturity of 0.95–1.16%Ro. Petrographic analysis, including kerogen maceral composition and fluorescence of petroleum fluid inclusions, reveals that the organic matter in the Montney Formation is closely linked to its host lithology. Organic-rich mudstone facies, with TOC values up to 3.5 wt %, contain primary kerogen (32–74 vol %) and solid bitumen (29–68 vol %). In contrast, the more organic-lean siltstone facies (TOC < 0.8 wt %) contain primarily pore-filling solid bitumen and lack structured kerogen. Kerogen within the organic-rich mudstone facies is mainly composed of liptinite macerals, including amorphinite, liptodetrinite, and alginite, subordinate amounts of acritarch and sporinite, and traces of inertinite and vitrinite macerals. The primary organic matter in the mudstone facies is presumed to be derived from marine sources (i.e., phytoplanktonic algae and bacterial biomass). Its preservation may result from the balance between periodic high productivity (potentially driven by river floods), rapid sedimentation to bury and preserve organic matter, and low dilution by siliciclastic material. Organic petrology analysis suggests an in situ generation of hydrocarbons in the mudstone beds and a potential subsequent short-distance migration to adjacent siltstone beds. Biomarker analysis supports the genetic linkage between rock extracts from these beds. Additionally, three families of petroleum fluid inclusions were systematically observed (using fluorescence microscopy) in several sets of contiguous siltstone and mudstone beds. These findings suggest that the organic-rich mudstone facies partially contributed to the present-day hydrocarbons of the Middle Montney Member in the study area.
Isoindolinedione-Benzamide Pyridinium Derivatives for Targeting Alzheimer’s Disease
Milad Noori - ,
Minoo Khalili Ghomi - ,
Navid Dastyafteh - ,
Najmeh Oliyaei - ,
Haleh Hamedifar - ,
Shahrzad Javanshir - ,
Nader Tanideh - ,
Elahe Sattarinezhad - ,
Fateme Sattari - ,
Masoud Haghani - ,
Hojjat Rahmani - ,
Bagher Larijani - ,
Mohammad Mahdavi - ,
Mir H. Hajimiri *- , and
Aida Iraji *
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An Isoindolinedione-benzamide pyridinium derivatives were designed through a structure-based strategy and synthesized as novel multifunctional anti-Alzheimer agents. The inhibitory activities of all 17 derivatives against acetylcholinesterase and butyrylcholinesterase were evaluated. Results exhibited that compound 7j displayed promising AChE inhibitory activity with an IC50 value of 0.26 ± 0.07 μM, and compound 7c exhibited an IC50 value of 0.08 ± 0.01 μM against BChE with 132-fold better inhibitory activity in comparison with positive control. Next, the enzyme kinetics studies and detailed binding mode via molecular docking were performed for the most potent compounds. Additionally, molecular dynamics simulations were accomplished to further investigate the potent compound’s interaction, orientation, and conformation over the related enzymes. The neurotoxicity of the most potent derivative was executed against SH-SY5Y, and the mRNA levels of GSK-3α and GSK-3β after treatment with 7c on SH-SY5Y were evaluated. Results exhibited the mRNA levels of GSK-3β were decreased compared to the control group. All these results indicate that 7c is a good starting point for developing a multifunctional anti-Alzheimer compound.
Fabrication of Bioactive Helix aspersa Extract-Loaded Chitosan-Based Bilayer Wound Dressings for Skin Tissue Regeneration
Merve Perpelek - ,
Sedef Tamburaci - ,
Ahmet Karakasli - , and
Funda Tihminlioglu *
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In recent years, there has been a notable shift toward exploring plant and animal extracts for the fabrication of tissue engineering structures that seamlessly integrate with the human body, providing both biological compatibility and physical reinforcement. In this particular investigation, we synthesized bilayer wound dressings by incorporating snail (Helix aspersa) secretions, comprising mucus and slime, into chitosan matrices via lyophilization and electrospinning methodologies. A nanofiber layer was integrated on top of the porous structure to mimic the epidermal layer for keratinocyte activity as well as acting as an antibacterial barrier against possible infection, whereas a porous structure was designed to mimic the dermal microenvironment for fibroblast activity. Comprehensive assessments encompassing physical characterization, antimicrobial efficacy, in vitro bioactivity, and wound healing potential were conducted on these bilayer dressings. Our findings revealed that the mucus and slime extract loading significantly altered the morphology in terms of nanofiber diameter and average pore size. Snail extracts loaded on a nanofiber layer of bilayer dressings showed slight antimicrobial activity against Staphylococcus epidermidis and Escherichia coli. An in vitro release study of slime extract loaded in the nanofiber layer indicated that both groups 1 and 2 showed a burst release up to 6 h, and a sustained release was observed up to 96 h for group 1, whereas slime extract release from group 2 continued up to 72 h. In vitro bioactivity assays unveiled the favorable impact of mucus and slime extracts on NIH/3T3 fibroblast and HS2 keratinocyte cell attachment, proliferation, and glycosaminoglycan synthesis. Furthermore, our investigations utilizing the in vitro scratch assay showcased the proliferative and migratory effects of mucus and slime extracts on skin cells. Collectively, our results underscore the promising prospects of bioactive snail secretion-loaded chitosan constructs for facilitating skin regeneration and advancing wound healing therapies.
Toward Sustainable Poly(lactic acid)/Poly(propylene carbonate) Blend Films with Balanced Mechanical Properties, High Optical Transmittance, and Gas Barrier Performance via Reactive Compatibilization and Biaxial Stretching
Xiaoying Ji - ,
Jia Guo - ,
Bingbing Zeng - ,
Xiaopeng Li - ,
Xue Liao - ,
Wanjiao Fang - ,
Juan Liu - ,
Yu Zheng - ,
Dongliang Li *- , and
Jinshan Lei *
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Sustainable poly(lactic acid) (PLA)/poly(propylene carbonate) (PPC) blends were compatibilized by the environmentally friendly epoxidized soybean oil (ESO) through the chemical reaction of epoxy functional groups on ESO with the terminated carboxyl and hydroxyl groups of PLA/PPC. The compatibilization effect of ESO was confirmed by Fourier transform infrared spectroscopy, rheological property testing, differential scanning calorimetry, and morphological observations. It was revealed that the molecular chain entanglement between PLA and PPC was significantly enhanced and the dispersed PPC phase size was decreased, which endowed the blend with high viscosity modulus, low tan δ, and great stretchability, especially for the blend containing 1.0 wt % ESO. The compatibilization effect dramatically reinforced the toughening modification of PPC on PLA, resulting in a great ductility with a fracture strain up to 187.3%, more than 20 times that of the pristine PLA, while maintaining a high strength of 44.5 MPa. Compared to the neat PLA and the PLA/PPC blend, the compatibilized blend showed a much larger draw ratio of up to 6.5 × 6.5 during biaxial stretching, producing a uniform film with balanced mechanical properties, high optical transparency, and good oxygen barrier performance. This work will be of vital importance for guiding the preparation of PLA-based films with superior comprehensive properties.
Sustainable Nanotechnology Based Techniques for Mitigating the Pollutants from Pulp and Paper Industry
Guddu Kumar Gupta - ,
Megha Sailwal - , and
Pratyoosh Shukla *
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Paper mills inevitably produce various pollutants, including chlorolignin, chlorophenols, chloroguaiacol, furan, cyanide, and heavy metals. These pollutants cause significant threats to aquatic and terrestrial life. The pulp and paper industries are looking for eco-friendly solutions for the disposal of effluents during paper processing. Moreover, environmental management practices are a key concern that may be addressed by removing these effluents using suitable bioremediation techniques. Therefore, we have discussed several eco-friendly nanotechnology based sustainable bioremediation technologies like the use of nanoparticles, nanomaterials, nanocomposites, nanoadsorbents, and several advanced methods such as electrocoagulation and photocatalysis, which may be utilized for the elimination of hazardous pollutants from paper industry effluents. This review finally includes critical insight into the potential use of the above-mentioned nanotechnology based interventions for mitigation of contaminants from the paper industry. Nevertheless, there are a few limitations and challenges toward implementation of such technologies, which are also discussed in this review.
Quantification of Antiretroviral Drug Emtricitabine in Human Plasma by Surface Enhanced Raman Spectroscopy
Marguerite R. Butler - ,
Terry A. Jacot - ,
Sucharita M. Dutta - ,
Gustavo F. Doncel - , and
John B. Cooper *
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In this study, reproducible label-free detection and quantification of the antiretroviral drug emtricitabine (FTC) down to 78 ng/mL in human plasma by surface enhanced Raman spectroscopy (SERS) is presented. A novel plasma sample pretreatment method using silver nitrate and silver colloidal nanoparticles (Ag CNPs) was used to prepare the plasma samples for analysis. The pretreated plasma samples were evaporated to dryness on an aluminum surface and a computer-controlled Raman scanning system was used to collect spatially resolved SERS spectra of the entire surface. Calibration curves of commercial human plasma samples containing FTC in a concentration range of 5000 to 78 ng/mL were calculated using three different methods. First, a conventional approach was taken, where all the spectra collected for each concentration were averaged, then the SERS intensity of a known FTC peak (792 cm–1) was used for calibrations (total population method). This approach was refined by utilizing a figure-of-merit (FOM) quality index (Qi) to sample spectra from each concentration that contained the highest signal-to-noise (S/N), before averaging and calculating the SERS intensity of the 792 cm–1 FTC peak (Qi sample method). Finally, the distribution of all Qi values for each concentration were modeled using cumulative distribution functions (CDFs) and were used for calibrations (CDF method). The CDF method exhibited the highest analytical sensitivity (slope = 3702.47) compared to the Qi sample method (slope = 1591.05) and the total population method (slope = 754.21). The Qi sample method exhibited the highest linearity (R2 = 0.99) compared to the CDF method (R2 = 0.95) and the total population average (R2 = 0.97). The CDF method exhibited the highest S/N in the concentration range of 5000 to 312 ng/mL (S/N range of 31.5–16.6). The Qi sample method exhibited the highest S/N for concentrations 156 and 78 ng/mL (S/N = 9.7 and 7.4, respectively). These results show that the Qi sample method is advantageous over all other methods when approaching the LOQ while the CDF method is advantageous over all methods at higher concentrations. The LOQ (78 ng/mL) was confirmed by principal component analysis (PCA). Together these results show that statistical treatment of a large population of SERS spectra, where the analyte signal intensity follows an exponential distribution, is superior to standard methods of averaging populations of spectra in terms of analytical sensitivity, linearity, and S/N. Additionally, it was found that the background signal had no interference with the quantitative data calculated for the total population and Qi sample methods after repeating both analyses with baseline-subtracted spectra. The results and methodology presented in this study establish a framework for integrating SERS into drug adherence monitoring for FTC-based treatment and prevention of infections by demonstrating consistent SERS detection and quantification of FTC in human plasma at therapeutically relevant concentrations.
Characterizing the Effect of Simultaneous Enhancements of Reducing Gas Species on Figaro Taguchi Gas Sensor Resistance Response
Adil Shah *- ,
Olivier Laurent - ,
Grégoire Broquet - ,
Pramod Kumar - , and
Philippe Ciais
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The resistance of the Figaro Taguchi Gas Sensor (TGS) decreases when exposed to reducing gas enhancements. TGS gas response can be characterized by comparing measured resistance to a reference resistance, representative of sampling in identical environmental conditions but with no reducing gas enhancement. Thus, this resistance ratio (RR) allows for characterization of reducing gas response, independent of other environmental effects. This work presents controlled laboratory experiments, measurements, and modeling for an analysis on the effect of reducing gas cross-sensitivities on RR. The methane mole fraction ([CH4]) was raised to approximately 9 ppm from a 0.492 ppm reference level, and carbon monoxide mole fraction ([CO]) was raised to approximately 4 ppm from a 0 ppm reference level, through multiple simultaneous steps. The independent effect of each gas on RR was directly multiplied, resulting in an inferior RR compared with measurements, implying an interdependence effect. For example, for one TGS unit, when deriving [CH4] from RR, a 6 ppm [CH4] measurement would be underestimated by 6% at 1 ppm [CO], but only by 1.6% at 0.1 ppm [CO]. A key implication of residual interdependence effects is that any gas characterization must be conducted with the same reference levels of each other reducing gas expected during field deployment, even if measuring a single gas. A first-order interdependence correction is proposed to account for such interdependence effects. Yet, each TGS behaves differently, and interdependence testing takes time. Therefore, the TGS best serves to detect single reducing gases, assuming all other reducing gases to remain constant at their reference levels.
Preparation of a Novel Composite Coating of APP/MMT/APTES on Polyurethane with Improved Flame-Retarding Performance
Changrui Liu - ,
Kui Chen *- ,
Bin Wu - ,
Weigen Sun - ,
Lijun Ji - , and
Yanyang Wu
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An environmentally friendly flame retardant coating for polyurethane composed of ammonium polyphosphate(APP)/montmorillonite(MMT)/(3-aminopropyl)triethoxysilane(APTES) has been prepared by deposition on a polyurethane surface through a one-step immersion, enhancing its flame retardancy. The coating of APP/MMT/APTES on the polyurethane sample surface has been verified from XPS and FTIR analysis. In comparison to untreated polyurethane, the amount of char residue after combustion of the flame-retardant polyurethane increases significantly, with a 50.8% increase in limiting oxygen index (LOI). The cone calorimetry test shows that the peak heat release rate (PHRR) and total smoke production (TSP) decreased by 80.28% and 66.7%, respectively. The formation of a dense carbon layer on the polyurethane surface restricts heat feedback from the combustion zone and reduces emission of volatiles. The preparation of polyurethane flame retardant coatings is carried out in an aqueous solution; the process is environmentally friendly and an attractive technology for polymer flame retarding.
Gelatin Methacryloyl/Sodium Alginate/Cellulose Nanocrystal Inks and 3D Printing for Dental Tissue Engineering Applications
Huihua Li - ,
Shangsi Chen - ,
Waruna Lakmal Dissanayaka *- , and
Min Wang *
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In tissue engineering, developing suitable printing inks for fabricating hydrogel scaffolds via 3D printing is of high importance and requires extensive investigation. Currently, gelatin methacryloyl (GelMA)-based inks have been widely used for the construction of 3D-printed hydrogel scaffolds and cell-scaffold constructs for human tissue regeneration. However, many studies have shown that GelMA inks at low polymer concentrations had poor printability, and printed structures exhibited inadequate fidelity. In the current study, new viscoelastic inks composed of gelatin methacryloyl (GelMA), sodium alginate (Alg), and cellulose nanocrystal (CNC) were formulated and investigated, with CNC being used to improve the printability of inks and the fidelity of printed hydrogel structures and Alg being used to form ionically cross-linking polymer networks to enhance the mechanical strength of printed hydrogel structures. Rheological results showed that GelMA/Alg/CNC inks with different Alg-to-CNC ratios possessed good shear-thinning behavior, indicating that GelMA/Alg/CNC inks were suitable for 3D printing. The quantitative evaluation of printability and fidelity showed that a high concentration of CNC improved the printability of GelMA/Alg/CNC inks and concurrently promoted the fidelity of printed GelMA/Alg/CNC hydrogels. On the other hand, compression tests showed that a high concentration of Alg could enhance the mechanical strength of GelMA/Alg/CNC hydrogels due to the increase in cross-link density. Furthermore, GelMA/Alg/CNC hydrogels exhibited good biocompatibility and could promote the proliferation of human dental pulp stem cells (hDPSCs), suggesting their great potential in dental tissue engineering.
Agronomic Biofortification of Unconventional Food Plants with Zinc
Aline da Silva Costa - ,
Marcelo Henrique Avelar Mendes - ,
Douglas Correa de Souza - ,
Betsy Carolina Muñoz de Páez *- ,
Thiago Sampaio Guerra - ,
Paula Aparecida Costa - ,
Paulo Cesar Ossani - ,
Maria Ligia de Souza Silva - , and
Luciane Vilela Resende
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Zinc (Zn) biofortification in food plants presents a good strategy to address inadequate Zn intake by humans, a major health concern. Unconventional food plants (UFPs), known for their rich nutritional profile, offer an accessible and nutritious alternative to the food system. This study evaluated the response of selected UFP species to Zn application. An experiment with a completely randomized design was conducted using a 5 × 3 × 2 factorial scheme with four replicates. Five UFP species: Lactuca cf. canadensis L (Lc), Pereskia aculeata (Pa), Rumex acetosa (Ra), Stachys byzantina (Sb), and Tropaeolum majus (Tm) were tested with three Zn doses (0, 2, and 10 kg ha–1) and two application methods (soil and foliar). The parameters evaluated included leaf number, chlorophyll content, fresh and dry mass, moisture, and mineral content. Foliar application proved to be the more efficient method, with Ra and Sb showing the greatest Zn accumulation. Kohonen’s self-organizing maps efficiently explored correlations and groupings, revealing that Zn application influenced these attributes. Biofortified leaves of UFPs show strong potential in mitigating Zn nutritional deficiencies.
Nonionic Demulsifier for Smart Demulsification of Crude Oil Emulsion at Room and Moderate Temperatures
Ahmad A. Adewunmi - ,
Muhammad Shahzad Kamal *- , and
Syed Muhammad Shakil Hussain *
This publication is Open Access under the license indicated. Learn More
This study reports the demulsification activity of a newly developed nonionic demulsifier (NID) via the condensation of glycolic acid ethoxylate lauryl ether with amine. The demulsification performance of the developed NID was assessed under room and moderate temperatures (25 and 60 °C), while the concentrations of NID were varied from 100 to 700 ppm at both temperatures in order to observe their oil–water separation efficiency. The demulsification mechanism was expatiated by determining the viscosity and elastic modulus of emulsion in the presence and absence of the NID. Adsorption at the oil and water interface was analyzed through a series of interfacial tension measurements. Accordingly, under the aforementioned temperatures, the optimal demulsification efficiency of the NID was 95% (25 °C) and 99% (60 °C) at 500 ppm. Viscosity determination at both temperatures revealed a drastic reduction in emulsion viscosity in the presence of NID, and the viscosity drop was of high magnitude at moderate temperatures (60 °C). Likewise, the elastic modulus measurements in bulk rheology revealed that the presence of NID in the emulsion weakened the elastic strength. Again, the interfacial modulus test exhibited the percolation of NID at the oil–water interface and the displacement of asphaltenes. Interfacial tension (IFT) measurements of the oil–water system at different NID concentrations showed that the particles were adsorbed at the oil–water interface. The IFT values of the oil–water system in the presence of NID ranged from 1.84 to 3.02 mN/m as compared to that of the NID-free oil–water system recorded as 16.11 mN/m. It is envisaged that this new nonionic demulsifier would be very useful in oilfields and petrochemical industries.
Unraveling the Nanomechanical and Vibrational Properties of the Mayaro Virus
Alefe Roger Silva França - ,
Joel Félix Silva Diniz-Filho - ,
Clenilton Costa dos Santos - ,
Laís Durço Coimbra - ,
Rafael Elias Marques - ,
Leandro R. S. Barbosa - ,
Ralph Santos-Oliveira - ,
Pedro Filho Noronha Souza *- , and
Luciana Magalhães Rebelo Alencar *
This publication is Open Access under the license indicated. Learn More
Mayaro virus (MAYV) is an emerging mosquito-borne viral pathogen whose infection results in arthritogenic disease. Despite ongoing research efforts, MAYV biology is largely unknown. Physical virology can assess MAYV nanoparticle metastability, assembly/disassembly, and polymorphism, allowing us to understand virion architecture and dynamics. Here, we employ atomic force microscopy (AFM) and surface enhancement Raman spectroscopy (SERS) to assess MAYV nanomechanical properties, including maps of adhesion force and Young’s modulus on individual viral particles. We established topographic maps of MAYV in two and three dimensions, revealing the three-dimensional arrangement and distribution of charges on viral spikes at the virus surface. Furthermore, the organization of the densely packaged RNA, which affords the viral particle exceptional mechanical resistance compared to chikungunya (CHIKV), was observed using MAYV adsorption patterns. The vibrational signature of MAYV particles differs from CHIKV, with more intense protein modes matching the distribution of E1/E2 dimers and the nucleocapsid, which are well structured and suggestive of mechanical strength.
An Investigation of the Sodium Nitroprusside Effects on Serum Lipids in an Animal Model of Schizophrenia by the Magnetic Resonance Study
João Guilherme de Moraes Pontes - ,
João Victor Silva Nani - ,
Banny Silva Barbosa Correia - ,
Tássia Brena Barroso Carneiro Costa - ,
Danijela Stanisic - ,
Mirian A. F. Hayashi *- , and
Ljubica Tasic *
This publication is Open Access under the license indicated. Learn More
Schizophrenia (SCZ) is a multifactorial mental illness with limited knowledge concerning pathogenesis, contributing to the lack of effective therapies. More recently, the use of a nitric oxide donor named sodium nitroprusside (sNP) was suggested as a potential therapeutic drug for the treatment of SCZ. Despite the mixed results regarding the effectiveness of the sNP in reducing SCZ symptoms, successful trials on sNP in treatment-resistant SCZ were published. We have also demonstrated the power of evaluating the lipidic profiles of human clinical and animal model samples to identify the biomarkers of the pharmacological response to the diagnosis of mental disorders. Aim of this work is to evaluate the sNP effects in an animal model for SCZ studies through lipidomic profiles assessed by magnetic resonance spectroscopy (NMR). Lipidic profiling of serum from these animals indicated a more pronounced effect of sNP on lipids in the 0.50–6.00 ppm spectral region. Chemometric analysis also indicated an approximation of the lipidic profiling of SCZ animal model rats treated with sNP compared to that of the control group. In addition, we have compared the sNP treatment with other antipsychotics classically used in the clinic, such as haloperidol and clozapine, and the sNP treatment evaluated herein confirms the potential of sNP for the treatment of SCZ.
Insights on Immobilization of Cd Contamination in Soil: Synergic Impacts of Water Management and Bauxite Residue
Tao Tian - ,
Chunyue Wu - ,
Liangshen Gong - ,
Chuangye Yao *- ,
Haifeng Xiao - ,
Lu Liu - , and
Feng Li
This publication is Open Access under the license indicated. Learn More
To immobilize the activity and bioavailability of soil Cd, the single treatment only flooding (F) and the combined treatments with flooding plus bauxite residue (F-B) or lime (F-L) were designed to investigate the impacts of different treatments on the toxicity and bioavailability of Cd in contaminated soil. Compared with the single treatment (F), the combined treatments (F-B and F-L) improved soil-associated organic functional groups and aggregated stability in soil. The average particle sizes of soil aggregates increased from 126 nm (F-treated soil) to 256 and 270 nm following F-B and F-L treatments, respectively. Relative to F treatment, the combined treatments (F-B and F-L) increased soil pH, soil EC, and residual Cd content in soil and reduced exchangeable Cd and acid-soluble Cd content in soil. The exchangeable Cd contents in soils were decreased to 3.17 and 3.42 mg/kg following F-B and F-L treatments in comparison with F-treated soils (4.31 mg/kg), respectively. For the soils with F-B and F-L treatments, soil residual Cd contents increased from 54% (F treatment) to 57 and 56%, respectively, and soil acid-soluble Cd contents decreased from 46% (F treatment) to 37 and 43%, respectively. A negative correlation was found in soil pH versus soil exchangeable Cd and soil acid-soluble Cd. In addition, the F-B treatment exhibited superiority in suppressing toxicity and bioavailability of soil Cd, owing to that F-B treatment is easy to induce neutralization reaction and immobilization effect in contaminated soil. The findings offer evidences that F-B treatment is a facile approach to suppress toxicity and bioavailability of soil Cd, which shows potential for immobilization of Cd in soil.
Discovering Influenza Virus Neuraminidase Inhibitors via Computational and Experimental Studies
Trung Hai Nguyen - ,
Ngoc Quynh Anh Pham - ,
Quynh Mai Thai - ,
Van V. Vu - ,
Son Tung Ngo *- , and
Jim-Tong Horng *
This publication is Open Access under the license indicated. Learn More
Influenza A and B viruses spread out worldwide, causing several global concerns. Discovering neuraminidase inhibitors to prevent influenza A and B viruses is thus of great interest. In this work, a machine learning model was trained and tested to evaluate the ligand-binding affinity to neuraminidase. The model was then used to predict the binding affinity of compounds from the CHEMBL database, which is a manually curated database of bioactive molecules with drug-like properties. The physical insights into the binding process of ligands to neuraminidase were clarified via molecular docking and molecular dynamics simulations. Experimental investigation on enzymatic activity validated our computational results and suggested that 2 compounds were potential inhibitors of neuraminidase of the influenza A and B viruses.
Probing Light-Matter Interactions: Fluorescence Lifetime Manipulation in a Crystalline Colloidal Array
Haley W. Jones - ,
Yuriy Bandera - , and
Stephen H. Foulger *
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The connection between a structured environment and the decay kinetics of an embedded emitter is explored by copolymerizing a naphthalimide derivative within polystyrene-based nanoparticles. The nanoparticles spontaneously self-assemble into a crystalline colloidal array, resulting in a partial photonic bandgap, or rejection wavelength, in the visible regime. The rejection wavelength of the liquid ordered array can be shifted across the emission spectrum of the nanoparticles by dilution with deionized water, which increases the interparticle spacing of the array. Time-resolved fluorescence of the ordered array at various rejection wavelength conditions is monitored at high- and low-energy electronic transition frequencies across the emission spectrum of the naphthalimide-copolymerized nanoparticles. Careful attention is given to the reference systems that are used to quantify photonic effects, the wavelengths at which decay kinetics are monitored, and the quantum yield of the naphthalimide-derived emitter. Increased and decreased excited-state lifetimes are observed, depending on the position of the rejection wavelength in relation to the emission of the emitter and the monitored wavelength, revealing critical insights in the context of quantum light-matter interactions and opportunities for strategic control over emitter decay pathways.
Carbon Nanotube-Based Segregated Thermoplastic Nanocomposites Structured via Electromagnetic Melt Processing
Madara Mohoppu - ,
Utsab Ayan - ,
Jacob Schwartz - ,
Ahmed Al-Ostaz - ,
Mine G. Ucak-Astarlioglu - , and
Byron S. Villacorta *
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A cutting-edge method that uses electromagnetic (EM) energy for the melt processing of thermoplastic polymer nanocomposites (TPNCs) is reported. The properties and microstructures of TPNCs produced via the proposed EM-processing method and TPNCs via conventional heat processing are contrasted. The EM-processed TPNCs prepared with EM-susceptible carbon nanotubes (CNTs) exhibited a significant enhancement in transport and mechanical properties, outperforming the conventionally processed TPNCs. Thus, the EM-processed TPNCs demonstrated an ultralow electrical percolation threshold (∼0.09 vol %) and a remarkable increase in volume electrical conductivity of 8 orders of magnitude (i.e., 1.1 × 10–5 S/m) at only 1.0 wt % CNT loading, compared to their hot-pressed counterparts. This highlights the superior network formation, level of segregation, and structuring enabled by EM processing. Differential scanning calorimetry (DSC) and X-ray diffraction (XRD) revealed that EM-processed TPNCs exhibited higher crystallinity (∼9% higher) and a predominantly α crystal phase compared to the hot-pressed TPNCs. Microstructural inspection by electron microscopy disclosed that EM processing led to segregated but interconnected multiscale networks of a thin and well-defined CNT interphase that encompassed from the nanoscale of the CNTs to the macroscopic scale of TPNCs. In contrast, conventional processing developed a more diffused CNT interphase with less interconnectivity. The EM-processed TPNCs developed a statistically higher stiffness (+20%) and in certain cases, even better strength (+10%) than the hot-pressed TPNCs. However, the EM-processed TPNCs displayed significantly lower ductility, owing to their higher crystallinity, more brittle crystal α phase, and the potential formation of microvoids in the bulk of the TPNCs inherent to the unoptimized EM processing. This work provides an understanding of an alternative and unconventional processing method capable of achieving higher structuring in nanocomposites with advanced multifunctional properties.
Multilayer Carbon Nanotube Film/Eucommia ulmoides Gum Composite Films with Excellent Electromagnetic Shielding Performance and Infrared-Triggered Shape Memory Behavior
Zhonglei Kang - and
Bo-xing Zhang *
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Due to the increasing pressure of environmental protection and the depletion of oil resources, Eucommia ulmoides gum (EUG) as a natural renewable and degradable biopolymer has attracted more and more attention. In this work, multilayer carbon nanotube film (CNF)/EUG composite films were fabricated through the infiltration and hot-pressing process. By taking advantage of the elasticity of EUG and the specific strength of CNF, composite films exhibited much more improved mechanical strength (maximum tensile stress up to 108.4 MPa) compared with pristine EUG and CNF alone. In addition, composite films prepared with five CNF layers and five infiltration cycles of EUG solution with a thickness of 181 μm can achieve the highest total shielding effectiveness value of 88 dB in 15.6 GHz. Moreover, the folded composite film can recover quickly to the fixed permanent shape when exposed to infrared light, demonstrating fascinating infrared-triggered shape memory behavior. This work provides a facile and general method to fabricate CNF/EUG composite films and is beneficial for pushing forward the practical application of EUG materials.
Lipoic Acid Nanoparticles Exert Effective Antiatherosclerosis Effects through Anti-Inflammatory and Antioxidant Pathways
Xinyi Li - ,
Mengjiao Zhang - ,
Anni Chen - ,
Xinqi Wang - ,
Lan Yang - ,
Yingjian Zhu *- , and
Zhaojun Li *
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Oxidative stress and inflammation are key pathological features of atherosclerotic plaques. Numerous nanomedicines have been developed to alleviate oxidative stress and reduce inflammation within plaques. However, nonbioactive carrier materials reduce the bioavailability of nanomedicines and may pose potential biological toxicity. In this study, we utilized the unique amphiphilic chemical structure of lipoic acid (LA) to prepare LA nanoparticles (LA NPs) via a self-assembly method. Leveraging the inherent anti-inflammatory and antioxidant properties of LA, these NPs were used for the treatment of atherosclerosis. In an inflammatory macrophage model, LA NPs exhibited superior anti-inflammatory activity compared to free LA. Through ultrasound imaging and pathological methods, we discovered that LA NPs demonstrated nice antiatherosclerotic effects in an atherosclerotic mice model. Immunofluorescence analysis further indicated that the antiatherosclerotic effects of LA were associated with the alleviation of oxidative stress within the plaques, reduced macrophage infiltration, and downregulation of inflammatory cytokine levels. Therefore, LA NPs offer a promising therapeutic strategy for the treatment of atherosclerosis.
Combined Treatment Methods for Removal of Antibiotics from Beef Wastewater
Bobbi S. Stromer *- ,
Bryan L. Woodbury - ,
Clinton F. Williams - , and
Mindy J. Spiehs
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Use of antibiotics is common practice in agriculture; however, they can be released into the environment, potentially causing antimicrobial resistance. Naturally mined diatomaceous earth with bentonite was tested as a remediation material for tylosin, chlortetracycline, and ceftiofur in wastewater from a beef cattle feedlot. Langmuir binding affinity in 10 mM sodium phosphate buffer at pH 6.7 was established prior to testing wastewater to determine binding potential. Chlortetracycline was found to have a binding affinity of 15.2 mM–1 and a binding capacity of 123 mg per g of diatomaceous earth while ceftiofur showed a much lower binding affinity and loading at 7.8 mM–1 and 3 mg per g of diatomaceous earth, respectively. From spiked wastewater, tylosin (50 μg mL–1, pH 8) and chlortetracycline (300 μg mL–1, pH 6) were removed (100 and 80%, respectively) when treated with 20 mg of diatomaceous earth while ceftiofur (300 μg mL–1, pH 8) remained in solution. When the spiked wastewater was flocculated with aluminum sulfate, a change in pH from 8 to 4 was observed, and chlortetracycline was removed from the wastewater; tylosin and ceftiofur remained in solution. When subsequently treated with diatomaceous earth, ceftiofur and tylosin were completely removed by diatomaceous earth from the flocculated wastewater.
Cholic-Acid Derived, Guanidine-Functionalized Polymers as Broad-Spectrum Antimicrobial Agents
Yijun Xiong - ,
Umeka Nayanathara - ,
Xiangfeng Lai - ,
Xiangyi Huang - ,
Changhe Zhang - ,
Daniel Yuen - ,
Parveen Sangwan - ,
Hsin-hui Shen - ,
Angus P. R. Johnston - ,
Benjamin W. Muir - , and
Georgina K. Such *
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In this study, we report the design of a new guanylated, cholic-acid-based monomer (GM) to combat antimicrobial resistance. The microbial activity stems from the interfacial amphiphilicity of cholic acid, while guanidine shows a strong association with phosphate, which promotes binding to membrane phospholipids. The monomer showed strong antimicrobial activity; however, surprisingly, homopolymers synthesized by photoiniferter reversible addition–fragmentation chain-transfer (RAFT) polymerization of GM completely lost their activity likely due to the conformation of the polymer. In contrast, the design of GM copolymers with poly(ethylene glycol) methyl ether methacrylate (PEGMA) or 2-hydroxyethyl methacrylate (HEMA) allowed recovery of their antimicrobial activity. Due to the existence of cholesterol in cell membranes, hemolysis was highly dependent on the content of GM incorporated. This study highlights the unique and intriguing properties of this novel amphiphilic monomer and its polymers, providing valuable insights into the development of more potent antimicrobial materials.
Supercritical CO2-Mediated Decellularization of Bovine Spinal Cord Meninges: A Comparative Study for Decellularization Performance
Eren Ozudogru - ,
Tugce Kurt - ,
Burak Derkus - ,
Ugur Cengiz *- , and
Yavuz Emre Arslan *
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The extracellular matrix (ECM) of spinal meninge tissue closely resembles the wealthy ECM content of the brain and spinal cord. The ECM is typically acquired through the process of decellularizing tissues. Nevertheless, the decellularization process of the brain and spinal cord is challenging due to their high-fat content, in contrast to the spinal meninges. Hence, bovine spinal cord meninges offer a promising source to produce ECM-based scaffolds, thanks to their abundance, accessibility, and ease of decellularization for neural tissue engineering. However, most decellularization techniques involve disruptive chemicals and repetitive rinsing processes, which could lead to drastic modifications in the tissue ultrastructure and a loss of mechanical stability. Over the past decade, supercritical fluid technology has experienced considerable advancements in fabricating biomaterials with its applications spreading out to tissue engineering to tackle the complications mentioned above. Supercritical carbon-dioxide (scCO2)-based decellularization procedures especially offer a significant advantage over classical decellularization techniques, enabling the preservation of extracellular matrix components and structures. In this study, we decellularized the bovine spinal cord meninges by seven different methods. To identify the most effective approach, the decellularized matrices were characterized by dsDNA, collagen, and glycosaminoglycan contents and histological analyses. Moreover, the mechanical properties of the hydrogels produced from the decellularized matrices were evaluated. The novel scCO2-based treatment was completed in a shorter time than the conventional method (3 versus 7 days) while maintaining the structural and mechanical integrity of the tissue. Additionally, all hydrogels derived from scCO2-decellularized matrices demonstrated high cell viability and biocompatibility in a cell culture. The current study suggests a rapid, effective, and detergent-free scCO2-assisting decellularization protocol for clinical tissue engineering applications.
November 24, 2024
Structural Characteristics of the Fault Zone and Fault-Controlled Hydrocarbon Accumulation in the Chenghai Area of Dagang Offshore
Yan Chen - ,
Haitao Liu *- ,
Zhenglong Jiang *- ,
Jinghui Sun - ,
Zhenyu Bai - ,
Xiaoying Guo - ,
Xiongying Dong - , and
Hongjun Li
This publication is Open Access under the license indicated. Learn More
The Chenghai area is a secondary structural unit within the Qikou sag of the Bohai Bay Basin, located in the southern part of the Dagang offshore area, known for its abundant oil and gas resources. Influenced by multiple episodes of tectonic activity, the Chenghai area exhibits a highly developed fault system, which significantly impacts oil and gas exploration in the region. To investigate the structural characteristics of fault zones in the Chenghai area and their petroleum geological significance, this study builds upon previous research by utilizing oilfield drilling data and relevant seismic information. Through methods such as fault growth index analysis, structural evolution history, and examination of typical oil and gas reservoir profiles, a detailed structural analysis of fault-controlled hydrocarbon accumulation in this petroleum region was conducted. The results reveal three types of fault classifications in the study area: basal-controlled continuously active faults, buried reactivated segmented growth-connected faults, and late-stage continuously active isolated growth faults. The structural evolution is divided into four stages: the pre-Paleogene basement formation stage, the Rifting I stage of intense extensional deformation, the Rifting II stage of extensional stress reversal and intense deformation, and the post-Eocene weak extensional deformation-stable burial stage. The fault-controlled accumulation models include three types: fault-guided longitudinal accumulation, lateral sealing fault masking accumulation, and far-source step-like fault-guided accumulation. The formation of fault zones and fault-controlled oil and gas reservoirs in the Chenghai area is primarily influenced by inherited development faults, which determine the overall macroscopic distribution of oil and gas. The formation of oil and gas reservoirs occurred relatively late, with a general trend of decreased fault activity during this period, facilitating the effective accumulation and sealing of hydrocarbons.
Ethidium Bromide Degradation by Cold Atmospheric Plasma in Water and the Assessment of Byproduct Toxicity for Environmental Protection
Reema Reema - ,
Tejas Bedmutha - ,
Nishanta Kakati - ,
Veera Venkata Satya Prasanna Kumari Rayala - ,
Pullapanthula Radhakrishnanand - ,
Chingakham Juliya Devi - ,
Debajit Thakur - , and
Kamatchi Sankaranarayanan *
This publication is Open Access under the license indicated. Learn More
Ethidium bromide (Et–Br) is a widely used fluorescent dye in molecular biology and biotechnology laboratories for visualizing nucleic acids in agarose gel electrophoresis. However, concerns have been raised about its environmental impact and potential health risks due to its persistence and toxicity. The potential accumulation and long-term effects on the environment necessitate the removal of Et–Br from water. This study investigates the potential of novel cold plasma technology for the degradation of Et–Br. Cold atmospheric plasma (CAP) is an environmentally friendly technology that does not produce secondary pollutants and generates a variety of potent chemical reactive oxidants such as hydroxyl radicals (•OH), H2O2, NO2, and NO3. In this study, Et–Br was treated with CAP for 15 min without the addition of any chemicals, resulting in substantial removal of Et–Br. The degradation kinetics revealed that the CAP-treated Et–Br followed a pseudo-first-order reaction, dependent on the treatment time of CAP. The degradation of Et–Br by CAP is distinctly evident through the results obtained from both high-performance liquid chromatography (HPLC) and liquid chromatography-mass spectrometry (LC-MS) analyses, providing clear evidence of the occurrence of degradation. Furthermore, toxicity analyses of the degradation products were conducted by evaluating the Et–Br intercalation ability with DNA before and after treatment of Et–Br with CAP. To supplement the assessment, the binding of Et–Br with BSA has also been studied before and after CAP treatment. The impact of CAP-treated Et–Br on the growth and colony-forming unit (CFU) counts of Escherichia coli was also evaluated. Results indicated an increase in bacterial growth with an increase in CAP treatment time, suggesting that the degradation products of Et–Br using CAP were nontoxic. This study highlights the potential of CAP as a clean and efficient technology for the degradation of Et–Br, presenting a promising solution for mitigating its environmental and health risks.
Machine Learning Approach for the Prediction of Biomass Waste Pyrolysis Kinetics from Preliminary Analysis
Kai Xiao - and
Xianghui Zhu *
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In the present work, artificial neural network (ANN)-based machine learning models are developed to predict biomass pyrolysis kinetics. Data sets of thermogravimetric analysis and feedstock characterization from a diverse range of biomasses were used to build and test the networks. The composition of the raw biomass material was classified and used as input parameters of ANN models. Three models, which use ultimate analysis, proximate analysis, and three components as input parameters, were developed in this study. A total of 32 types of biomass raw materials were used, and 270 sets of kinetic data were obtained according to different pyrolysis conversion rates ranging from 0.1 to 0.9. Results show that increasing the number of neurons can improve the prediction accuracy. The optimized neuron number is 7–11. The largest relative deviation between experimental and modeling results for the three models are 20.80%, 14.06% and 12.85%, respectively, which proves that using cellulose, hemicellulose, and lignin as input parameters of the neural network model can better predict the activation energy of pyrolysis at each reaction stage. The particle swarm optimization algorithm could significantly improve the prediction accuracy of the BP-ANN model. The largest deviation for activated energy prediction decreases from 12.85% to 6.72%.
Lyophilized T Cell Reference Materials with Quantified Proportions of Subtypes
Yinbo Huo - ,
Jiaqi Yang - ,
Yanli Wen - ,
Wen Liang - ,
Qing Tao - ,
Juan Yan - ,
Hui Xu - ,
Lanying Li - ,
Yan Li - ,
Li Xu - ,
Min Ding - ,
Feiyan Gong - , and
Gang Liu *
This publication is Open Access under the license indicated. Learn More
The accurate quantification of T cell subtypes and their proportions is of great significance in cell-based biomanufacturing, diagnosis, and advanced therapy. The development and application of a cell reference material (RM) provide a solid foundation for reliable and consistent T cell quantification worldwide. However, creating a cell RM that is both accurate and practical remains a challenge. In this study, we have developed a series of T cell RMs with a certified subtype proportion based on traceable accurate quantification and stable long-term preservation. We developed a quantitative flow cytometry method for the ratio of T cell subtypes with improved accuracy by using the calibration of certified reference materials of polystyrene beads. The relative standard deviation (RSD) for the quantification of CD3+, CD4+, and CD8+ subtypes was 0.43%, 0.64%, and 1.31%, respectively. To ensure long-term stability, an innovative lyophilization preservation technique was developed for our T cell RMs. The morphology and surface antigens (CD45, CD3, CD4, and CD8) of T cell RMs were characterized after lyophilization using immunofluorescence, demonstrating their equally good integrity compared with fresh cells. Their stability at 4 °C was demonstrated by continuous monitoring over 12 months. The final value assignment of the RMs was performed through quantification using flow cytometry in different laboratories. One of our RMs has been applied for the calibration of 54 different flow cytometry instruments. The T cell RMs have outstanding potential in the quality control of multiparameter flow cytometry measurements, and we believe they have great application prospects for the establishment and validation of T cell assays.
Facile Synthesis of Bamboo Biochar for Efficient Adsorption of Quinolone Antibiotics: Effects and Mechanisms
Erming Ouyang - ,
Ruiyue Zhang - ,
WenJie Fu - ,
Rui Zhao *- ,
Hongwei Yang - ,
Hanrui Xiang - , and
Wanyuan He
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The harmful effects of quinolone antibiotics on ecology and human health have attracted widespread attention. In this study, bamboo biochar synthesized at different pyrolysis temperatures was used to remove quinolone antibiotics (moxifloxacin (MFX), ciprofloxacin (CIP), and ofloxacin (OFLX) as models). The pyrolysis temperature of 700 °C led to a high pore volume and average pore size of biochar. The biochar produced at 700 °C presented high adsorption properties for MFX, CIP, and OFLX. The maximum adsorption capacities for MFX, CIP, and OFLX were 135.56, 151.31, and 116.40 mg/g, respectively. The adsorption performance could be described by the Langmuir isotherm model and pseudo-second-order kinetic model. Biochar produced from waste bamboo could be applied as low-cost environmental adsorbents for quinolone antibiotics removal.
Analyzing the Effect of Resveratrol on Pharmacokinetics of Antituberculosis Drug Bedaquiline in Rats by a Novel UPLC-MS/MS Approach
Yun Ye - ,
Zhe Chen - ,
Yuxin Shen - ,
Hualu Wu - ,
Ren-Ai Xu *- , and
Chen-Jian Zhou *
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Bedaquiline (BDQ), a diarylquinoline compound, is an inhibitor of mycobacterial ATP synthase, specifically with FDA approval as a treatment for multidrug-resistant tuberculosis (MDR-TB). M2 is the main metabolite of BDQ and is active against tuberculosis. The objective of this study was to establish and validate a sensitive and convenient ultraperformance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) approach to concurrently quantify BDQ and M2 in rat plasma and to examine whether resveratrol, a CYP3A4 inhibitor, could influence the pharmacokinetics of BDQ and M2 in rats. Plasma samples containing the internal standard (IS) linezolid were formulated by adding acetonitrile for a simple one-step protein precipitation, and the analytes in samples were quantified by the UPLC-MS/MS method. BDQ and M2 were successfully calibrated in the ranges of 0.5–1000 and 1.0–200 ng/mL, where the lower limit of quantification (LLOQ) was 0.5 and 1.0 ng/mL, respectively. The precisions and accuracies of BDQ and M2 were in compliance with the FDA analytical standards. Recoveries and matrix effects of the analytes were satisfactory, and the analytes remained stable under four different temperatures and conditions. The well-validated UPLC-MS/MS method was successfully applied to the study of the food-drug interaction in rats. Remarkably, resveratrol increased the level of exposure of BDQ. Furthermore, the effect of resveratrol on the metabolism of BDQ and M2 needs further clinical studies.
Ferroelasticity and Canted Antiferromagnetism in Two-Dimensional Organic–Inorganic Layered Perovskite [C6H9(CH2)2NH3]2FeCl4
Naoto Tsuchiya - ,
Tatsuya Ishinuki - ,
Yuki Nakayama - ,
Xianda Deng - ,
Goulven Cosquer - ,
Takahiro Onimaru - ,
Sadafumi Nishihara - , and
Katsuya Inoue *
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Two-dimensional organic–inorganic perovskites have been attracted as candidates for multiferroic materials that exhibit two or more ferroic orders such as ferromagnetism, ferroelectricity, ferroelasticity, and ferrotoroidicity. Here, we introduce the structure, ferroelastic domains and magnetic properties of the two-dimensional organic–inorganic perovskite [C6H9(CH2)2NH3]2FeCl4 (CHEA-Fe) composed of 2-(1-cyclohexenyl)ethylammonium and FeCl42–. CHEA-Fe underwent two ferroelastic phase transitions from tetragonal to orthorhombic at 332 K and to monoclinic at 232 K with decreasing temperature and exhibited ferroelastic domains under polarized light as a consequence of these ferroelastic phase transitions. Magnetization measurements exhibited two magnetization jumps at the transition temperature, which agrees with ferroelastic phase transitions. Furthermore, CHEA-Fe acted as canted antiferromagnetism below TN = 85.7 K. The isothermal magnetization revealed a magnetic hysteresis when the magnetic field was applied along the stacking axis of the layers.
Highly Electrically Conductive PEDOT:PSS Films via Layer-By-Layer Electrostatic Self-Assembly
Muhammad Khurram - ,
Sven Neuber - ,
Annekatrin Sill - , and
Christiane A. Helm *
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Electrically conductive films of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) are usually formed by spin coating of aqueous dispersions with PEDOT:PSS nanoparticles. To better understand the film formation, the adsorption conditions are investigated using dip coating and a flow cell with different flow rates. Multilayer films are formed by sequential adsorption of oppositely charged macromolecules or nanoparticles. PEDOT:PSS serves as polyanion, and PDADMA is the polycation. In the dip coating process, the first layer consists of a ≈70 nm thick PEDOT:PSS nanoparticle monolayer. Subsequent PDADMA/PEDOT:PSS bilayers have a constant thickness (9.5 nm). Using the flow cell (0.2 mL/min) for film preparation led to constant PDADMA/PEDOT:PSS bilayer thickness (7.5 nm). PEDOT:PSS nanoparticle monolayers were only observed after PEDOT:PSS adsorption when the washing step was omitted. The electrical conductivity is independent of the number of deposition cycles for both preparation methods. Films prepared by dip coating show low conductivity (26 kS/m) and high surface roughness, whereas films prepared by flow cell show high conductivity (230 kS/m) and low roughness (2–4 nm). We propose that the adsorption in a flow cell leads to a flat orientation of the PEDOT molecules, which increases charge carrier mobility. It is hoped that a better understanding of the relationship between adsorption conditions and carrier mobility will further improve electrical conductivity.
November 23, 2024
Deciphering Structural Dynamics of Atherosclerosis Proteins: Insights from Crataegus oxyacantha Phytochemicals that Interceded Functional and Structural Changes in Targeted Atherosclerotic Proteins
Praveen Jeeva - ,
Anusuyadevi Muthusamy - , and
Jayachandran Kesavan swaminathan *
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Atherosclerosis (ASC) is characterized by foam cell-mediated plaque formation, vascular endothelial inflammation, and lipidosis and is the rudimentary cause of cardiovascular diseases. This is the pre-eminent global factor of mortality. This etiological paradigm is significantly influenced by several proteins, where 23 pivotal proteins involved in ASC were meticulously gleaned on the basis of literature studies. The crux of the present study was aimed to probe the drugability of four active phytochemicals from Crataegus oxyacantha (COC): epicatechin, gallate, tyramine, and vitexin against the selected 23 proteins. The molecular docking analysis was judiciously administered via Glide, the binding free energy was calculated in detail utilizing the prime molecular mechanics-generalized Born surface area (MM-GBSA) module, and a deeper comprehensive investigation of protein–ligand dynamic associations was elucidated through Desmond. Drawing from the upper echelons of our docking results, the molecular dynamics simulation outcomes revealed that the macrophage migration inhibitory factor and prethrombin-1 showed persistent binding nature with gallate. The bioactive compound known as gallate sourced from COC shows the best molecular association with pivotal proteins involved in ASC and has a promising therapeutic potential for drug development endeavors.
Diclofenac Removal by Alkylammonium Clay Minerals Prepared over Microwave Heating
Denise B. França - ,
Alice P. N. Silva - ,
Josy A. Osajima - ,
Edson C. Silva-Filho - ,
Santiago Medina-Carrasco - ,
Maria del Mar Orta - ,
Maguy Jaber - , and
Maria G. Fonseca *
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Diclofenac is an emerging contaminant widely detected in water and has had adverse effects on the biota. In this study, the adsorbents were prepared by reacting tetradecyl-(C14), hexadecyl-(C16), and octadecyltrimethylammonium (C18) bromides with sodium vermiculite (Na-Ver) and used for the removal of the first time for diclofenac sodium from aqueous solution. Synthesis was carried out in a microwave-assisted reactor operating at 50 °C for 5 min, using proportions of organic salts in 100 and 200% of the phyllosilicate cation exchange capacity. The stability of loaded alkylammonium solids was evaluated under drug adsorption conditions. Adsorption was mainly influenced by the amount of surfactant incorporated into the clay mineral according to the thermogravimetric and CHN elemental analysis data. Samples prepared with 200% CEC presented lower stability at pH 6.0 and 8.0. Drug adsorption was more effective for C14-Ver-200%, C16-Ver-200%, and C18-Ver-200% samples, with a maximum retention of 97.8, 110.1, and 108.0 mg g–1, respectively. The adsorptive capacities of C14-Ver-200%, C16-Ver-200%, C18-Ver-200%, C14-Ver-100%, C16-Ver-100%, and C18-Ver-100% were reduced to 29.0, 36.8, 41.0, 61.0, 50.4, and 58.0%, respectively, compared with their initial value after three adsorption cycles. X-ray diffraction (XRD) patterns revealed that diclofenac was adsorbed into the interlayer region of organovermiculites. Fourier transform infrared spectroscopy (FTIR), Zeta potential results, and the pH study of adsorption indicated that van der Waals interactions are dominant in the adsorption mechanism.
Preparation of an Fe3O4 Nanoparticle/Carbonized Hemp Fiber Composite with Superior Microwave Absorption Performance
Wanxi Li *- ,
Boqiong Li - ,
Yali Zhao *- ,
Yingfen Wang - ,
Hengliang Liang - , and
Baoliang Lv
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The increasing concern over the negative impact of electromagnetic radiation and interference on humans has led to a growing interest in microwave-absorbing materials that are cost-effective, have a wide frequency range, and have high efficiency. In this paper, an Fe3O4 nanoparticle/carbonized hemp fiber composite was successfully prepared using hemp fibers as the primary material and template. By carefully regulating the concentration of the iron nitrate impregnation solution, accurate loading of Fe3O4 nanoparticles onto the carbonized hemp fiber was achieved. Due to its unique porous structure, the balance between impedance matching, and electromagnetic loss, the prepared Fe3O4 nanoparticle/carbonized hemp fiber composite exhibits light weight, high absorption strength, and broadband absorption characteristics. The broadest absorption bandwidth of 6.1 GHz can be achieved, covering the entire Ku-band, and the minimum refection loss is as low as −49.7 dB. More interestingly, the Fe3O4 nanoparticle/carbonized hemp fiber composite exhibits attractive microwave absorption performance in both the X-band and Ku-band even with a wide range of Fe3O4 nanoparticle loading. Furthermore, simulations of the radar cross section (RCS) have confirmed that the Fe3O4 nanoparticle/carbonized hemp fiber composite is effective in attenuating electromagnetic waves in a real environment. This work presents an economical and efficient method for the development of porous carbon-based absorbents.
Mapping the Binding Hotspots and Transient Binding Pockets on V-Domain Immunoglobulin Suppressor of T Cell Activation Protein Surface
Bingjie Li - ,
Lixiu Xu - ,
Chu Chen - , and
Jiqing Ye *
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V-domain immunoglobulin suppressor of T cell activation (VISTA), an inhibitory immune checkpoint present on both immune and tumor cells, has emerged as a highly promising target for cancer therapy due to its potential to overcome resistance encountered with existing immune checkpoint treatments. VSIG-3 is determined as an inhibitory ligand for VISTA, leading to the suppression of T cell proliferation. However, hotspots between VISTA/VSIG-3 protein–protein interaction remain ambiguous, mainly attributed to the lack of the structure of the VISTA/VSIG-3 complex. Therefore, in this study, in order to determine the energetic contributions of the interfacial residues on VISTA, we first constructed VISTA/VSIG-3 complex models by the protein docking method, followed by molecular dynamics simulations, binding free-energy decomposition, and alanine scanning. Results suggested that the putative hotspots in VISTA comprise residues His32, Tyr37, Thr35, Glu47, Val48, Gln49, Glu53, Arg54, Gln73, His122, and His126. Moreover, the distribution of the hotspots was clustered into two regions (hot regions I and II), and by using the TRAPP tool, transient subpockets within the hot regions were identified. Furthermore, conformational states of the binding pockets exhibiting druggability scores higher than those observed in the crystal structure were found. Overall, we hope that the findings outlined in this study can be used to facilitate the development of inhibitors targeting the VISTA/VSIG-3 immune checkpoint pathway in the future.
Adsorption of Bacteria Extracellular Polysaccharide Substances on the Graphite (002) Surface: A DFT and MD Study
G. Plason Zuerkanah Plakar *- ,
Fredy Harcel Kamgang Djioko - ,
Emeka Emmanuel Oguzie *- , and
Kanayo L. Oguzie
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Understanding the principle of the bacteria–anode surface interaction can enhance electron transfer in microbial fuel cells and aid in antibiofouling. In this article, we investigate the adsorption propensity of common adhesins [N-acetylglucosamine (NAG), d-glucose, and alginate] found in microbial biofilms on the surface of unmodified and modified graphite through density functional theory and molecular dynamics simulations. DFT results showed that all the molecules could interact with the graphite surface, with NAG (ΔEgap = 3.677 eV) being the most reactive molecule. The Fukui function results show that the most active sites were located at O, C13, and N on the adsorbates. The optimum conditions were basic medium at 303 K across all systems. All adsorbates show energetically favorable adsorption, with NAG showing the maximum adsorption energy irrespective of the modification. The modified graphite system showed increased adsorption compared to the unmodified graphite system. Electrostatic interactions, H-bonding, and π–π stacking or interactions are the driving forces responsible for the chemical bond formation in the adsorbates–adsorbent complexes. Altogether, this research provides theoretical support for bacterial adhesin adsorption onto graphite anodes and new ideas for studying bacteria–anode interactions in fuel cells, biofouling and antifouling, dental science, clean energy production, and wastewater treatment.
November 22, 2024
Probing Electronic Doping in CVD Graphene Crystals Treated by HNO3 Vapors
Nikos Delikoukos - ,
Stavros Katsiaounis *- ,
John Parthenios - ,
Labrini Sygellou - ,
Dimitrios Tasis - , and
Konstantinos Papagelis *
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In this work, we present a comprehensive protocol for achieving hole doping in graphene through exposure to nitric acid (HNO3) vapors. We demonstrate gradual p-type surface doping of CVD-grown graphene on a Si/SiO2 substrate by thermally depositing nitric acid molecules to form self-assembled charge transfer complexes. Detailed analysis of charge carrier concentration and Fermi energy shifts was conducted using Raman, X-ray and ultraviolet photoelectron spectroscopies (XPS/UPS). Our methodology, including a novel PMMA coating step, ensures stability and efficiency of the doping process, highlighting its effectiveness in inducing permanent hole doping while maintaining the structural integrity of the graphene.
Exploring the Potential Fungicidal Applications of a Cu(II) Complex with Schiff Base and Carboxylates against Fusarium equisetum
Arun Kuila - ,
Ribhu Maity - ,
Prasun Acharya - ,
Tuhin Sarkar - ,
Ankika Bhakat - ,
Paula Brandao - ,
Satyajit Pattanayak - ,
Tithi Maity - ,
Sudipta Dalai *- ,
Keka Sarkar *- , and
Bidhan Chandra Samanta *
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Given the critical need to preserve agricultural sustainability, there is an urgent call to address fungal infections. Our study presents a promising approach by focusing on SIX (Secreted in Xylem) proteins as a pivotal target for the development of innovative fungicidal strategies. Within the sphere of this study, we meticulously scrutinize the antifungal efficacy of our synthesized Cu(II) complex formulated as [Cu(L1)2(L2)]+(ClO4)−, where L1 represents (E)-cyclohexyl–N(pyridine-2-xlmethylene) methanamine and L2H denotes cinnamic acid, compared against a commercially available fungicide comprising 4% hexaconazole and 68% zineb. Employing in silico methodologies, we undertake a comparative analysis targeting SIX proteins to discern the potency of our compound. The X-ray diffraction, 1H NMR, and FTIR spectroscopic techniques were utilized to elucidate the structure of the complex methodically. The lipophilicity test of the complex signifies its potential lipophilic nature and prompted further investigation into the complex’s interaction with DNA (DNA) and bovine serum albumin (BSA). The binding constant values suggested a notable interaction between the complex and both DNA and BSA. The antifungal test reveal that our complex emerges as a potent contender in the battle against Fusarium equisetum (F.E.), exhibiting a commendable efficacy that positions it as a viable substitute for the incumbent commercial fungicide. This discovery predicts well the prospect of bolstering agricultural resilience and safeguarding global food security in the face of pervasive fungal threats.
In Vitro Effects of Some Chemotherapeutics on Human Erythrocyte Glucose-6-Phosphate Dehydrogenase Enzyme
Çiğdem Çoban - ,
Yusuf Temel *- , and
Mehmet Çiftci
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In this study; the in vitro effects of some drugs used in chemotherapy on the glucose-6-phosphate dehydrogenase enzyme (G6PD; E.C. 1.1.1.49) purified from human erythrocyte lysate were investigated. In the first stage of the study, G6PD enzyme was purified from human erythrocyte lysate (with a specific activity of 0.243 EU/mg protein, 68.75% yield and 162 purificaion fold) by ammonium sulfate precipitation and 2′, 5′ Adenosine diphosphate (ADP)-Sepharose 4B gel affinity chromatography. The purity of the enzyme was checked by the sodium dodecyl sulfate–polyacrylamide gel electrophoresis (SDS-PAGE). In the second stage of the study, the in vitro effects of some chemotherapy drugs such as ibandronic acid, fluorouracil, oxaliplatin, carboplatin, cyclophosphamide, doxorubicin, metoart con and cisplatin on the activity of the purified enzyme were investigated. As a result of the in vitro studies, the drugs ibandronic acid, oxaliplatin and carboplatin, have an inhibitory effect on the enzyme, and IC50 values were calculated as 1.34, 2.05, and 2.43 mM, respectively. In addition, in order to determine the Ki constants and inhibition types for the drugs oxaliplatin and carboplatin, activity measurements were made at five different substrates and three fixed inhibitor concentrations and Lineweaver–Burk graphs were drawn. With the help of these graphs, the Ki constant of oxaliplatin was determined as 19.46 ± 3.38 mM and the Ki constant of carboplatin was 22.37 ± 3.19 mM. It was determined that the inhibition type of both drugs was competitive. It was determined that the drugs fluorouracil, cyclophosphamide, doxorubicin, metoart con, and cisplatin did not have a significant effect on the enzyme activity.
A High-Throughput Method for Screening Peptide Activators of G-Protein-Coupled Receptors
Yagya Prasad Paudel - ,
Pedro A. Valiente - ,
Jisun Kim - , and
Philip M. Kim *
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Here, we describe an innovative and efficient method for screening peptide activators of G-protein-coupled receptors (GPCRs) utilizing a protein–protein interaction (PPI) approach. We designed a library of 92,918 peptides fused with transmembrane domains of glycosylphosphatidylinositol-anchored proteins (GPI-APs). We employed a pooled lentiviral system to promote the expression of these proteins at the cellular membrane and evaluate their ability to activate GPCRs. We then used fluorescence-activated cell sorting (FACS) to screen the GPI-AP-peptide library and identify novel peptide activators of the glucagon-like peptide-1 receptor (GLP-1R). We discovered one peptide PepA3 derived from the Frizzled-like (FZ) domain of human Carboxypeptidase Z (CPZ), a regulated secreted metallocarboxypeptidase. Notably, PepA3 and its two related variants, PepA and PepA2, activated the GLP-1R receptor with less potency but comparable efficacy to that of GLP-1. We then hypothesized that all of these peptides will bind differently to the GLP-1R than the normal ligand. Our technology could identify novel GPCR-activating peptides for structure–function or drug discovery research.
Toward Sustainable Polyurethane Foams: Effects of Corn Cob Fibers and Silver Nanoparticles on Mechanical Properties and Antimicrobial Activity
Gabriel Vinicius Alves Silva *- ,
Gabriel Fornazaro - ,
Gabriel Vinicius Inacio Benati - ,
Mychelle Vianna Pereira Companhoni - ,
Francielle Pelegrin Garcia - ,
Jean Halison de Oliveira - ,
Eduardo Radovanovic - , and
Silvia Luciana Fávaro
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Polyurethane foams (PFs) are widely used in mattresses, upholstery, and insulation, but disposal is difficult due to the disintegration time and environmental hazards of synthetic polyol. This work investigates a sustainable alternative by replacing poly(ethylene glycol) (PEG) with corn cob fibers and incorporating antibacterial silver nanoparticles (AgNPs). Corn cob fibers and sodium hydroxide-treated fibers were used to make foams, with corn cob fibers substituting PEG at 5–30 wt %. In terms of durability and elastic modulus, low-fiber-content foams matched nonfiber counterparts. Higher fiber content (more than 20%) resulted in divergent properties with potential benefits. In terms of viscoelastic qualities, foams with a 15% fiber content outperformed nonfiber foam. Antimicrobial testing revealed that AgNP-infused foams with 15% corn cob fibers effectively inhibited microbiological growth.
A Modular Approach to Obtain HER2-Targeting DM1-Loaded Nanoparticles for Gastric Cancer Therapy
Hui Zhang - ,
Lijiao Guo - ,
Xue Li - ,
Hongtao Liu - ,
Zibin Zhao - ,
Guangling Ji - ,
Yue Huang *- , and
Xiaodong Wang *
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Antibody-based tumor-targeting nanomedicines, despite their high efficacy, present significant challenges in preparation and long-term storage. We introduce a novel approach for the synthesis of durable, ready-to-use, antibody-coupled nanomedical drugs. Our research centers on the development of HER2-targeting DM1-loaded nanoparticles for gastric cancer treatment using a modular methodology. We synthesized Fc-PLG-Mal, conjugated DM1 through a “click” reaction, and subsequently bound the resultant compound with the HER2 antibody trastuzumab. The nanoparticles demonstrated a high drug loading content, stable particle size, and effective HER2 targeting. HER2-PLG-DM1 exhibited significant cytotoxicity against NCI-N87 gastric cancer cells, with an IC50 of 0.35 nM. Biodistribution revealed rapid and substantial tumor accumulation, 6-fold higher than that of nontargeting IgG-PLG-DM1. HER2-PLG-DM1 significantly inhibited tumor growth in NCI-N87 tumor-bearing mice, achieving a 90.8% tumor inhibition rate, and displayed dose-dependent effects without significant liver and kidney toxicity. These studies offer an efficient and stable method for the preparation of antibody-coupled drugs.
Coupling UiO-66 MOF with a Nanotubular Oxide Layer Grown on Ti-W Alloy Accelerates the Degradation of Hormones in Real Water Matrices
Isabela Disigant - ,
Juliana de Almeida - ,
Débora Noma Okamoto - ,
Rodnei Bertazzoli - , and
Christiane de Arruda Rodrigues *
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To enable the photoelectrocatalytic treatment of large volumes of water containing low concentrations of pollutants, this study introduces a hybrid photocatalyst, composed of nanotubular oxides grown on TixW alloy (x = 0.5 and 5.0 wt %) modified with UiO-66 MOF, for degradation of estrone (E1) and 17α-ethinyl estradiol (EE2). The oxide layer (Nt/TixW) was prepared via anodization, while UiO-66 nanoparticles were synthesized by using a solvothermal process. Different techniques for modifying nanotubular oxides were evaluated to maximize the photocatalytic activity and the sorption process. In photo(electro)catalytic experiments using low concentrations of E1 and EE2 synthetic solutions and UV–vis radiation (100 W/cm2), all modified materials exhibited approximately 40% higher degradation compared to the unmodified photocatalyst, keeping the same sequential performance of the photocatalysts (Nt/TiO2 < Nt/Ti-0.5W < Nt/Ti-5.0W) independent of the treatment. This enhancement was attributed to the MOF’s increased hormone sorption, with no synergistic interaction observed between the photocatalyst and the adsorbent. In real water supply matrices, the photoelectrocatalytic removal rate of E1 using Nt/Ti-5.0W modified UiO-66 under UV–vis radiation and 1.3 V was 0.168 s–1, while for EE2, it was 0.310 min–1, approximately 1.78 and 18.21 times faster than obtained with the unmodified photocatalyst. The slower degradation rate of EE2 compared to that of E1 is attributed to the formation of denser intermediates that compete with smaller organic molecules in the real matrix. The cooperative effect between NT/TixW and UiO-66 favored the confinement of pollutants and by-products within the UiO-66 cavity, minimizing the diffusion effects and promoting the degradation of these compounds by the OH· radical generated at the oxide/solution interface. Among the tested electrodes, NT/Ti5W modified with UiO-66 demonstrated the highest efficiency and stability during the recycle tests. This highlights its promise for applications in photocatalytic processes for treating water supplies with low pollutant concentrations.
Enhancement of 5-Aminolevulinic Acid-Mediated Photodynamic Inactivation of Proteus mirabilis Using Phosphoric and Bisaminophosphinic Acids as Permeabilizing Agents
Anna Zdubek - ,
Irena Maliszewska *- ,
Agnieszka Grabowiecka - ,
Rafał Kowalczyk - , and
Bartosz Turek
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The purpose of this work was to examine the effect of phosphoric and bisaminophosphinic acids on the effectiveness of photoinactivation of Proteus mirabilis with 5-aminolevulinic acid (5-ALA) as a precursor of protoporphyrin IX. Two diode lasers λ = 404 nm (radiation intensity 26 mW cm–2) and λ = 630 nm (radiation intensity 55 mW cm–2) were used as sources of light. The most effective agent was (R)-(−)-1,1′-binaphthyl-2,2′-diylhydrogen phosphate, and a significant improvement in bactericidal effect of 5-ALA-aPDI was achieved by pretreating P. mirabilis with this compound at nontoxic concentrations of 0.368 mM. It was found that 15 min of blue light illumination was enough to achieve bacterial cell mortality of 99.999%. Photoelimination of this pathogen using red light was less effective, and the required killing effect (at least 99.99%) was not achieved until 45 min of exposure. The mechanism of increased pathogen destruction by the examined acids is multifaceted and includes not only the destabilization of the outer bacterial cell membrane by organophosphates but also an increase in the level of protoporphyrin IX in cells due to chelation of iron ions. Furthermore, a synergistic effect of intracellular photosensitizers and (R)-(−)-1,1′-binaphthyl-2,2′-diylhydrogen phosphate acting as an additional blue/red light-induced photosensitizer cannot be excluded.
Constructions, Purifications and Applications of DNA-Antibody Conjugates: A Review
Tao Wang - ,
Xuelin Wang - ,
Shuhong Luo - ,
Peng Zhang - ,
Na Li - ,
Can Chen - ,
Jianwen Li - ,
Hao Shi - ,
Hua Dong *- , and
Ruo-Pan Huang *
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A DNA-antibody conjugate is a synthetic molecule that combines the unique functions of both an antibody and DNA. With the increased accessibility of commercialized kits, the procedure for constructing conjugates is simplified and the requirement for chemistry background is reduced. As a result, the difficulty of preparing a DNA-antibody conjugate has been significantly lowered. Therefore, the application of DNA-antibody conjugates has attracted more interest in recent years. The most common application of DNA-antibody conjugates is based on the amplifiable property of DNA through PCR. This includes single-conjugate-based immuno-PCR, paired-conjugates-based proximity ligation assay, and proximity extension assay. These methods achieve highly sensitive or specific detection of target proteins. The conjugated single stranded DNA molecules can also specifically hybridize with another strand containing its complementary sequence. This property can be used to selectively bind fluorophore labeled DNA strands, which plays an important role in tissue imaging and spatial omics. All these factors make DNA-antibody conjugates have a broad range of applications in research, diagnosis, and potentially therapy.
Self-Assembly Systems Based on Betaine-Type Hydrophobic Association Polymer Used in Acid Stimulation: Effects of Surfactant and Salt Ion
Yuling Hu - ,
Hongping Quan *- ,
Peng Shen - ,
Xuewen Chen - ,
Yingze Pei - , and
Zhiyu Huang *
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Hydrophobic association polymers containing various functional groups have a great deal of application potential as a self-thickening agent in carbonate acidification, while the improvement of their viscosification ability under high temperature conditions remains a significant challenge. A kind of betaine-type hydrophobic association polymer (PASD) intended for use as an acid thickener was synthesized through aqueous solution polymerization with sulfobetaine and a soluble hydrophobic monomer. The structure of PASD was characterized by FT-IR and 1H NMR. It is found that during the acid-rock reaction, the physical cross-linking between PASD and cationic surfactants (STAC) occurs through noncovalent bonding forces such as micellar interaction and electrostatic interaction, forming a self-assembly acid. The optimum conditions for the construction of the self-assembly acid and its viscosification properties, rheological properties, temperature, and salt resistance were evaluated by a six-speed rotating viscometer and a HAAK MARSIII rheometer. The results suggest that the main source of the viscosity rise of the self-assembly acid is the CaCl2 produced during the acid-rock reaction. As the acid-rock reaction progresses, the hydrodynamic radius of the self-assembly acid increases, and tighter aggregation structures form. The viscosity of the self-assembly spent acid still keeps in 140 mPa·s under 140 °C shearing for 1 h at 170 s–1, which indicates that the self-assembly acid has excellent viscosification ability and temperature resistance. Compared to PASD acid, the self-assembly acid can be used at a wider range of temperatures, and its research and development have given rise to novel ideas for the use of HAWPs as an acid thickener.
Diterpenoids and Triterpenoids from the Aerial Parts of Isodon serra and Their Biological Activities
Wen-Jing Ren - ,
Rong Jiang - ,
Kei-Fong Ng - ,
Meng-Yu Bao - ,
Xiao-Mei Liu - ,
Wei Zhang - ,
Zhi-Hong Jiang - ,
Yu-Hong Liu *- , and
Guo-Yuan Zhu *
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Five undescribed diterpenoids, serranins A–E (1–5), and four novel triterpenoids, serratic acids A–D (6–9), along with 32 known terpenoids (10–41) were isolated from the aerial parts of Isodon serra. The planar structures of 1–9 and their relative configurations were established on the basis of extensive spectroscopic analysis. Structurally, compounds 6–9 are the first examples of 18,19-seco-ursane p-coumaric or ferulic esters, while compounds 1–5 further enriched the plant’s diterpene profile. Bioactivity evaluation revealed that four diterpenoids (2, 10, 12, and 13) exhibited potent cytotoxic activity against four cancer cell lines (B16–F10, A375, A549, and MDA-MB-231) with IC50 values below 10 μM. Remarkably, 7 and 38 exhibited a comparable antimelanogenesis effect to that of positive control (kojic acid) in B16–F10 cells.
November 21, 2024
Facile Synthesis of Natural Kaolin-Based CuO Catalyst: An Efficient Heterogeneous Catalyst for the Catalytic Reduction of 4-Nitrophenol
Zinabu Gashaw Asmare - ,
Belete Asefa Aragaw *- , and
Minaleshewa Atlabachew *
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Water contamination by nitro compounds from various industrial processes has significantly contributed to environmental pollution and severely threatened aquatic ecosystems. Inexpensive, efficient, and environmentally benign catalysts are required for the catalytic reduction of such nitro compounds. This study reports the fabrication of various nanocomposites (NCs) of copper oxide nanoparticles (CuO NPs) supported on a kaolin sheet using straightforward and simple one-pot synthesis procedures that control the metal precursor to kaolin ratios. The selected as-synthesized CuO/kaolin NC was characterized using a range of advanced spectroscopic and microscopic methods, such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), ultraviolet–visible (UV–vis) spectroscopy, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), high-angle annular dark-field scanning TEM (HAADF-STEM), and N2 adsorption/desorption analysis. The characterization results confirmed the successful incorporation of CuO NPs into the kaolin sheets, which had an average size of about 18.7 nm. The fabricated CuO/kaolin NC was used as a heterogeneous catalyst for the efficient reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in the presence of sodium borohydride (NaBH4) in an aqueous system at room temperature. The catalyst demonstrated superior catalytic performance with high 4-NP conversion into 4-AP (>99%) in the aqueous phase (50 mL, 20 mg L–1) within 6 min. In addition, the reaction kinetics of 4-NP reduction was also investigated, and the reaction followed the pseudo-first-order kinetics equation with the apparent rate constant of 1.76 min–1. Furthermore, the Arrhenius and Eyring parameters for the catalytic hydrogenation reaction of 4-NP were calculated in order to investigate the catalytic reaction process in more detail. Moreover, the catalyst exhibited excellent reusability and stability over seven repeated catalytic test cycles without any noticeable decline in catalytic activity. Therefore, this paper could provide a novel, efficient, and environmentally promising clay-based non-noble metal oxide nanocatalyst to reduce nitro compounds in the aqueous system.
Spaced Hybrid TiO2/Au Nanotube Arrays with Tailored Optical Properties for Surface-Enhanced Raman Scattering
Morteza Afshar - ,
Subrata Ghosh - ,
Luca Mascaretti *- ,
Štěpán Kment - ,
Carlo Spartaco Casari *- , and
Alberto Naldoni *
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Controlling the overall geometry of plasmonic materials allows for tailoring their optical response and the effects that can be exploited to enhance the performance of a wide range of devices. This study demonstrates a simple method to control the size and distribution of gold (Au) nanoparticles grown on the surface of spaced titanium dioxide (TiO2) nanotubes by varying the deposition time of magnetron sputtering. While shorter depositions led to small and well-separated Au nanoparticles, longer depositions promoted the formation of quasi-continuous layers with small interparticle gaps. The optical spectra of Au/TiO2 nanotubes showed a region of strong absorption (200–550 nm) for all samples and a region of decreasing absorption with an increase of effective Au thickness (550–1100 nm). This behavior led to distinct trends in the Raman signal enhancement of the underlying TiO2 nanotubes depending on the excitation laser wavelength. Furthermore, the quasi-continuous layers formed at higher effective Au thicknesses promoted an amplification of the signal and an improvement in the detection limit of target molecules in surface-enhanced Raman scattering (SERS) experiments. These findings suggest a simple method for designing efficient devices with tailored light absorption and potential applications in detectors and other optical devices.
Combustion versus Gasification in Power- and Biomass-to-X Processes: An Exergetic Analysis
Simone Mucci - ,
Alexander Mitsos - , and
Dominik Bongartz *
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Residual biomass is a promising carbon feedstock for the production of electricity-based organic chemicals and fuels since, unlike carbon dioxide captured from point sources or air, it also has a valuable energy input. Biomass can be converted into an intermediate stream suitable for Power-to-X processes mainly via combustion or gasification. Such combined processes are generally called biohybrid or Power- and Biomass-to-X processes. To investigate the potential of biomass utilization in Power- and Biomass-to-X processes and identify inherent efficiency differences between these pathways, we model the process units with simple mass and energy balances considering empirical parameters for the key process units and perform an exergetic analysis. The analysis is conducted for several molecules of interest for the chemical and transport sectors with different C:H:O ratios, i.e., methane, methanol, dimethyl ether, and dodecane. For all considered products, the Power- and Biomass-to-X processes with biomass gasification, either with pure oxygen or steam as oxidizing agents, have a significantly higher (∼15–20 percentage points) exergy efficiency. This difference is mainly due to the lower exergy loss for water electrolysis since a lower amount of hydrogen is needed and to the higher exergy efficiency of the gasification unit compared to that of the combustion unit. Therefore, gasification-based Power- and Biomass-to-X processes have clear thermodynamic advantages in the ideal case. These conclusions obtained with the simple models are confirmed by modeling a Power- and Biomass-to-Methanol process in detail, also accounting for practical factors such as side reactions, incomplete reactant conversion, and ash formation.
Out-of-Plane Longitudinal Sound Speed Determination in GaS by Broadband Time-Domain Brillouin Scattering
Watheq Al-Basheer *- ,
Christian Viernes - ,
Ruofei Zheng - ,
Sam Netzke - ,
Kostyantyn Pichugin - , and
German Sciaini *
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Two-dimensional semiconducting gallium sulfide (GaS) has garnered notable interest for its distinct structural and optical properties, which position it as a promising candidate material for various applications ranging from photodetection and photovoltaics to nonlinear frequency conversion. In this work, we determined the out-of-plane longitudinal sound velocity, vL, via impulsive time-domain femtosecond broadband Brillouin scattering measurements performed on a single flake-like GaS crystal. We obtained a value vL= (3140 ± 20) m/s, which yields an out-of-plane compressive elastic constant, C33= (38.1 ± 0.5) GPa.
Machine Learning-Assisted Designing and Screening of Polymers with a High Melting Point: Database Visualization and Synthetic Feasibility Assessment
Zaheer Ahmed Dayo - ,
Jiang Guosong *- ,
Mohamed A. El-Tayeb - ,
Syed Shoaib Ahmad Shah - , and
Sumaira Naeem
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In this study, a novel approach leveraging machine learning (ML) techniques for the design and screening of polymers with high melting points is introduced. More than 40 ML models are trained for the prediction of the melting point. One best model is selected for further analysis. 10,000 polymers are generated using an automatic approach. The generated database of polymers is visualized and analyzed to find the hidden trends. Synthetic feasibility assessment is conducted to prioritize candidate polymers for future experimental work. Chemical similarity of chosen polymers is analyzed using cluster analysis and a heatmap. This research contributes to the advancement of polymer design methodologies, offering insights into the development of heat-resistant polymers for a wide range of industrial applications.
Preparation, Isolation, and Structural Characterization of Lewis Base Iminium Salts of 1,8-Diazabicyclo[5.4.0]undec-7-ene and Their Application as Green Reagents in an Aqueous Medium
Swathi Thangalipalli - ,
Siddaramagoud Bandalla - ,
Nagaraju Kerru - ,
Jhansi Rani Vadala - ,
Chandra Sekhar Vasam - ,
Chandra Kiran Neella *- , and
Sreekantha B. Jonnalagadda *
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We report a state-of-the-art synthesis and isolation procedure for 13 Lewis base iminium salts (LBI) of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), confirming their structures meticulously by different spectral data. The LBIs are distinct from their parent compound (DBU), which provides emphatic support in favor of LBI formation in various DBU-catalyzed reactions. Density functional theory studies of N-sulfonyl LBI of DBU have given new insight into alternate iminium salts, offering a new opportunity for further investigation. We describe the applications of three LBIs as direct reagents for base-free functionalization, broadening their scope as eco-friendly reagents in aquatic media. The Lewis base is recoverable and reusable to prepare the LBI after the reaction. We also document the influence of the N substituent on the chemical shift of these iminium salts.
Acute Ecotoxicity and Bioconcentration Tests for Se(IV) in Nile tilapia (Oreochromis niloticus)
Pedro Henrique da Costa - ,
Nathalia dos Santos Ferreira - ,
Ana Rita de Araujo Nogueira - ,
Eduardo Bessa Azevedo - , and
Mario Henrique Gonzalez *
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Selenium is one of the most important trace element micronutrients for the global biota, mainly due to its role in protecting against oxidative stress. However, this element can become toxic when present at concentrations slightly higher than those needed for metabolic purposes. It can be transferred through the food chain toward higher trophic levels, with bioaccumulation and biomagnification leading to possible toxicity. This study investigates the bioconcentration and toxicity potential of Se(IV) in Nile tilapia (Oreochromis niloticus). After 7 days of exposure, Se concentrations in the fish tissues were in the order: liver ≫ stomach > gills > muscle. In bioconcentration tests, the uptake constant (ka) ranged from 0.34 to 4.68 mL g–1 d–1, while the clearance rate constant (kd) ranged from 0.12 to 0.36 d–1. The tissues presented high bioconcentration factors (BCF) ranging from 2.67 to 12.73, demonstrating the ability of Se(IV) to concentrate in muscle, gills, and stomach. Although the data for the liver could not be fitted by the model used, the measured Se(IV) concentrations were approximately six times higher than those found for the stomach, indicating that the ka, kd, and BCF values were very high. Estimated LC50 values lower than 10 mg L–1 suggested that Se(IV) could be considered very toxic to the fish.
l-Cysteine-Modified Carbon Dots Derived from Hibiscus rosa-sinensis for Thiram Pesticides Identification on Edible Perilla Leaves
Tanima Bhattacharya - ,
Rahul Joshi - ,
Lemma Teshome Tufa - ,
Mahendra Goddati - ,
Jaebeom Lee - ,
Ameeta Tewari - , and
Byoung-Kwan Cho *
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In this work, environmentally friendly fluorescent carbon dots (C-dots) were developed for the purpose of thiram identification in the leaves of perilla plants. Powdered plant petals from Hibiscus rosa-sinensis were hydrothermally combined to create C-dots. Analytical techniques, such as scanning electron microscopy, energy dispersive X-ray spectroscopy, high resolution transmission electron microscopy, Raman spectroscopy, ultraviolet spectroscopy, Fourier transmission infrared spectroscopy, and photoluminescence were employed to examine the properties of C-dots. To enhance their functionality, an l-cysteine dopant was added to the C-dots. Since this process produces highly soluble C-dots in water, it is simple, inexpensive, and safe. The excitation process and the size of the blue luminescent C-dots both affect their photoluminescent activity. Furthermore, thiram in aqueous solutions was effectively identified by using the generated C-dots. Additionally, the ImageJ program was used to measure the colors red, green, and blue. High-resolution TEM (HR-TEM) revealed that the l-cysteine-doped carbon dots had an average particle size of 2.208 nm. Additionally, the lattice fringes observed in the HRTEM image showed a d-spacing of around 0.285 nm, which nearly corresponds to the (100) lattice plane of graphitic carbon. A Raman spectrum study was also performed to investigate the relationship between carbon dots and pesticides in the actual samples. In the end, thiram levels in perilla leaves with nondoped and doped C-dots could be distinguished with 100% accuracy using the constructed partial least-squares discriminant analysis machine learning model. The information gathered therefore demonstrated that the synthetic C-dots successfully and efficiently provide rapid and sensitive detection of hazardous pesticides in edible plant products.
Effect of Acetonitrile on the Conformation of Bovine Serum Albumin
Samal Kaumbekova - ,
Masatake Sugita - ,
Naoya Sakaguchi - ,
Yuta Takahashi - ,
Akira Sadakane - , and
Masakazu Umezawa *
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The use of organic solvents in drug delivery systems (DDSs) either to produce albumin nanoparticles or to manipulate the binding of target molecules to albumin, a promising nanocarrier material, presents challenges due to the conformational changes induced in the protein. In this study, we investigated the alterations in the conformation of bovine serum albumin (BSA) caused by acetonitrile (ACN) in aqueous solution by using a combination of spectroscopic analysis and molecular dynamics (MD) simulations. Ultraviolet (UV) absorption, fluorescence, and infrared (IR) absorption spectroscopy were used to analyze the BSA conformation in the solutions containing 0–60 vol % ACN. Additionally, MD simulations were conducted to elucidate the interactions between BSA and solvent components, focusing on the structural changes in the hydrophobic pocket with Trp residues of the albumin. Increasing the ACN concentration leads to significant changes in the BSA conformation, as evidenced by shifts in UV fluorescence wavelength, decreased intensity, and alterations in IR absorption bands. Furthermore, the formation of protein aggregates was observed at high ACN concentration (30 vol % ACN), shown by increased hydrodynamic diameter distribution. MD simulations further demonstrate that the presence of ACN molecules near the hydrophobic pocket with the Trp-213 residue increases the fluctuations in the positions of amino acids observed near the hydrophobic pocket with Trp-213. Moreover, the intrusion of water molecules into the hydrophobic pocket under 60% ACN conditions with highly decreased solvent polarity was correlated with the changes in the BSA secondary structure. These findings enhance our understanding of how solvent polarity affects the albumin conformation, which is crucial for optimizing albumin-based DDS applications.
Heterostructured S-Scheme BiOBr/Cu2O Nanocomposite for Photocatalytic Degradation of Glyphosate
Albert Gonzalez - ,
Abelline Fionah - ,
Gbemisola J. Bamiduro - , and
Elsayed M. Zahran *
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Metal oxide semiconductor-activated photocatalysis has become a promising sustainable technology for the mitigation of emerging organic pollutants. The rational design of a photocatalyst heterojunction allows the degradation of a broad range of organic contaminants. Herein, we optimized hydrothermal approaches for the facial synthesis of well-defined BiOBr/Cu2O heterojunction photocatalysts. Tuning the synthesis condition enhanced the interfacing of BiOBr and Cu2O nanostructures in the heterojunction photocatalyst, as confirmed by STEM, TEM, XPS, XRD, and BET analysis. The optimized BiOBr/Cu2O heterostructured photocatalyst demonstrated substantial activity in the degradation of both anionic and cationic dyes compared to the individual components. The enhanced nanocomposite exhibited complete degradation of glyphosate in 10 min of light irradiation and demonstrated high stability after five photocatalytic cycles. Our mechanistic and photoelectrochemical studies suggest that establishing an S-scheme heterojunction between BiOBr and Cu2O enhances the separation of photogenerated charge carriers and expands the redox potentials of the nanocomposite to allow high catalytic efficiency. These findings indicate that tuning the design of metal oxide heterojunctions promises applications in the remediation of a wide range of organic contaminants.
Simulation Study on the Stabilization Control Performance of Low-Calorific-Value Waste Combustion in Waste Incinerators
Qian Wang - ,
Dehong Gong *- ,
Zhengguang Huang - ,
Changyang Peng - ,
Jiandong Chen - ,
Jie Luo - ,
Jiangdong Zhu - , and
Qingling Luo
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To address the instability of low-calorific-value waste incineration processes and suppress the generation of toxic dioxins, this study examines a 600 t/day waste incineration furnace as a case study. Numerical simulations of the incineration process were conducted by using bed calculation software FLIC and Fluent. A waste incineration cleanliness index was defined, and the impact of the reduced calorific value of the incoming waste on the temperature distribution within the incineration furnace was explored. The effectiveness of biomass steady combustion was compared to that of natural gas steady combustion, leading to the development of a control model for biomass steady combustion of low-calorific-value waste. The results indicate that a decrease in the calorific value of incoming waste reduces the cleanliness index; when the calorific value is 4739 kJ/kg, the cleanliness index drops to 0.96. The residence time of flue gas in the high-temperature zone of the first flue duct is less than 2 s, which is insufficient to effectively suppress dioxin formation. Therefore, steady combustion control measures are necessary. Both biomass and natural gas steady combustion can effectively increase the temperature of the incineration furnace; however, biomass, as a carbon-free energy source, significantly reduces carbon emissions compared with natural gas. A biomass-mixed control model for steady combustion of low-calorific-value waste was constructed and validated, achieving precise residence times in the high-temperature zones of 2.18 and 2.11 s, both exceeding 2 s, thereby achieving the desired control effect.
Progress in the Application of Multifunctional Composite Hydrogels in Promoting Tissue Repair
Yuan Hui - ,
Xuexuan Zheng - ,
Ziling Zheng - ,
Chuling Wu - ,
Yan Hao *- , and
Bin Zhou *
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Tissue repair is an extremely complex process, and effectively promoting tissue regeneration remains a significant clinical challenge. Hydrogel materials, which exhibit physical properties closely resembling those of living tissues, including high water content, oxygen permeability, and softness, have the potential to revolutionize the field of tissue repair. However, the presence of various complex conditions, such as infection, ischemia, and hypoxia in tissue defects, means that hydrogels with simple structures and functions are often insufficient to meet the diverse needs of tissue repair. Researchers have focused on integrating multiple drugs, nanomaterials, bioactive substances, and stem cells into hydrogel matrices to develop novel multifunctional composite hydrogels for addressing these challenges, which have superior antibacterial properties, hemostatic abilities, self-healing capacities, and excellent mechanical properties. These composite hydrogels are designed to enhance tissue repair and have become an important direction in the current research. This review provides a comprehensive review of the recent advances in the application of multifunctional composite hydrogels in promoting tissue repair, including drug-loaded hydrogels, nanomaterial composite hydrogels, bioactive substance composite hydrogels, and stem cell composite hydrogels.
November 20, 2024
Printed Potentiometric Ammonium Sensors for Agriculture Applications
Anju Toor *- ,
Payton Goodrich - ,
Tyler L. Anthony - ,
Claire Beckstoffer - ,
Haeshini Jegan - ,
Whendee L. Silver - , and
Ana Claudia Arias
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Ammonium (NH4+) concentration is critical to both nutrient availability and nitrogen (N) loss in soil ecosystems but can be highly variable across spatial and temporal scales. For this reason, effectively informing agricultural practices such as fertilizer management and understanding of mechanisms of soil N loss require sensor technologies to monitor ammonium concentrations in real time. Our work investigates the performance of fully printed ammonium ion-selective sensors used in diverse soil environments. Ammonium sensors consisting of a printed ammonium ion-selective electrode and a printed Ag/AgCl reference were fabricated and characterized in aqueous solutions and three different soil types (sand, peat, and clay) under the range of ion concentrations likely to be present in soil (0.01–100 mM). The response of ammonium sensors was further evaluated under variable gravimetric moisture content in the soil to reflect their reliability under field conditions. Ammonium sensors demonstrated a sensitivity of 53.6 ± 5.1 mV/decade when tested in aqueous solution, and a sensitivity of 55.7 ± 11 mV/dec, 57.5 ± 4.1 mV/dec, and 43.7 ± 4 mV/dec was measured in sand, clay, and peat soils, respectively.
Comparison of Cell-Penetrating and Fusogenic TAT-HA2 Peptide Performance in Peptideplex, Multicomponent, and Conjugate siRNA Delivery Systems
Metin Uz *- ,
Volga Bulmus - , and
Sacide Alsoy Altinkaya
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In this study, the performance of the cell-penetrating and fusogenic peptide, TAT-HA2, which consists of a cell-permeable HIV trans-activator of transcription (TAT) protein transduction domain and a pH-responsive influenza A virus hemagglutinin protein (HA2) domain, was comparatively evaluated for the first time in peptideplex, multicomponent, and conjugate siRNA delivery systems. TAT-HA2 in all three systems protected siRNA from degradation, except in the conjugate system with a low Peptide/siRNA ratio. The synergistic effect of different peptide domains enhanced the transfection efficiency of multicomponent and conjugate systems compared to that of peptideplexes, which was attributed to the surface configuration of TAT-HA2 peptides depending on the nature of attachment. Particularly, the multicomponent system showed better cellular uptake and endosomal escape than the peptideplexes, resulting in enhanced siRNA delivery in the cytoplasm. In addition, the presence of cleavable disulfide bonds in multicomponent and conjugate systems promoted the effective siRNA delivery in the cytoplasm, resulting in improved gene silencing activity. The multicomponent system reduced the level of luciferase expression in SKOV3 cells to 45% (±4). In contrast, the conjugate system and the commercially available siRNA transfection agent, Lipofectamine RNAiMax, caused luciferase suppression down to 55% (±2) at a siRNA dose of 100 nM. For the same dose, the peptideplex system could only reduce the luciferase expression to 65% (±5). None of the developed systems showed significant toxicity at any dose. Overall, the TAT-HA2 peptide is promising as a siRNA delivery vector; however, its performance depends on the nature of attachment and, as a result, its surface configuration on the developed delivery system.
Laser-Induced Nanostructured Si and SiGe Layers for Enhanced Optical and Thermoelectric Performance
Joumana El-Rifai *- ,
Eliane Bsaibess - ,
Stavros Christopoulos - ,
Fabien Giovannelli - ,
Ahmed Slimani - , and
Valerie Laux-Le Guyon
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We investigate a method for fabricating layers that exhibit both high optical absorption and promising thermoelectric properties. Using plasma-enhanced chemical vapor deposition (PECVD), amorphous Si and Si72Ge28 layers are deposited on glass substrates and subsequently processed via laser annealing to achieve nanostructured layers. Our results show that a single laser annealing pulse at 40 mJ yields the highest power factor, approximately 90 μW/m·K2. Additionally, we observe a maximum absorbance enhancement factor of 60 times in the spectral region near 880 nm for samples treated with a single pulse of 60 mJ compared to untreated samples. The effects of laser energy, the number of pulses, and material choice are further discussed.
Clean and Efficient Green Protocol of N,N′-Bis(2-(arylazo)-2-(aroyl)vinyl)ethane-1,2-diamines in Aqueous Medium without Catalyst: Synthesis and Photophysical Characterization
Abdulrahman M. Alazemi *- ,
Kamal M. Dawood *- ,
Hamad M. Al-Matar - , and
Wael M. Tohamy
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An interesting platform for the construction of novel N,N′-bis(2-(arylazo)-2-(aroyl)vinyl)ethane-1,2-diamines is reported in this work. These bis-arylazo compounds were assembled based on the reaction of ethylenediamine with various 2-arylhydrazono-3-oxopropanals in aqueous conditions under both conventional stirring and microwave conditions at ambient temperature. The factors affecting the optimization conditions were intensively practiced. The structures of the new products were established from their spectroscopic analyses and X-ray single crystals. The photophysical behavior of the bis-arylazo derivatives was examined. The UV–vis spectra showed maximum absorption band in the range of 348–383 nm with molar extinction coefficients ranging from 0.89 × 104 to 4.02 × 104 M–1 cm–1. The highest molar absorptivity coefficient (∼45 × 103 M–1 cm–1) was observed in CHCl3 solvent. The fluorescence properties showed that some compounds were interesting fluorophore materials with high Stokes shifts. The photoluminescence study of some compounds was promising, with maximal emission peaks ranging between 417–436 nm.
Multistage Template-Oriented Design and Tailoring of the Hierarchical Porous Biocarbon Materials for High-Performance Supercapacitors
Guimei Jin - ,
Qihang Zhou *- ,
Zhiyuan Duan - ,
Kaiyuan Shen - ,
Zhiwei Dong - ,
Shukang Deng - , and
Peizhi Yang
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Interfacial regulation is crucial for the enhancement of the specific surface area and supercapacitive performance in porous carbon materials. However, traditional porous carbon obtained through potassium hydroxide activation is confronted with a complicated preparation process. Herein, hierarchical porous biocarbons (HPBC) were facilely prepared by using the multiscale template method and wheat flour as a precursor without any activation. A spherical SiO2 template and wheat flour can be closely combined by gelatinization so as to effectively confine and spatially orient carbon materials. Benefiting from the hierarchical porous structure achieved through the use of templates at different sizes, HPBC-3 has the best electrochemical performance of 223.6 F·g–1 at 1 A·g–1. Moreover, the assembled HPBC-3//HPBC-3 symmetrical supercapacitor demonstrates a remarkable energy density of 15.6 W h·kg–1 and exhibits exceptional cycling performance with a capacitance retention rate of 106% after 5000 cycles. The results fully demonstrate the promising application of the obtained hierarchical porous carbon in supercapacitors.
Novel Nanocomposite of Carbonized Chitosan-Zinc Oxide-Magnetite for Adsorption of Toxic Elements from Aqueous Solutions
Dalia A. Ali *- ,
Ganna G. Ismail - ,
Ahmed I. Osman *- ,
Salwa B. Alreshaidan - , and
Ahmed S. Al-Fatesh
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Herein, a novel nanocomposite (carbonized chitosan-zinc oxide-magnetite, CCZF) was developed to effectively remove toxic elements in water remediation. Combining the high adsorption capacities of chitosan with the magnetic properties of magnetite and the chemical stability of zinc oxide, the combination of these unique properties makes it an efficient and versatile material that offers a sustainable solution for water purification. The (CCZF) nanocomposite was synthesized through the coprecipitation method and characterized using various techniques, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer–Emmett–Teller (BET) analysis, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and zeta potential analysis. The results showed impressive maximum adsorption capacities of 891.34 mg/g for Ni2+, 1269.35 mg/g for Co2+, and 1502.67 mg/g for Cu2+, fitting well with a modified Langmuir isotherm model. The adsorption process was spontaneous and endothermic, characterized by low positive enthalpy (ΔH) values ranging from 10.95 to 34.9 kJ/mol, indicative of the physical adsorption mechanism. Additionally, the nanocomposite demonstrated good reusability over multiple adsorption and desorption cycles. This research highlights the potential of the (CCZF) nanocomposite as a highly efficient, reusable adsorbent for the removal of toxic elements from aqueous solutions, contributing significantly to environmental remediation efforts and pollution control.
Flowable Oxygen-Release Hydrogel Inhibits Bacteria and Treats Periodontitis
Feng Wang - ,
Shengnan Wei - ,
Jingya He - ,
Aili Xing - ,
Yuan Zhang - ,
Zhongrui Li - ,
Xiangxiang Lu - ,
Bin Zhao *- , and
Bin Sun *
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Periodontitis, the chronic inflammation of the periodontal tissues caused by bacteria in plaque, is the leading cause of tooth loss in adults in the world. Currently, periodontitis is effectively treated with mechanical cleaning and the use of antibiotics. However, these treatments only temporarily remove plaque, which can rapidly proliferate and multiply in periodontal pockets over time. Although antibiotics have positive antimicrobial effects, their long-term use increases the risk of the emergence of drug-resistant strains. The emergence of resistant strains reduces the effectiveness of periodontitis treatment and makes the disease more difficult to control. Herein, this paper reports the development of an injectable self-oxygenating composite hydrogel for periodontal therapy, which was produced by loading CaO2 nanoparticles and ascorbic acid into an injectable alginate hydrogel. CaO2 can improve the periodontal pocket microenvironment by reacting with water to generate oxygen, calcium ions can be used as a bone regeneration material, and ascorbic acid protects cells. The authors further showed that the composite hydrogel inhibited growth and colonization of anaerobic bacteria, reduced the degree of inflammation, and promoted alveolar bone regeneration. In conclusion, these findings suggest that the composite hydrogel can be used as a biocompatible, convenient, and effective method for periodontitis treatment.
Characterization of a New Hybrid Compound (C3H8N6)2ZnCl4·2Cl: X-ray Structure, Hirshfeld Surface, Vibrational, Thermal Stability, Dielectric Relaxation, and Electrical Conductivity
Sahar Zaghden - ,
Hadhemi Ben Attia - ,
Mohammed S. M. Abdelbaky - ,
Abderrazek Oueslati - ,
Santiago García-Granda - ,
Mohamed Dammak *- , and
Lilia Ktari
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A novel organic–inorganic material (C3H8N6)2ZnCl4·2Cl was synthesized via a slow evaporation approach and subjected to extensive characterization. Techniques involving X-ray diffraction, SEM/EDX, Hirshfeld surface examination, IR/Raman spectroscopy, thermal behavior (TG/DTG/SDTA and DSC), and electric and dielectric studies were applied. Examination of the crystal structure reveals that the synthesized material adopts a monoclinic system, particularly belonging to the P21/c space group with unit cell parameters a = 11.7274(3) Å, b = 6.2155(2) Å, c = 25.7877(8) Å, β = 94.27(1)°, V = 1874.50(4) Å3, and Z = 4. Purity confirmation was established via powder X-ray diffraction analysis. Composition verification was conducted using semiquantitative EDXS analysis. The asymmetric unit comprises isolated tetrachlorozincate [ZnCl4]2– anions, two (C3H8N6)2+ organic cations, and two free chlorine atoms, forming a 0D anionic network. N–H···Cl and N–H···N hydrogen bonding combined to form a 2D hydrogen-bonded network, maintaining crystal stability. Hirshfeld surface analysis elucidated intermolecular interactions, supported by 2D fingerprint plots. IR and Raman spectra analysis corroborated compound characteristics at room temperature. Thermal analysis revealed two phase transitions at 343 and 358 K, consistent with dielectric studies. Impedance spectroscopy highlighted the compound’s electrical properties, confirming thermal transitions. Conductivity studies exhibited an Arrhenius behavior. Frequency-dependent dielectric constant variations and modulus studies underscored grain and grain boundary effects, confirming the effective protonic conduction in the material.
Silk Fibroin Nanoparticles as a Drug Delivery System of 3,3′-Diindolylmethane with Potential Antiobesogenic Activity
Calef Sánchez-Trasviña - ,
Helen Y. Lorenzo-Anota - ,
Aleyda M. Escobar-Fernández - ,
David Lezama-Aguilar - ,
Adriana Morales-Martínez - ,
Ana Vélez-Barceló - ,
Jorge Benavides - ,
Omar Lozano - ,
Marco Rito-Palomares - , and
Karla Mayolo-Deloisa *
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Obesity is a global disease characterized by excessive lipid accumulation in the adipose tissue. There is an urgent need to explore alternative compounds to treat obesity. Low-molecular-weight compounds from plants, like 3,3′-diindolylmethane (DIM), are emerging as potential alternatives for obesity treatment. In this work, DIM is encapsulated into silk fibroin nanoparticles (SFNP) to evaluate the antiobesogenic potential. The obtained spherical-like SFNPs have a particle size between 165 and 200 nm, a polydispersity index between 0.11 and 0.15, and a zeta potential from −27 to −37 mV. DIM does not modify the nanoparticle shape but changes the secondary structure of fibroin and generates smaller nanoparticles (145 nm). DIM-loaded SFNP (SFNP-DIM) enhance their antioxidant capacity by 4.4-fold compared to SFNP. SFNP-DIM does not show cytotoxicity on white-like adipocytes, unlike 3T3-L1 preadipocytes, where cell viability decreased in a concentration-dependent manner. The SFNP-DIM treatment (5 μM, 0.03 mg SFNP mL–1) does not modify the morphology of white-like adipocytes. It produces an apparent augmentation in the size and number of intracellular lipid droplets and increases by 2.18 ± 0.4-fold of triglyceride content. These findings demonstrated that SFNPs could be a potential delivery system of DIM, suggesting a potential therapeutic agent for treating obesity.
Chemical Resistance of Modified Wood Veneers in Sustainable Load Bearing Elements
Sebastian Wurm - ,
Alexa Scheer - ,
Georg Baumann - ,
Markus Wagner - ,
Kevin Vitzthum - ,
Stefan Spirk *- , and
Florian Feist *
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In the pursuit of sustainable engineering solutions, material selection is increasingly directed toward resources that offer functional efficacy, economic feasibility, and minimal environmental impact. To replace environmentally damaging materials like aluminum with more sustainable alternatives like wood-based materials, it is essential to improve the durability and longevity of wood. This study explores the potential suitability of modified veneers as an outer protective layer for unmodified wooden load-bearing elements, providing a cost-effective and resource-efficient alternative to bulk modification. Unmodified, acetylated, furfurylated, and physically densified birch rotary-cut wood veneers were exposed to liquid chemical reagents (acids, base, solvents, and water) and characterized thereafter in tensile tests. The chemical resistance was evaluated based on the deterioration of tensile strength. Additionally, infinite focus microscopy, infrared spectroscopy, and contact angle measurements were performed to track morphological and chemical changes in the veneers. The results demonstrated that acetylation and furfurylation significantly enhanced chemical resistance against the tested reagents.
Nonlinear van’t Hoff Behavior in the Interaction of Two Water-Soluble Porphyrins with Bovine Serum Albumin (BSA)
Fabio C. Bezerra - ,
Ernanni D. Vieira - ,
Pablo J. Gonçalves *- , and
Iouri E. Borissevitch *
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Thermodynamic analysis of the binding process of water-soluble negatively charged meso-tetrakis(p-sulfonatophenyl) (TPPS4) and positively charged meso-tetrakis(4-methylpyridyl) (TMPyP) porphyrins with bovine serum albumin (BSA) at different temperatures was carried out based on the data of BSA quenching fluorescence by porphyrins. The comparison of binding constants (Kb) shows that negatively charged TPPS4 possesses higher affinity to BSA than positively charged TMPyP. Thermodynamic characteristics of the binding process were obtained in accordance with the van’t Hoff theory by processing nonlinear dependences of ln Kb on inverse absolute temperature within the framework of two models: taking into account the dependence or independence of the change in the standard heat capacity (ΔC0) on temperature. A comparison of thermodynamic characteristics with the data obtained from the Förster fluorescence quenching theory and with literature data leads to the conclusion that TPPS4 is bound to the Sudlow I site (subdomain IIA), while TMPyP is bound to the Heme site (between the subdomains IA and IB). The analysis of ΔC0 changes with temperature demonstrates that binding of TPPS4 promotes hydration of nonpolar groups in the protein, which increases with the increase of temperature, while binding of TMPyP decreases the hydration of polar groups of the protein, the effect increasing with rising temperature. The obtained information may be useful for elucidating the mechanisms of interaction of porphyrins with albumins and the effect of this interaction upon the effectiveness of porphyrins in photodynamic therapy and in fluorescence diagnostics of cancer.
Correction to “Does the Red Shift in UV–Vis Spectra Really Provide a Sensing Option for Detection of N-Nitrosamines Using Metalloporphyrins?”
Marko Trampuž - ,
Mateja Žnidarič - ,
Fabrice Gallou - , and
Zdenko Časar *
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November 19, 2024
Synergistic Effect in Hybrid Plasmonic Conjugates for Photothermal Applications
Viktoriia Savchuk *- ,
Ruizheng Wang - ,
Lyle Small - , and
Anatoliy Pinchuk
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Photothermal conversion efficiency (η) plays a crucial role in selecting suitable gold nanoparticles for photothermal therapeutic applications. The photothermal efficiency depends on the material used for the nanoparticles as well as their various parameters, such as size and shape. By maximizing the light-to-heat conversion efficiency (η), one can reduce the concentration of nanoparticle drugs for photothermal cancer treatment and apply lower laser power to irradiate the tumor. In our study, we explored a new hybrid plasmonic conjugate for theranostic (therapy + diagnostic) applications. We conjugated PEG-functionalized 20 nm gold nanospheres with cyanine IR dyes via a PEG linker. The resulting conjugates exhibited significantly enhanced photothermal properties compared with bare nanoparticles. We experimentally showed that a proposed new hybrid plasmonic conjugate can achieve almost four times larger conversion efficiency (47.7%) than 20 nm gold nanospheres (12%). The enhanced photothermal properties of these gold conjugates can provide the required temperature for the photothermal treatment of cancer cells with lower concentrations of gold nanoparticles injected in the body as well as with lower applied incident laser power density. Moreover, the improved photothermal properties of the conjugates can be explained by a synergistic effect that has not been observed in the past. This effect results from the coupling between the metal nanosphere and the organic dye.
Methane Hydrate-in-Oil Systems in the Presence of Natural Amino Acid-Equilibrium Phase Condition Measurements
Abdulrab Abdulwahab Almashwali - ,
Bhajan Lal *- , and
Siak Foo Khor
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This experimental study reports the thermodynamic influence of three different amino acids on methane hydrate in oil-dominated systems, namely, glycine, proline, and alanine. To thoroughly examine the effect of selected amino acids on methane (CH4) hydrate formation compared to the commercial inhibitor monoethylene glycol (MEG) in the presence of oil, the hydrate liquid–vapor equilibrium (H-Lw-Lo-V) curve is used to measure amino acid aqueous solutions. All experiments are performed at a concentration of 10 wt % by using the isochoric T-cycle technique in a high-pressure reactor cell at the selected range of pressures with temperatures of 4.0–9.0 MPa and 276.5–286.0 K, respectively. Results show that all studied amino acids inhibit hydrate formation of methane; the inhibition trend shows as glycine > alanine > proline in both systems; in the brine water system, the inhibition performance was higher than in the pure water system due to the presence of NaCl. Glycine showed the highest inhibition strength in both systems with an average reduced temperature in pure and brine water of 0.92 and 1.75 K, respectively, at 10 wt %, making the inhibition performance of glycine comparable to the commercial inhibitor MEG. The inhibition effect is attributed to the amino acid’s hydrogen bonding energies and side group alkyl chain. Calculating the dissociation enthalpies of methane hydrates in the presence of amino acids using the Clausius–Clapeyron equation implies that the amino acids do not occupy the cage structures during methane hydrate formation.
Trifluoromethylative and Pentafluoroethylative Heterofunctionalization (C–O, C–S, and C–N) of Alkenes Using Visible Light Photocatalysis
Ye Rin Choi - ,
Seongeun Kang - ,
Junyeon Hwang - ,
Hongchan An *- , and
Ki Bum Hong *
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A mild and general method for photoredox-catalyzed trifluoromethylative and pentafluoroethylative heterofunctionalization of alkenes is proposed. In this reaction, the Togni reagent serves as a CF3- or CF2CF3-radical source for the regioselective formation of the C–CF3 and C–CF2CF3 bonds from alkenes, and additional nucleophiles (O, S, N) provide C–O, C–S, and C–N bonds, respectively. These reactions provide a common gateway to access the fluoroalkylative heterofunctionalization of alkenes.
Laser-Induced Graphene for Electrochemical Sensing of Antioxidants in Biodiesel
Daniel R. Sevene - ,
Tiago A. Matias *- ,
Diele A. G. Araújo - ,
Nélio I. G. Inoque - ,
Marcelo Nakamura - ,
Thiago R.L.C. Paixão - , and
Rodrigo A. A. Muñoz *
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Synthetic antioxidants are often introduced to biodiesel to increase its oxidative stability, and tert-butyl hydroquinone (TBHQ) has been selected due to its high efficiency for this purpose. The monitoring of antioxidants in biodiesel therefore provides information on the oxidative stability of biodiesels. Herein, a laser-induced graphene (LIG) electrode is introduced as a new sensor for detecting tert-butyl hydroquinone (TBHQ) in biodiesel samples. An infrared CO2 laser was applied for LIG formation from the pyrolysis of polyimide (Kapton). Based on the voltammetric profile of a reversible redox probe, the fabrication of LIG electrodes was set using 1.0 W power and 40 mm s–1 speed, which presented an electroactive area of 0.26 cm2 (higher than the geometric area of 0.196 cm2). Importantly, lower engraving speed resulted in higher electroactive area, probably due to a more efficient graphene formation. Scanning-electron microscopy and Raman spectroscopy confirmed the creation of porous graphene induced by laser. The sensing platform enabled the differential-pulse voltammetric determination of TBHQ from 5 and 450 μmol L–1. The values of detection limit (LOD) of 2 μmol L–1 and RSD (relative standard deviation) of 2.5% (n = 10, 10 μmol L–1 of TBHQ) were obtained. The analysis of spiked biodiesel samples revealed recoveries from 88 to 106%. Also, the method provides a satisfactory selectivity, as it is free of interference from metallic ions (Fe3+, Mn2+, Cr2+, Zn2+, Pb2+, and Cu2+) commonly presented in the biofuel. These results show that LIG electrodes can be a new electroanalytical tool for detecting and quantifying TBHQ in biodiesel.
Attenuated Total Reflectance Crystal of Silicon for Rapid Nitrate Sensing Combining Mid-Infrared Spectroscopy
Liping Xu - ,
Fei Ma - ,
Jianmin Zhou - , and
Changwen Du *
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Rapid detection of NO3–-N is critical to address the challenges of food security, environmental degradation, and climate change. Conventional methods for sensing NO3–-N in water demand pretreatments and chemical reagents, which are time- and cost-consuming. Consequently, Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy has been well applied for the determination of NO3–-N. However, the conventional ATR crystals, i.e., zinc selenide (ZnSe) and diamond, showed a weakness in duration or cost since the ZnSe material was relatively soft and diamond was relatively expensive. In this study, comparing with ZnSe-ATR and diamond-ATR, a silicon-based ATR (Si-ATR) accessory was developed and used to explore the applicability and stability for sensing NO3–-N combining mathematic algorithms. It was found that partial least-squares regression (PLSR) showed a good performance comparing with the algorithms of principal component analysis (PCA) and linear regression (LR), and it was recommended for quantifying NO3–-N. For ZnSe-ATR, the residual prediction deviation (RPD) was more than 1.80, the determination coefficient (R2) was more than 0.7725, and the root-mean-square error (RMSE) was less than 2.73 mg L–1. For diamond-ATR, the RPD was more than 1.76, the R2 was more than 0.7309, and the RMSE was less than 8.22 mg L–1. For Si-ATR, the RPD was more than 1.42, the R2 was 0.5198, and the RMSE was less than 11.02 mg L–1. It was confirmed that all three types of ATR could be applied in the quantification of NO3–-N in water for high nitrate concentrations. However, for the quantification of low nitrate concentrations (0–1 mg L–1 NO3–-N), ZnSe-ATR and diamond-ATR acquired the same accuracy, while Si-ATR had a lower accuracy. The pretreatment of Si-ATR-based spectra using the deconvolution algorithm could improve the prediction accuracy compared to water deduction for predicting low NO3–-N. Furthermore, a Si-ATR accessory was developed using Si-ATR, which was reliable for NO3–-N concentration quantification in water with the advantage of its low cost and long durability. Totally, samples with high nitrate concentrations implied a more reliable prediction for all crystals, and comprehensively, ZnSe-ATR was recommended for sensing low nitrate concentrations; diamond-ATR was recommended for samples with strong acid or base corrosion; and for sensing relatively high nitrate concentrations, such as in natural water bodies, Si-ATR was more economical because of its low cost and relatively long use life.
Study for Hydrogen Migration Characteristics in the Elbow of a Hydrogen-Doped Natural Gas Pipeline under Normal Transport and Shutdown Conditions
Jiuqing Ban - ,
Li Zhou - ,
Yun Jiang - ,
Yan Wu - ,
Wei Yang - ,
Duo Chen - , and
Gang Liu *
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During the transportation of hydrogen-doped natural gas (HCNG), there is a risk of uneven distribution of hydrogen at the elbow, causing hydrogen damage to the pipeline. Therefore, based on the basic principles of computational fluid dynamics, this paper uses a hybrid model to describe the flow process of HCNG in an elbow. The results show that under normal transportation, the hydrogen volume fraction varies within 0.2% with the influence of pressure, flow velocity, temperature, hydrogen volume fraction, and undulating angle, and the uneven distribution of hydrogen in the elbow can be ignored. However, in the shutdown state, the hydrogen slip rate gradually slows down, the hydrogen volume fraction is distributed in a horizontal concentration gradient along the vertical direction, and it gradually accumulates at the height of the undulating tube. The difference in hydrogen volume fraction reaches 50%, and the stratification phenomenon is obvious.
High-Pressure Low-Temperature Study of LnCa4O(BO3)3 (Ln = Pr, Nd, Gd, Er, Tm)
Fatiha Azrour - ,
Romain Viennois - ,
Jérôme Long - ,
Dominique Granier - ,
Fapeng Yu - ,
Shujun Zhang - ,
Frederico Alabarse - ,
Mickael Beaudhuin - , and
Jérôme Rouquette *
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We investigated the site-disorder and thermal expansion of LnCa4O(BO3)3 (Ln = Pr, Nd, Gd, Er, Tm) through a single crystal structural study conducted between 100 and 300 K. Additionally, a high-pressure synchrotron X-ray diffraction study at low temperatures was conducted to determine the compressibility of both ordered and disordered prototype oxyborate lanthanides, specifically NdCa4O(BO3)3 and ErCa4O(BO3)3. The study revealed distinct behaviors consistent with their respective ionic radii. Furthermore, satellite reflections at 50 K, along with the onset of a triple a-parameter in the Nd crystal, indicate that the ground state of this extensively studied family may be different from what was previously reported.
Effect of Size-Controlled Nanofluid on Mechanical Properties, Microstructure, and Rheological Behavior of Cement Slurry for Oil Well Cementing
Ramaswamy Gautam - ,
Abhinav Hazra - ,
Prashant Faujdar - ,
Suvendu Sen - ,
Bibhash Chandra Mishra - ,
Tushar Sharma *- , and
Shailesh Kumar
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The optimal design of cement slurry by balancing various cement additives and cement is critical for effective oil well cementation job. However, given adverse circumstances of application, existing additives may not be sufficient to perform suitably in challenging conditions, leading to premature cement hydration, formation of microcracks, and gas channeling pathways. Thus, this study explores the use of a single-step silica nanofluid (NP size: 5–10, 90–100, and 250–300 nm and concentration: 1, 3, and 5 wt %) as an additive and explores its effect on thickening time, fluid loss, and rheological behavior of class G cement slurry at high-pressure and high-temperature (HPHT) conditions (135 °C and 3625 psi). The improvement in thickening time, fluid loss, and rheology of conventional slurry was greater for low NP size than the nanofluid of high NP size: the nanofluid size, e.g., 5–10 nm, and concentration (1 wt %) were found to accelerate the thickening time by 30–40% while reducing fluid loss from 38 mL (no silica, slurry CS) to 30 mL (with silica, slurry C1). The rheological behavior was studied via shear (viscosity) and dynamic (elastic moduli, G′) modes to evaluate the viscosity, hysteresis, and elastic response of slurry with and without nanofluid. The inclusion of nanofluid slightly reduced the slurry viscosity; however, all slurries exhibited shear thinning with superior fitting with the power law model. As compared to slurry CS, hysteresis of slurry C1 was least dependent on shear deformation, and thus, it showed that it almost matched viscosity profiles during loading and unloading cycles. The addition of silica was found to maintain the original properties of cement slurry, establishing that cement had not agglomerated, and no sedimentation was observed even at shear rates of 1000 s–1. The results of this study greatly promote the use of silica nanofluid as an important additive in class G cement for cementation operations, which is unlikely with a two-step nanofluid where nanoparticles are expensive, and upon mixing, they tend to agglomerate and make large size clusters.
Metal–Organic Frameworks (MOFs) and Their Composites for Oil/Water Separation
Abdullah M. Abudayyeh - ,
Lila A.M. Mahmoud - ,
Valeska P. Ting - , and
Sanjit Nayak *
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Contamination of water by oil-based pollutants is a major environmental problem because of its harmful impact on human life, marine life, and the environment. As a result, a wide range of materials are being investigated for the effective separation of oil from water. Among these materials, metal–organic frameworks (MOFs) and their composites have emerged as excellent candidates due to their ultraporous structures with high surface areas that can be engineered to achieve high selectivity for one of the phases in an oil/water mixture for efficient water filtration. However, the often nanocrystalline/microcrystalline form of MOFs combined with challenges of processability and poor stability in water has largely limited their use in industrial and environmental applications. Hence, considerable efforts have recently been made to improve the performance and stability of MOFs by introducing hydrophobic functional groups into the organic linkers and fabricating polymer-MOF composites to increase their stability and recyclability. In addition, the use of biobased or biodegradable MOF composites can be particularly useful for applications in natural environments. This Review presents recent advances in the field of hydrophobic MOFs and MOF-based composites studied for the separation of oil from oil/water mixtures, with an account of future challenges in this area.
Preparation and Biological Activity of Lignin–Silver Hybrid Nanoparticles
Dominik Maršík *- ,
Matěj Danda - ,
Jaroslav Otta - ,
Petter P. Thoresen - ,
Olga Mat́átková - ,
Ulrika Rova - ,
Paul Christakopoulos - ,
Leonidas Matsakas *- , and
Jan Masák
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Silver nanoparticles (AgNPs) are excellent antimicrobial agents and promising candidates for preventing or treating bacterial infections caused by antibiotic resistant strains. However, their increasing use in commercial products raises concerns about their environmental impact. In addition, traditional physicochemical approaches often involve harmful agents and excessive energy consumption, resulting in AgNPs with short-term colloidal stability and silver ion leaching. To address these issues, we designed stable hybrid lignin–silver nanoparticles (AgLigNPs) intended to effectively hit bacterial envelopes as a main antimicrobial target. The lignin nanoparticles (LigNPs), serving as a reducing and stabilizing agent for AgNPs, have a median size of 256 nm and a circularity of 0.985. These LigNPs were prepared using the dialysis solvent exchange method, producing spherical particles stable under alkaline conditions and featuring reducing groups oriented toward a wrinkled surface, facilitating AgNPs synthesis and attachment. Maximum accumulation of silver on the LigNP surface was observed at a mass reaction ratio mAg:mLig of 0.25, at pH 11. The AgLigNPs completely inhibited suspension growth and reduced biofilm development by 50% in three tested strains of Pseudomonas aeruginosa at a concentration of 80/9.5 (lignin/silver) mg L–1. Compared to unattached AgNPs, AgLigNPs required two to eight times lower silver concentrations to achieve complete inhibition. Additionally, our silver-containing nanosystems were effective against bacteria at safe concentrations in HEK-293 and HaCaT tissue cultures. Stability experiments revealed that the nanosystems tend to aggregate in media used for bacterial cell cultures but remain stable in media used for tissue cultures. In all tested media, the nanoparticles retained their integrity, and the presence of lignin facilitated the prevention of silver ions from leaching. Overall, our data demonstrate the suitability of AgLigNPs for further valorization in the biomedical sector.
Effect of Salt Stress on Botanical Characteristics of Some Table Beet (Beta vulgaris L.) Cultivars
Ayah T. Zaidalkilani - ,
Aman H. Al-Kaby - ,
Amira M. El-Emshaty *- ,
Sadeq K. Alhag - ,
Laila A. Al-Shuraym - ,
Zakaria A. Salih - ,
Amro Ahmed Taha - ,
Ammar M. Al-Farga - ,
Ashmawi E. Ashmawi - ,
Saleh A. Hamad - ,
Hany S. Abd El-Raouf - ,
Shahinaz E. Ahmed - ,
Ahmed M. El-Taher - ,
Moses V. M. Chamba *- , and
Taghreed A. Badawi
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Salinity inhibits the uptake of nitrogen, which slows down the growth and prevents plant reproduction. Certain ions, especially chloride, are poisonous to plants; when their concentration increases, the plant becomes poisoned and eventually perishes. The adaptability of several table beet cultivars (Beta vulgaris L.) to saline water irrigation creates new opportunities for extending beet production, increases the added economic value, and has a positive environmental impact. A pot experiment is carried out for two successive seasons, 2019/2020 and 2020/2021, to investigate the effect of irrigation with agriculture saline drainage water on the growth and biochemical traits of three selected cultivars (Detroit Dark Red, Red Ball, and Red Ace). Four levels of salinity are applied (1000, 2000, 3000, and 4000 ppm) along with tap water of 260 ppm salinity, which serves as the control. Detroit Dark Red beets show the best results among the other cultivars under consideration. Irrigation with the first level of saline water (1000 ppm) at both seasons of cultivation results in a significant increase rate in growth parameters (13–23%). The second level of salinity (2000 ppm) shows the maximum increase rate of some chemical constituents, such as ascorbic acid (16.26%), nitrogen (58.21%), phosphorus (11.94%), potassium (34.66%), and sodium (85.14%). The levels of total soluble solids (TSS), anthocyanins, proline, total sugars, water saturation deficit, and sodium increase significantly in proportion to saline water concentrations. The selected table beet mature leaves show slight variations in anatomical structure, especially in the B. vulgaris L. cv. Detroit Dark Red under the highest salinity concentration (4000 ppm) was less than that of the control and the other two cultivars. Other cultivars may be the subject in the near future to study the effect of their salinity tolerance with the aim of increasing productivity, enhancing their characteristics, and preserving the environment.
Quercetin and Astragaloside IV Mitigate the Developmental Abnormalities Induced by Gestational Exposure to Zinc Oxide Nanoparticles
Li Ji - ,
Qiuru Huang - ,
Yujuan Qi - ,
Zihan Wang - ,
Xiuwen Kong - ,
Xiaoqi Zhu - ,
Binbin Yang - ,
Jiaxin Li - ,
Xuxin He - ,
Xiaonan Deng - ,
Xinmeng Cheng - ,
Hao Yu - ,
Yi Shi - ,
Ziwen Lin - ,
Xinyuan Zhao *- ,
Xiaorong Wang *- , and
Jun Yu *
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Zinc oxide (ZnO) nanoparticles (NPs) are extensively utilized in the commercial and biomedical sectors, posing heightened risks of potential cytotoxicity through various mechanisms. Nonetheless, the regulatory framework governing the gestational toxicity of ZnO NPs and the corresponding intervention strategies remain largely obscure. In this study, using the Drosophila model, we observed that gestational exposure to ZnO NPs led to growth and developmental anomalies in a dose-dependent manner when compared with the control (no ZnO NP exposure). Subsequent dietary administration of Quercetin and Astragaloside IV resulted in effective mitigation of the developmental toxicity induced by exposure to ZnO NPs. Moreover, the latter also triggered activation of the ferroptosis pathway. The associated parameters were successfully ameliorated by the administration of Quercetin and Astragaloside IV. Notably, treatment with Ferrostatin-1 also alleviated developmental disorders arising from exposure to ZnO NPs. In conclusion, our investigation demonstrated that exposure to ZnO NPs during gestation interfered with growth and development via the ferroptosis pathway, underscoring the significance of dietary supplementation with Quercetin and Astragaloside IV for protection against developmental toxicity.
Catalytic Application of Biochar Functionalized Copper-l-histidine for the Chemo and Homoselective Conversion of Cyanides to Amides and Reduction of Nitroarenes to anilines
Mahrokh Farrokh - ,
Maryam Hajjami *- ,
Mohammad Ali Zolfigol *- , and
Sepideh Jalali-Mola
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In our study, we aimed to use olive pomace, food industry waste, as biomass to produce biochar nanoparticles. The surface of the biochar was functionalized with the l-histidine ligand, and then cupric acetate was added to prepare Cu-l-histidine@biochar as a final catalyst for the chemo- and homoselective synthesis of amide and aniline derivatives. To characterize the novel catalyst, we employed various techniques. Another notable feature of this catalyst is its reusability, which maintained significant efficiency even after multiple uses in reactions.
Detecting the Major Degradation Products of Phosphorothioate Oligonucleotides by Chemical Derivatization and Weak Anion Exchange Chromatography
Stilianos G. Roussis *- ,
Christopher M. Gabriel - ,
Andrew A. Rodriguez - , and
Claus Rentel
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Novel polar cysteine analogues have been synthesized for the derivatization of oligonucleotide depurination impurities that may be formed under acidic conditions. Depurination impurities belong to a group that includes deamination and phosphate diester impurities, which are similar in chemical structure to each other and the parent oligonucleotide, and thus coelute by most chromatographic separation methods. The polar cysteine analogues react with depurination impurities and enable their complete separation from the parent oligonucleotide by weak anion exchange (WAX) chromatography. Optimized conditions for the derivatization reaction and the WAX analysis are presented. The ability of the WAX method to chromatographically separate deamination and phosphate diester impurities is also demonstrated, and therefore, the combination of chemical derivatization and WAX chromatography permits detection and quantification of the three major degradation products of phosphorothioate (PS) oligonucleotides.
miR-210 Mediated Hypoxic Responses in Pancreatic Ductal Adenocarcinoma
Maria Mortoglou - ,
Mutian Lian - ,
Francesc Miralles - ,
D. Alwyn Dart - , and
Pinar Uysal-Onganer *
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Pancreatic ductal adenocarcinoma (PDAC) is one among the most lethal malignancies due to its aggressive behavior and resistance to conventional therapies. Hypoxia significantly contributes to cancer progression and therapeutic resistance of PDAC. microRNAs (miRNAs/miRs) have emerged as critical regulators of various biological processes. miR-210 is known as the “hypoxamir” due to its prominent role in cellular responses to hypoxia. In this study, we investigated the multifaceted role of miR-210 in PDAC using miR-210 knockout (KO) cellular models to elucidate its functions under hypoxic conditions. Hypoxia-inducible factor-1α (HIF1-α), a key transcription factor activated in response to low oxygen levels, upregulates miR-210. miR-210 maintains cancer stem cell (CSC) phenotypes and promotes epithelial–mesenchymal transition (EMT), which is essential for tumor initiation, metastasis, and therapeutic resistance. Our findings demonstrate that miR-210 regulates the expression of CSC markers, such as CD24, CD44, and CD133, and EMT markers, including E-cadherin, Vimentin, and Snail. Specifically, depletion of miR-210 reversed EMT and CSC marker expression levels in hypoxic Panc-1 and MiaPaCa-2 PDAC cells. These regulatory actions facilitate a more invasive and treatment-resistant PDAC phenotype. Understanding the regulatory network involving miR-210 under hypoxic conditions may reveal new therapeutic targets for combating PDAC and improving patient outcomes. Our data suggest that miR-210 is a critical regulator of HIF1-α expression, EMT, and the stemness of PDAC cells in hypoxic environments.
Machine Learning-Driven Methods for Nanobody Affinity Prediction
Hua Feng - ,
Xuefeng Sun - ,
Ning Li - ,
Qian Xu - ,
Qin Li - ,
Shenli Zhang - ,
Guangxu Xing - ,
Gaiping Zhang - , and
Fangyu Wang *
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Because of their high affinity, specificity, and environmental stability, nanobodies (Nbs) have continuously received attention from the field of biological research. However, it is tough work to obtain high-affinity Nbs using experimental methods. In the current study, 12 machine learning algorithms were compared in parallel to explore the potential patterns between Nb–ligand affinity and eight noncovalent interactions. After model comparison and optimization, four optimized models (SVMrB, RotFB, RFB, and C50B) and two stacked models (StackKNN and StackRF) based on nine uncorrelated (correlation coefficient <0.65) optimized models were selected. All the models showed an accuracy of around 0.70 and high specificity. Compared to the other models, RotFB and RFB were not capable of predicting nonaffinitive Nbs with lower precision (<0.44) but showed higher sensitivity at 0.6761 and 0.3521 and good model robustness (F1 score and MCC values). On the contrary, SVMrB, C50B, and StackKNN were able to effectively predict the future nonaffinitive Nbs (specificity >0.92) and reduce the number of true affinitive Nbs (precision >0.5). On the other hand, StackRF showed intermediate model performance. Furthermore, an in-depth feature analysis indicated that hydrogen bonding and aromatic-associated interactions were the key noncovalent interactions in determining Nb–ligand binding affinity. In summary, the current study provides, for the first time, a tool that can effectively predict whether there is an affinity between nanobodies and their intended ligands and explores the key factors that influence their affinity, which could improve the screening and design process of Nbs and accelerate the development of Nb drugs and applications.
November 18, 2024
Kinetics and Optimization Studies of Controlled 5-Fluorouracil Release from Graphene Oxide Incorporated Vegetable Oil-Based Polyurethane Composite Film
Ebru Kahraman *- ,
Tugba Hayri-Senel - , and
Gulhayat Nasun-Saygili
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The current study focuses on investigating the potential of produced graphene oxide (GO)/oil-based polyurethane composite films as a drug carrier for 5-fluorouracil (5-FU). Polyurethane was synthesized starting from blends of castor oil and sunflower oil-based glyceride, followed by GO and 5-FU anticancer drug bearing film production by solution casting. GO/PU composite film samples were characterized by FTIR, TGA and SEM analysis, confirming the PU production and distribution of 5-FU drug at a homogeneous level in GO/PU films. Experimental design studies were carried out to provide insight into the influence of GO incorporation, the amount of loaded drug, and the release medium pH value on 5-FU release behavior. The amount of 5-FU delivered from GO/PU composites displayed a tendency to increase at high GO ratios and high pH values, with the obtained maximum ratio of 91.4%. From release kinetics studies, the pH-sensitive behavior of GO/PU composites was observed following a Higuchi or zero-order kinetic model depending on the GO ratio, indicating a sustained release of the drug. The in vitro cytotoxicity effect of GO/PU film through 5-FU drug release was confirmed against the MCF-7 human breast cancer cell line, while good biocompatibility of the drug-free GO/PU film against the L-929 mouse fibroblast cell line was confirmed via MTT assay test. Overall, the findings support that produced GO/PU composites hold potential for clinical drug delivery applications as a 5-FU drug carrier.
Multi-Scale Temporal-Spatial Feature-Based Hybrid Deep Neural Network for Remaining Useful Life Prediction of Aero-Engine
Zhaofeng Liu - ,
Xiaoqing Zheng - ,
Anke Xue - , and
Ming Ge *
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Remaining useful life (RUL) prediction is crucial for simplifying maintenance procedures and extending the lifespan of aero-engines. Therefore, research on RUL prediction methods for aero-engines is increasingly gaining attention. In particular, some existing deep neural networks based on multiscale features extraction have achieved certain results in RUL predictions for aero-engines. However, these models often overlook two critical factors that affect RUL prediction performance: (i) different time series data points have varying importance for RUL prediction, and (ii) the connections and similarities between different sensor data in both directions. This paper aims to extract valuable multiscale features from raw monitoring data containing multiple sensor measurements, considering the aforementioned factors, and leverage these features to enhance RUL prediction results. To this end, we propose a novel deep neural network based on multiscale features extraction, named Multi-Scale Temporal-Spatial feature-based hybrid Deep neural Network (MSTSDN). We conduct experiments using two aero-engine data sets, namely C-MAPSS and N-CMAPSS, to evaluate RUL prediction performance of MSTSDN. Experimental results on C-MAPSS data set demonstrate that MSTSDN achieves more accurate and timely RUL predictions compared to 12 existing deep neural networks specifically designed for predicting RUL of aero-engine, especially under multiple operational conditions and fault modes. And experimental results on N-CMAPSS data set eventually indicate that MSTSDN can effectively track and fit with the actual RUL during the engine degradation phase.
Dynamic-Covalent Mesoporous Silica Nanohybrid with pH/ROS-Responsive Drug Release for Targeted Tumor Therapy
Yurong Leng - ,
Yanmei Wu - ,
Wenjing Xiao - ,
Xiaoquan Su - , and
Zhe Liu *
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Nanomedicine provides promising new methodologies for the treatment of tumors but still faces several limitations, including poor colloidal stability, uncontrollable drug release, and insufficient drug targeting. Herein, hyaluronic acid (HA) was used to modify the surface of mesoporous silica nanoparticles (MSNs) via a dynamic-covalent linker, phenylborate ester (PBAE), termed MA. The HA modifier provided enhanced colloidal stability to the hybrid nanoparticles. As expected, MA exhibited an improved biocompatibility and high potential for biomedical applications. Moreover, MA with a negatively charged surface effectively adsorbed the drug Doxorubicin (DOX) inside the carriers, ensuring minimal drug leakage. In an acidic and reactive oxygen species (ROS)-containing condition mimicking the tumor microenvironment, MA@DOX (MAD) continuously released its payloads, likely due to the cleavage of the pH/ROS-sensitive PBAE. Compared with free DOX, MAD had 2.2 times higher accessibility to tumor cells than free DOX. The favorable stability and cancer-selective drug release make this nanoformulation a promising platform for potent cancer treatment.
Synthesis of Bis-Thioacid Derivatives of Diarylethene and Their Photochromic Properties
Pramod Aryal - ,
Jonathan Bietsch - ,
Gowri Sankar Grandhi - ,
Richard Chen - ,
Surya B. Adhikari - ,
Ephraiem S. Sarabamoun - ,
Joshua J. Choi - , and
Guijun Wang *
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Diarylethenes (DAEs) are an important class of photoswitchable compounds that typically undergo reversible photochemical conversions between the open and closed cyclized forms upon treatment with UV light or visible light. In this study, we introduced thioacid functional groups to several photochromic dithienylethene (DTE) derivatives and established a method that can be used to prepare these photoswitchable thioacids. Four thioacid-functionalized diarylethene derivatives were synthesized through the activation of carboxylic acids with N-hydroxysuccinimide, followed by reactions with sodium hydrosulfide with yields over 90%. These derivatives exhibited reversible photoswitching and photochromic properties upon treatment with ultraviolet (UV) and visible lights. The thioacid groups on these compounds can act as reaction sites for attaching other desirable functionalities. The photochromic properties of these new derivatives were characterized by using ultraviolet–visible (UV–vis) spectroscopy. The photocyclizations of one of the derivatives and its potassium salt were also characterized by using nuclear magnetic resonance (NMR) spectroscopy. The anions of the thioacid formed water-soluble photochromic systems, and their applications as colorimetric sensors in agarose hydrogels were demonstrated.
Machine Learning Models for Efficient Property Prediction of ABX3 Materials: A High-Throughput Approach
Soundous Touati - ,
Ali Benghia - ,
Zoulikha Hebboul - ,
Ibn Khaldoun Lefkaier - ,
Mohammed Benali Kanoun - , and
Souraya Goumri-Said *
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Recently, ABX3 materials have garnered significant attention due to their diverse applications in photovoltaics, catalysis, and optoelectronics as well as their remarkable efficiency in energy conversion. However, progress has been somewhat slow due to the high expenses of the experiment or the time-consuming density functional theory (DFT) calculation. In this study, we utilized the extreme gradient boosting (XGBoost) algorithm to facilitate the discovery and characterization of ABX3 compounds based on vast data sets generated by DFT calculations. While the XGBoost algorithm provides a powerful tool for accelerating the discovery of ABX3 compounds, it is crucial to acknowledge that different DFT approximation levels can significantly impact the predicted band gaps, potentially introducing discrepancies when compared with experimental values. In the first step, we predict the space group of 13947 oxides and halides using the Open Quantum Materials Database and elemental features. Our analysis yields classification accuracies ranging from 82.39% to 99.14% across these materials. Following this, XGBoost regression algorithms are employed to interrogate the data set, enabling predictions of volume (achieving an optimal accuracy of 98.41%, with a mean absolute error (MAE) of 2.395 Å3 and a root-mean-square error (RMSE) of 4.416 Å3), formation energy (an optimal accuracy of 97.36%, with an MAE of 0.075 eV/atom and an RMSE of 0.132 eV/atom), and band gap energy (an optimal accuracy of 87.00%, an MAE of 0.391 eV, and an RMSE of 0.574 eV). Finally, these prediction models are employed to identify the possible space groups for each of the 1252 new ABX3 formulas. Then, we predict the volume, the formation energy, and the band gap energy for each candidate space group. Through these predictive models, machine learning accelerates the exploration of new materials with enhanced performance and functionality.
Sulfonic Acid-Functionalized Solid Polymer Catalyst from Crude Cashew Nut Shell Liquid: Synthesis of Tetra(indolyl)methanes and Bis(indolyl)methanes from Xylochemicals
Gayatri D. Kotkar - and
Santosh G. Tilve *
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Xylochemistry presents a sustainable solution to the depletion of petroleum resources, contributing to the success of the circulatory economy. The development of reusable carbonaceous materials as heterogeneous acid catalysts has garnered significant attention in both research community and industry. Catalysis research has an intrinsic connection with low-cost synthetic routes, sustainable raw materials, and chemical and thermal stability. We designed and made a solid acid catalyst that can be used more than once from cheap, naturally occurring, crude cashew nut shell liquid (CNSL). Identification of practical applications for waste biomass is a component of the objectives of sustainable development. We treated the black-colored crude CNSL with varying amounts of formaldehyde and further sulfonated the resulting crude resins with chlorosulfonic acid. The solid with the most sulfonic acid groups was used as a Bronsted acid catalyst (CNSLF-SO3H) for the Friedel–Craft reactions of indoles and furfuraldehydes. We synthesized 15 novel di[bis(indolyl)methane] derivatives from secondary xylochemical 2,5-diformylfuran (DFF) and 15 bis(indolyl)methanes from 5-hydroxymethylfurfural (5-HMF).
Conjugation of Antibodies and siRNA Duplexes to Polymer Nanoparticles via Maleimide–Thiol Chemistry
Elise C. Hoover - ,
Chitran Roy Chowdhury - ,
Olivia M. Ruggiero - , and
Emily S. Day *
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Polymeric nanoparticles (NPs) have shown great promise as highly modifiable platforms that can be applied across many different disease states. They are advantageous because they can encapsulate a range of hydrophobic and hydrophilic cargoes while having customizable surface properties. Depending on the desired biointerfacing capabilities, the surface of polymeric NPs can be modified with moieties, such as antibodies, peptides, nucleic acids, and more. The work presented here is intended to provide mechanistic insight into how different parameters influence the loading of antibodies, small interfering ribonucleic acids (siRNAs), or both on the surface of poly(lactic-co-glycolic acid) (PLGA) NPs via maleimide–thiol chemistry. Some of the conjugation parameters investigated include the buffer concentration, maleimide to protein ratio, and the addition of an excipient such as Tween-20. Through variation in the concentration of FZD7 antibodies added to the reaction mixture, we established tunable conjugation and found the upper limit of their loading density under the conditions tested. We also confirmed antibody conjugation through two different mechanisms: via a thiol-modified antibody or a thiol-modified poly(ethylene glycol) (PEG) linker. Conjugation of thiolated siRNA duplexes targeting β-catenin was also investigated through variations in both Tween-20 concentration and CaCl2 buffer concentration. Finally, the coconjugation of both antibodies and siRNA duplexes was explored. Overall, this work outlines a basis for tunable biomolecule loading on polymer NPs using maleimide–thiol chemistry and reveals the incredible versatility of polymer NP platforms.
Ignition and Combustion Performance of B@HMX Composite Microunit Prepared by Recrystallization of Solvent Evaporation
Changlin Zhu - ,
Yang Qin - ,
Kaiwei Liu - ,
Qiaoe Liu - ,
Xiangdong Gao - , and
Jie Liu *
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Fuel boron (B) has the advantage of a high calorific value. However, a coating of boron oxide (B2O3) is present on the outermost layer of the B particles, which will greatly hinder the oxidation of B. In this study, the high-energy 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) is used to increase the activity of B powder, so as to enhance the ignition and combustion performance of B. Samples with various HMX contents are successfully prepared by recrystallization of the solvent evaporation method. The study of morphology and composition reveals that HMX is coated on the surface of B particles to form composite microunits. Interestingly, the heat and gas released during the decomposition of HMX facilitated the evaporation and destruction of the oxide film. Consequently, this promotes the oxidation reaction of B and results in a reduction in its initial oxidation temperature to 762.45 °C. The results of ignition and combustion tests show that the shortest ignition delay time of the sample with the mass ratio of B to HMX of 1:5 is 1.11 s, which is 0.38 s earlier than that of the physical mixed sample. In addition, the maximum height and width of the combustion flame are the largest. These results show that B@HMX composite microunits with a high energy activation effect provide an effective strategy for better application of B powder.
Accurate Coal Classification Using PAIPSO-ELM with Near-Infrared Reflectance Spectroscopy
Yiyang Wang - ,
Boyan Li - ,
Haoyang Li - , and
Dong Xiao *
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China has vast proven coal reserves, encompassing a wide variety of types. However, traditional coal classification methods have limitations, often leading to inaccurate classification and inefficient utilization of coal resources. To address this issue, this paper introduces the Extreme Learning Machine (ELM) as a novel coal classification method, based on the near-infrared reflectance spectroscopy (NIRS) of coal. Initially, we collected NIRS data from coal samples using the SVC-HR-1024 spectrometer. Given the high dimensionality and strong linear correlations in NIRS data, we conducted preprocessing to enhance the usefulness of the data. In experiments, the ELM model demonstrated good classification performance. However, due to the random generation of input layer weights and hidden layer biases in the ELM model, its performance can be unstable, preventing the model from fully realizing its potential. To overcome this shortcoming, we employed the Particle Swarm Optimization (PSO) algorithm to optimize the parameters of the ELM model. Simulation results showed that the PSO-ELM model achieved a 9.68% improvement in classification accuracy compared to the original ELM model. Furthermore, we optimized the PSO algorithm by introducing exponentially decaying inertia factors and position-variant particles to further reduce the risk of the algorithm falling into local optima. The improved Position-Adaptive Inertia PSO-ELM (PAIPSO-ELM) model achieved an additional 2% increase in classification accuracy over the PSO-ELM model, without a significant increase in training time. In summary, this paper proposes a coal spectral classification method based on the PAIPSO-ELM model, effectively overcoming the limitations of traditional classification methods while meeting industrial demands for classification accuracy and speed.
Synthesis, Structural, and Raman Investigation of Lanthanide Nitride Powders (Ln = La, Ce, Nd, Sm, Gd, Tb, Dy, Er, Lu)
Kiersten Kneisel *- ,
Mohsen Maddah - ,
Jay Chan - ,
Ying Xu - ,
Caitlin Casey-Stevens - ,
Kiri Van Koughnet - ,
William Holmes-Hewett - ,
Harry Joseph Trodahl - , and
Franck Natali *
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Lanthanide nitride (LnN) materials have garnered significant interest in recent years due to their promising potential as heterogeneous catalysts for green ammonia synthesis under low temperature and pressure reaction conditions. Here, we report on the synthesis of an extended series of lanthanide (Ln) nitride powders (Ln = lanthanum, cerium, neodymium, samarium, gadolinium, terbium, dysprosium, erbium, lutetium) and their structural and vibrational properties. Polycrystalline powders were fabricated using a ball milling mechanochemical process, and their structural properties were assessed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The experimental lattice constants deduced from XRD and TEM were compared with density functional theory-based calculated lattice constants using the Perdew–Burke–Ernzerhof exchange-correlation functional. We show that the calculated lattice constants are within 1–1.5% of the experimental values for the majority of the LnN species─a notable increase in accuracy over prior computational approaches. The frequencies of Raman scattering from the LO(Γ) phonon are reported across the series and compare well with published thin-film data on a smaller selection of the series. As expected, there is a linear relationship between the LO(Γ) phonon frequency and atomic number. Finally, we demonstrate that Raman spectroscopy can be used to detect the presence of a nanoscale oxide layer on the surface of ErN powders.
Amorphous Titanium Dioxide Nanoparticles and Their Unexpected Fragmentation in MALDI-TOF/MS
Artur L. Hennemann - ,
Helton P. Nogueira - ,
Miguel D. Ramos Jr.- ,
Thiago C. Correra - ,
Bruno L. Hennemann *- , and
Koiti Araki *
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Amorphous 3 nm large ultrasmall (usTiO2) and 7 nm large anatase (nTiO2) nanoparticles (NPs) were successfully prepared and characterized by TEM, FTIR, DRX, UV–vis, and DLS techniques. The MALDI-TOF/MS was shown to be effective in assessing the surface chemistry but fragmentation processes precluded its use for evaluation of particle size distribution. In fact, the laser causes the fragmentation not only of amorphous TiO2 NPs but also of the material subjected to heat treatment and crystallization at 450 °C for 4 h upon interaction with the DHB matrix and TFA ionizing agent. No significant difference could be observed in the spectrum by varying the particle size, indicating the high stability of the TiO2 dimer and its low aggregates in the gaseous phase. In short, MALDI-TOF/MS is effective for the direct analysis of nanoparticle surfaces, especially the interaction of functionalizing molecular species with the inorganic components, which in combination with the other techniques demonstrated to be ideal for the detailed characterization of nanomaterials.
Hydrates of N-((10-Chloroanthracen-9-yl)methyl)-3-(1H-imidazol-1-yl)propan-1-ammonium Cobalt(II), Copper(II), and Zinc(II) 2,6-Pyridinedicarboxylate: Reversible Crystallization
Abhay Pratap Singh - and
Jubaraj B. Baruah *
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In a quest to explore interconvertible assemblies of hydrates of cobalt(II), copper(II), and zinc(II) 2,6-pyridinedicarboxylate (26-pdc), complexes having cation of a chloro-substituted analogue N-{(10-chloroanthracen-9-yl)methyl}-3-(1H-imidazol-1-yl)propan-1-amine were investigated. In the case of cobalt and copper complexes, a crystallized stable hydrate and a less stable methanol hydrate were guided by concentration-dependent crystallizations. The unit-cells of the crystals of the methanol hydrates of the two cobalt and copper complexes each belong to the P1̅ space group but have different stoichiometries as well as large differences in packing. These hydrates could be reversibly crystallized in a predictable manner. The unit-cell volumes of the methanol hydrate of the cobalt complex were four-times smaller than that of the respective stable form (C2/c space group), whereas similar hydrates of the copper complex had a two-times smaller unit-cell volume than that of the stable form. The cations of the stable forms assembled together and formed zigzag ladder-like chains. The spaces present in between the assembled chains were filled with clusters of face to face stacked anions. The transformation to stable form required a bottom-up building process of the unit-cell starting from a smaller unit-cell of the less stable hydrates. Fluorescence spectroscopic studies showed the possibility of two forms of assemblies of the zinc-complex in solution, but crystallization had yielded only the stable form.
Cancer Cells Show Higher Sensitivity to Melatonin-Tamoxifen Drug Conjugates than to Combination of Melatonin and Tamoxifen
Mohamed Akmal Marzouk - ,
Sara Greco - ,
Florence Gbahou - ,
Jenni Küblbeck - ,
Nedjma Labani - ,
Ralf Jockers - ,
Ulrike Holzgrabe - ,
Lisa Wiesmüller - , and
Darius P. Zlotos *
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Drug conjugates of tamoxifen and melatonin linked through the amide side chain of melatonin (4a,4b) were reported as promising agents for future treatment of breast cancer, possibly reversing the adverse effects of tamoxifen. Here, we report the synthesis and pharmacological evaluation of a novel series of anticancer drug conjugates linking melatonin with tamoxifen through polymethylene spacers through the ether oxygen of melatonin (16a–c, 19a–c, 21) and compare them to the previously reported amide-linked analogues 4a and 4b. All hybrid ligands are antagonists of estrogen receptor alpha and agonists of the melatonin MT1 receptor with variable potencies. Several drug conjugates including the (CH2)4-linked analogues 4a and 16a and the (CH2)6-linked compound 16c showed higher potency to inhibit cell viability than the combination of melatonin and tamoxifen on at least one cancer cell line including MCF-7, MDA-MB-231, and HT-1080.
Carbazole–Phosphazene Based Polymer for Efficient Extraction of Gold and Precious Elements from Electronic Waste
Evren Cucu - ,
Betul Ari Engin - ,
Murat Tunc - ,
Ramazan Altundas - , and
Ali Enis Sadak *
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The continuous advancement of industry and technology has significantly increased electronic waste, which contributes to the depletion of valuable metal reserves. Therefore, it is crucial to recycle precious metals in electronic waste effectively and sustainably. This study introduces a novel approach by applying a carbazole–phosphazene-based polymer, EBE-06, in a two-stage leaching method for efficient metal extraction. In the first leaching stage, tin is selectively separated using an acid solution at a controlled pH. In the second stage, valuable metals such as gold are recovered through adsorption onto EBE-06. The polymer exhibited a 99% gold adsorption rate within 1 h, independent of pH, and a maximum adsorption capacity of 1.787 g of gold per gram of polymer. The desorption process yielded 95% efficiency, with the polymer maintaining 94% efficiency over three cycles of use.
November 16, 2024
Electronic, Excitonic, and Optical Properties of Zinc Blende Boron Arsenide Tuned by Hydrostatic Pressure
Elisangela da Silva Barboza - ,
Alexandre C. Dias - ,
Luis Craco - ,
Sabrina S. Carara - ,
Diego R. da Costa *- , and
Teldo A. S. Pereira *
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Based on first-principles calculations combined with a maximally localized Wannier function tight-binding method and the Bethe–Salpeter equation formalism, we theoretically investigate the effects of hydrostatic pressure on the electronic, excitonic, and optical properties of zinc blende boron arsenide. Our findings show: (i) a pressure-induced semiconductor-to-metallic phase transition without causing any change in the structural crystallographic ordering, (ii) a decrease in excitonic binding energy with increasing pressure as a consequence of band gap engineering, and (iii) a small excitonic response in the indirect absorption regime due to the indirect band gap.
November 6, 2024
Plant-Based Diet and Sports Performance
Tatiana Cantarella Sarmento - ,
Rosângela dos Santos Ferreira - , and
Octávio Luiz Franco *
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Recently, interest in plant-based diets has grown significantly, driven by health and environmental concerns. Plant-based diets offer potential health benefits, including decreased risk of cardiovascular disease, weight management, and blood glucose regulation. This diet profile is rich in complex carbohydrates, antioxidants, dietary fiber, and phytochemicals. However, antinutrients in some plant foods can make nutrient absorption difficult, necessitating careful dietary planning. Plant-based diets can also improve sports performance; in addition, they can positively influence the intestinal microbial community, which can promote health and performance. The present study covered a review from 1986 to 2024 and involved an experimental design with human participants. The main objective was to evaluate the impact of plant-based diets on sports performance. Recent research suggests that plant-based diets do not harm athletic performance and may positively impact sports performance by improving blood flow and reducing oxidative stress. These findings have potential clinical significance, particularly for athletes seeking to optimize their physical capabilities through dietary interventions
October 31, 2024
Screen-Printed Nanohybrid Palladium-Based Electrodes for Fast and Simple Determination of Estradiol in Livestock
Claudio Sabbatini Capella Lopes - ,
Francisco Walison Lima Silva - ,
Juliana dos Santos Fernandes - ,
Julia Oliveira Fernandes - ,
João H. A. Ferreira - ,
Felipe Zandonadi Brandão - ,
Ricardo Erthal Santelli - ,
Thiago C. Canevari - , and
Fernando Henrique Cincotto *
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One of the main challenges in animal breeding systems is determining estradiol (E2) in livestock samples as simple and minimally invasive as possible, Thus, a nonenzymatic biosensor screen-printed electrode (SPE) was developed by modifying nanohybrid palladium nanoparticles (PdNPs), and carbon dots anchored on a nanosilica particle (PdNPs/C.dots/SiO2), denominated SPE/PdNPs/C.dots/SiO2, and successfully tested for the direct detection of estradiol in livestock samples. PdNPs were directly obtained by a one-step synthesis through carbon dot reduction. Hybrid nanomaterials were characterized by atomic force microscopy, high-resolution transmission electron microscopy, and electrochemical impedance. The combination of PdNPs with C.dots resulted in a nonenzymatic biosensor supported on a screen-printed platform with superior electrocatalytic properties regarding the oxidation of E2 when compared to unmodified sensors. Modifications in the working electrode resulted in high sensitivity toward E2 determination within a linear range from 0.005 to 14.0 μmol L–1 with a limit of detection of 1.0 nmol L–1. The recovery rate of E2 in bovine serum samples and urine samples ranged from 92 to 106%. Interference studies showed that peak current variation (Δip) among all interferents evaluated and E2 did not exceed ±2%. The newly developed sensor stands out not only for its high sensitivity but also for its quick and simple way of production while also being disposable after analysis, providing a simple, sensitive, and practical approach for the determination of reproductive hormones in livestock.