Localized surface plasmon excitations in metal nanostructures have a strong impact on light scattering, absorption, and local field intensities at the nanoscale. Tweaking the nanoparticle shape, size, and material enables researchers to engineer the resonance wavelength position, the nanoparticles’ local field enhancement, and their scattering properties. In particular, by breaking the symmetry of originally symmetric nanostructures, additional degrees of freedom can be explored. One particular example of a highly investigated nanostructure is the so-called semishell (or nanocup or nanocrescent moon). In this issue of ACS Nano, King et al. report on the angular and spectral scattering properties of plasmonic semishells and the effect of a high-index substrate on these properties.

In comparison with linear polymers, dendrimers’ multivalency and nanostructure confer substantial advantages in drug delivery including rapid cell entry, targetability, and easier passage across biological barriers. Previous work has shown that phosphorus-containing dendrimers capped with anionic azabisphosphonate (ABP) end groups prompt anti-inflammatory activation of human monocytes. By using two mouse models of arthritis mimicking human rheumatoid arthritis (RA), Hayder et al. recently demonstrated that intravenous injection of dendrimer ABP inhibits the secretion of proinflammatory cytokines and osteoclastogenesis—two fundamental monocyte-dependent processes of inflammation and bone erosion in RA. While available biological therapies for RA target only one of the cytokines involved in inflammation or bone erosion, dendrimer ABP, by virtue of its double action on both processes in mice, might become a more active and cost-saving alternative for RA patients. This Perspective highlights this important development and the challenges that lie ahead.

Nature is a school for human beings. Learning from nature has long been a source of bioinspiration for scientists and engineers. Multiscale structures are characteristic for biological materials, exhibiting inherent multifunctional integration. Optimized biological solutions provide inspiration for scientists and engineers to design and to fabricate multiscale structured materials for multifunctional integration.

Noncovalent systems are adaptive and allow facile processing and recycling. Can they be at the same time robust? How can one rationally design such systems? Can they compete with high-performance covalent materials? The recent literature reveals that noncovalent systems can be robust yet adaptive, self-healing, and recyclable, featuring complex nanoscale structures and unique functions. We review such systems, focusing on the rational design of strong noncovalent interactions, kinetically controlled pathway-dependent processes, complexity, and function. The overview of the recent examples points at the emergent field of noncovalent nanomaterials that can represent a versatile, multifunctional, and environmentally friendly alternative to conventional covalent systems.

We extend designs of perfect lenses to the focusing of surface plasmon polaritons (SPPs) propagating at the interface between two anisotropic media of opposite permittivity sign. We identify the role played by the components of anisotropic and heterogeneous tensors of permittivity and permeability, deduced from a coordinate transformation, in the dispersion relation governing propagation of SPPs. We illustrate our theory with three-dimensional finite element computations for focusing of SPPs by perfect flat and cylindrical lenses. Finally, we propose a design of a flat SPP lens consisting of dielectric cylinders arranged in a periodic fashion (along a hexagonal array) on a metal plate.

Nonvolatile memory devices using gold nanoparticles (AuNPs) and reduced graphene oxide (rGO) sheets were fabricated in both horizontal and vertical structures. The horizontal memory device, in which a singly and doubly overlayered semiconducting rGO channel was formed by simply using a spin-casting technique to connect two gold electrodes, was designed for understanding the origin of charging effects. AuNPs were chemically bound to the rGO channel through a π-conjugated molecular linker. The π-conjugated bifunctional molecular linker, 4-mercapto-benzenediazonium tetrafluoroborate (MBDT) salt, was newly synthesized and used as a molecular bridge to connect the AuNPs and rGOs. By using a self-assembly technique, the diazonium functional group of the MBDT molecular linker was spontaneously immobilized on the rGOs. Then, the monolayered AuNPs working as capacitors were covalently connected to the thiol groups of the MBDT molecules, which were attached to rGOs (AuNP-frGO). These covalent bonds were confirmed by XPS analyses. The current–voltage characteristics of both the horizontal and vertical AuNP-frGO memory devices showed noticeable nonlinear hysteresis, stable write–multiple read–erase–multiple read cycles over 1000 s, and a long retention time over 700 s. In addition, the vertical AuNP-frGO memory device showed a large current ON/OFF ratio and high stability.

We perform large-scale molecular dynamics simulations to measure the contact-angle hysteresis for a nanodroplet of water placed on a nanopillared surface. The water droplet can be in either the Cassie state (droplet being on top of the nanopillared surface) or the Wenzel state (droplet being in contact with the bottom of nanopillar grooves). To measure the contact-angle hysteresis in a quantitative fashion, the molecular dynamics simulation is designed such that the number of water molecules in the droplets can be systematically varied, but the number of base nanopillars that are in direct contact with the droplets is fixed. We find that the contact-angle hysteresis for the droplet in the Cassie state is weaker than that in the Wenzel state. This conclusion is consistent with the experimental observation. We also test a different definition of the contact-angle hysteresis, which can be extended to estimate hysteresis between the Cassie and Wenzel state. The idea is motivated from the appearance of the hysteresis loop typically seen in computer simulation of the first-order phase transition, which stems from the metastability of a system in different thermodynamic states. Since the initial shape of the droplet can be controlled arbitrarily in the computer simulation, the number of base nanopillars that are in contact with the droplet can be controlled as well. We show that the measured contact-angle hysteresis according to the second definition is indeed very sensitive to the initial shape of the droplet. Nevertheless, the contact-angle hystereses measured based on the conventional and new definition seem converging in the large droplet limit.

Metal diffusion in nanoscale materials is of great interest, yet the detailed kinetic behavior of such diffusion remains elusive. We observe direction-controlled Cu diffusion during unconventional galvanic replacement reactions between surface-limited Cu nanocrystals (NCs) and HAuCl₄. Using presynthesized Cu–Cu_1.81S hetero-oligomer and Cu–Cu₂S heterodimer NCs as templates and reactants, the controlled addition of HAuCl₄ leads to the preferential outward diffusion of Cu, visualized by the formation of single-crystalline and straight, or polycrystalline and kinked, CuAu nanowires, respectively. The time-dependent growth of these nanowires enables determination of nanoscale diffusion coefficients of Cu during these processes, for the first time.

The concept of growing nanosize particles on polarized ferroelectric domain areas is known as ferroelectric lithography (FL). Here, a further step of technical development was achieved by combining nanoembossing technique with the FL to realize the selective growth of silver on the polarized areas induced by nanoembossing. The induced rearrangements of domain distributions by embossing in the ferroelectric films have been characterized by piezoresponse force microscopy (PFM). The selective photochemical reduction of silver particles on the embossed nanostructures associated with the underlying domain patterns created by the nanoembossing process has been successfully demonstrated. This nanoembossing induced ferroelectric lithography (NIFL) developed in this work is expected to create an alternative route for nanoscale patterning of metals.

Carbon nanomaterials (CNM) are targets of great interest because they have multiple applications in industry but also because of the fear of possible harmful heath effects of certain types of CNM. The high aspect ratio of carbon nanotubes (CNT), a feature they share with asbestos, is likely the key factor for reported toxicity of certain CNT. However, the mechanism to explain this toxicity is unclear. Here we investigated whether different CNM induce a pro-inflammatory response in human primary macrophages. Carbon black, short CNT, long, tangled CNT, long, needle-like CNT, and crocidolite asbestos were used to compare the effect of size and shape on the potency of the materials to induce secretion of interleukin (IL) 1-family cytokines. Our results demonstrated that long, needle-like CNT and asbestos activated secretion of IL-1β from LPS-primed macrophages but only long, needle-like CNT induced IL-1α secretion. SiRNA experiments demonstrated that the NLRP3 inflammasome was essential for long, needle-like CNT and asbestos-induced IL-1β secretion. Moreover, it was noted that CNT-induced NLRP3 inflammasome activation depended on reactive oxygen species (ROS) production, cathepsin B activity, P2X₇ receptor, and Src and Syk tyrosine kinases. These results provide new information about the mechanisms by which long, needle-like materials may cause their harmful health effects. Furthermore, the techniques used here may be of use in future risk assessments of nanomaterials.

We have investigated the interface electronic states in self-assembled (Ti_0.8Co_0.2O₂/Ti_0.6Fe_0.4O₂)_n superlattices by X-ray photoelectron spectroscopy. A charge of about −0.3 electron is transferred from Fe to Co ions across the interface and induces a major reconstruction of the orbital occupation at the interfacial (Ti_0.8Co_0.2O₂/Ti_0.6Fe_0.4O₂) layers. Supported by first-principles calculations, the Co³⁺ state is partially occupied at the interface by superlattice formation, and this new magnetic state directly influences the coupling between Ti_0.8Co_0.2O₂ and Ti_0.6Fe_0.4O₂ nanosheets. These data indicate that the orbital reconstruction is indeed realized by the interface charge transfer between Co and Fe ions in the adjoined nanosheets, and the generic feature of engineered interfaces can be extended to self-assembled superlattices of oxide nanosheets.

We compare the single-particle plasmonic sensitivity of silver and gold nanorods with similar resonance wavelengths by monitoring the plasmon resonance shift upon changing the environment from water to 12.5% sucrose solution. We find that silver nanoparticles have 1.2 to 2 times higher sensitivity than gold, in good agreement with simulations based on the boundary-elements-method (BEM). To exclude the effect of particle volume on sensitivity, we test gold rods with increasing particle width at a given resonance wavelength. Using the Drude-model of optical properties of metals together with the quasi-static approximation (QSA) for localized surface plasmons, we show that the dominant contribution to higher sensitivity of silver is the lower background polarizability of the d-band electrons and provide a simple formula for the sensitivity. We improve the reversibility of the silver nanorod sensors upon repeated cycles of environmental changes by blocking the high energy parts of the illumination light.

Here we present a single-step all-aqueous approach to encapsulate biomolecules such as enzymes and proteins into stable microreactors. Key in this method is the use of spray-drying of the biomolecules of interest in combination with oppositely charged polyelectrolytes and mannitol as the sacrificial template. Remarkably, upon spray-drying in the presence of polyelectrolyte, mannitol crystallization is suppressed and the obtained amorphous mannitol offers enhanced preservation of the biomolecules’ activity. Moreover, the use of mannitol allows the formation of nanopores within the microparticles upon rehydration of the microparticles in aqueous medium and subsequent dissolution of the mannitol. The oppositely charged polyelectrolytes provide a polymeric framework which stabilizes the microparticles upon rehydration. The versatility of this approach is demonstrated using horseradish peroxidase as the model enzyme and ovalbumin as the model antigen.

We report herein the synthesis of a novel type of hybrid compound that consists of a poly(ethylene oxide) (PEO) functionalized β-sheet peptide sequence covalently linked to an alkylated quaterthiophene moiety. Compounds of this class are highly promising for technological applications because their self-assembly and stimuli-responsive behavior, which is mainly caused by the peptide moieties, combined with the potential semiconducting properties of oligothiophenes provides unprecedented opportunities for the design of advanced materials at the nanoscale in such areas as, for example, organic electronics and sensor design for chemical and biomedical applications. The compound presented herein is experimentally shown to form stable fibrillar aggregates that are visualized by both transmission electron and atomic force microscopy. We developed a theoretical methodology to study the possible intermolecular arrangements and their characteristic features with the help of all-atom MD simulations, while simultaneously incorporating available experimental data into the model. Large-scale atomistic simulations of several fibrillar aggregates with different molecular arrangements were performed. The results of the simulations are compared with experimental data, which leads to the proposition of a likely model for the arrangement of the individual molecules within the observed aggregates.

The integration of multiple functionalities into individual nanoelectronic components is increasingly explored as a means to step up computational power, or for advanced signal processing. Here, we report the fabrication of a coupled nanowire transistor, a device where two superimposed high-performance nanowire field-effect transistors capable of mutual interaction form a thyristor-like circuit. The structure embeds an internal level of signal processing, showing promise for applications in analogue computation. The device is naturally derived from a single NW via a self-aligned fabrication process.

Reproducible dry and wet transfer techniques were developed to improve the transfer of large-area monolayer graphene grown on copper foils by chemical vapor deposition (CVD). The techniques reported here allow transfer onto three different classes of substrates: substrates covered with shallow depressions, perforated substrates, and flat substrates. A novel dry transfer technique was used to make graphene-sealed microchambers without trapping liquid inside. The dry transfer technique utilizes a polydimethylsiloxane frame that attaches to the poly(methyl methacrylate) spun over the graphene film, and the monolayer graphene was transferred onto shallow depressions with 300 nm depth. The improved wet transfer onto perforated substrates with 2.7 μm diameter holes yields 98% coverage of holes covered with continuous films, allowing the ready use of Raman spectroscopy and transmission electron microscopy to study the intrinsic properties of CVD-grown monolayer graphene. Additionally, monolayer graphene transferred onto flat substrates has fewer cracks and tears, as well as lower sheet resistance than previous transfer techniques. Monolayer graphene films transferred onto glass had a sheet resistance of ∼980 Ω/sq and a transmittance of 97.6%. These transfer techniques open up possibilities for the fabrication of various graphene devices with unique configurations and enhanced performance.

We demonstrate the water-assisted supergrowth of vertically aligned single-walled carbon–nitrogen nanotubes (SWNNTs) using a simple liquid/gas-phase precursor system. In situ characterization of gas-phase nitrogen-containing precursors and their correlation to growth identifies HCN as the most active precursor for SWNNT growth, analogous to C₂H₂ for single-walled carbon nanotubes (SWNTs). Utilizing Raman spectroscopy, combined with XPS and in situ mass spectrometry during growth, we demonstrate the ability to probe N atoms at low concentrations (10^–5 at. % N) in the SWNNT. Additionally, we demonstrate sensitivity of SWNNT optical transitions to N-doping through absorbance measurements, which appear to be a sensitive fingerprint for SWNNT doping. Finally, we demonstrate the fabrication of SWNT/SWNNT heterojunctions in the self-assembled carpet morphology that can be printed to arbitrary host substrates and facilitate potential emerging applications for this material. This work brings together new aspects regarding the growth, characterization, and materials processing that can yield advanced material architectures involving electronically tuned SWNNT array networks.

Anodic aluminum oxide (AAO) is a porous material having aligned cylindrical compartments with 55–60 nm diameter pores, and being several micrometers deep. A protocol was developed to generate pore-spanning fluid lipid bilayers separating the attoliter-sized compartments of the nanoporous material from the bulk solution, while preserving the optical transparency of the AAO. The AAO was selectively functionalized by silane chemistry to spread giant unilamellar vesicles (GUVs) resulting in large continuous membrane patches covering the pores. Formation of fluid single lipid bilayers through GUV rupture could be readily observed by fluorescence microscopy and further supported by conservation of membrane surface area, before and after GUV rupture. Fluorescence recovery after photobleaching gave low immobile fractions (5–15%) and lipid diffusion coefficients similar to those found for bilayers on silica. The entrapment of molecules within the porous underlying cylindrical compartments, as well as the exclusion of macromolecules from the nanopores, demonstrate the barrier function of the pore-spanning membranes and could be investigated in three-dimensions using confocal laser scanning fluorescence imaging.

Stable dispersions of nanofibers are virtually unknown for synthetic polymers. They can complement analogous dispersions of inorganic components, such as nanoparticles, nanowires, nanosheets, etc. as a fundamental component of a toolset for design of nanostructures and metamaterials via numerous solvent-based processing methods. As such, strong flexible polymeric nanofibers are very desirable for the effective utilization within composites of nanoscale inorganic components such as nanowires, carbon nanotubes, graphene, and others. Here stable dispersions of uniform high-aspect-ratio aramid nanofibers (ANFs) with diameters between 3 and 30 nm and up to 10 μm in length were successfully obtained. Unlike the traditional approaches based on polymerization of monomers, they are made by controlled dissolution of standard macroscale form of the aramid polymer, that is, well-known Kevlar threads, and revealed distinct morphological features similar to carbon nanotubes. ANFs are successfully processed into films using layer-by-layer (LBL) assembly as one of the potential methods of preparation of composites from ANFs. The resultant films are transparent and highly temperature resilient. They also display enhanced mechanical characteristics making ANF films highly desirable as protective coatings, ultrastrong membranes, as well as building blocks of other high performance materials in place of or in combination with carbon nanotubes.

We develop graphene-based devices fabricated by alternating current dielectrophoresis (ac-DEP) for highly sensitive nitric oxide (NO) gas detection. The novel device comprises the sensitive channels of palladium-decorated reduced graphene oxide (Pd-RGO) and the electrodes covered with chemical vapor deposition (CVD)-grown graphene. The highly sensitive, recoverable, and reliable detection of NO gas ranging from 2 to 420 ppb with response time of several hundred seconds has been achieved at room temperature. The facile and scalable route for high performance suggests a promising application of graphene devices toward the human exhaled NO and environmental pollutant detections.

Paclitaxel, a potent chemotherapeutic utilized in a variety of cancers, can be limited in its effectiveness due to inherent insolubility in aqueous media and acquired chemoresistance within certain cells. An approach has been developed for increasing Paclitaxel solubility and effectiveness by covalent attachment to gold nanoparticles via DNA linkers. The resulting conjugates are highly soluble in aqueous buffer, exhibiting greater than a 50-fold increase in solubility over the unconjugated drug. DNA linkers are labeled with a fluorophore, which affords a convenient means of visualizing resultant conjugates within cells. Internalized conjugates demonstrate increased activity as compared with free drug across a variety of cell types, including a Paclitaxel-resistant cell line. Attachment to DNA–nanoparticle conjugates may become a general strategy for solubilizing and enhancing a wide variety of therapeutic agents in aqueous media.

Health and environmental impacts of graphene-based materials need to be thoroughly evaluated before their potential applications. Graphene has strong cytotoxicity toward bacteria. To better understand its antimicrobial mechanism, we compared the antibacterial activity of four types of graphene-based materials (graphite (Gt), graphite oxide (GtO), graphene oxide (GO), and reduced graphene oxide (rGO)) toward a bacterial model—Escherichia coli. Under similar concentration and incubation conditions, GO dispersion shows the highest antibacterial activity, sequentially followed by rGO, Gt, and GtO. Scanning electron microscope (SEM) and dynamic light scattering analyses show that GO aggregates have the smallest average size among the four types of materials. SEM images display that the direct contacts with graphene nanosheets disrupt cell membrane. No superoxide anion (O₂^•–) induced reactive oxygen species (ROS) production is detected. However, the four types of materials can oxidize glutathione, which serves as redox state mediator in bacteria. Conductive rGO and Gt have higher oxidation capacities than insulating GO and GtO. Results suggest that antimicrobial actions are contributed by both membrane and oxidation stress. We propose that a three-step antimicrobial mechanism, previously used for carbon nanotubes, is applicable to graphene-based materials. It includes initial cell deposition on graphene-based materials, membrane stress caused by direct contact with sharp nanosheets, and the ensuing superoxide anion-independent oxidation. We envision that physicochemical properties of graphene-based materials, such as density of functional groups, size, and conductivity, can be precisely tailored to either reducing their health and environmental risks or increasing their application potentials.

We report the scanning probe microscope (SPM)-based single-molecule recognition of biomolecular interactions between protein kinase and small ligands (i.e., ATP and Imatinib). In general, it is difficult to sense and detect the small ligands bound to protein kinase (at single-molecule resolution) using a conventional atomic force microscope (AFM) due to the limited resolution of conventional AFM for detecting the miniscule changes in molecular size driven by ligand binding. In this study, we have demonstrated that Kelvin probe force microscopy (KPFM) is able to articulate the surface potential of biomolecules interacting with ligands (i.e., the protein kinase–ATP interactions and inhibition phenomena induced by antagonistic molecules) in a label-free manner. Furthermore, measured surface potentials for biomolecular interactions enable quantitative descriptions on the ability of protein kinase to interact with small ligands such as ATP or antagonistic molecules. Our study sheds light on KPFM that allows the precise recognition of single-molecule interactions, which opens a new avenue for the design and development of novel molecular therapeutics.

The endothelial lining of the lumen of blood vessels is a key therapeutic target for many human diseases. Polymeric filomicelles that self-assemble from polyethylene oxide (PEO)-based diblock copolymers are long and flexible rather than small or rigid, can be loaded with drugs, and—most importantly—they circulate for a prolonged period of time in the bloodstream due in part to flow alignment. Filomicelles seem promising for targeted drug delivery to endothelial cells because they can in principle adhere strongly, length-wise to specific cell surface determinants. In order to achieve such a goal of vascular drug delivery, two fundamental questions needed to be addressed: (i) whether these supramolecular filomicelles retain structural integrity and dynamic flexibility after attachment of targeting molecules such as antibodies, and (ii) whether the avidity of antibody-carrying filomicelles is sufficient to anchor the carrier to the endothelial surface despite the effects of flow that oppose adhesive interactions. Here we make targeted filomicelles that bear antibodies which recognize distinct endothelial surface molecules. We characterize these antibody targeted filomicelles and prove that (i) they retain structural integrity and dynamic flexibility and (ii) they adhere to endothelium with high specificity both in vitro and in vivo. These results provide the basis for a new drug delivery approach employing antibody-targeted filomicelles that circulate for a prolonged time yet bind to endothelial cells in vascular beds expressing select markers.

Graphene with unique physical and chemical properties has shown various potential applications in biomedicine. In this work, a photosensitizer molecule, Chlorin e6 (Ce6), is loaded on polyethylene glycol (PEG)-functionalized graphene oxide (GO) via supramolecular π–π stacking. The obtained GO-PEG-Ce6 complex shows excellent water solubility and is able to generate cytotoxic singlet oxygen under light excitation for photodynamic therapy (PDT). Owing to the significantly enhanced intracellular trafficking of photosensitizers, our GO-PEG-Ce6 complex offers a remarkably improved cancer cell photodynamic destruction effect compared to free Ce6. More importantly, we show that the photothermal effect of graphene can be utilized to promote the delivery of Ce6 molecules by mild local heating when exposed to a near-infrared laser at a low power density, further enhancing the PDT efficacy against cancer cells. Our work highlights the promise of using graphene for potential multifunctional cancer therapies.

We investigated how pulsed laser annealing can be applied to process thin films of colloidal nanocrystals (NCs) into interconnected nanostructures. We illustrate the relationship between incident laser fluence and changes in morphology of PbSe NC films relative to bulk-like PbSe films. We found that laser pulse fluences in the range of 30 to 200 mJ/cm² create a processing window of opportunity where the NC film morphology goes through interesting transformations without large-scale coalescence of the NCs. NC coalescence can be mitigated by depositing a thin film of amorphous silicon (a-Si) on the NC film. Remarkably, pulsed laser annealing of the a-Si/PbSe NC films crystallized the silicon while NC morphology and translational order of the NC film are preserved.

We investigated and compared the concentration-dependent cytotoxicity of single-walled carbon nanotubes (SWCNTs) and SWCNTs functionalized with polyethylene glycol (SWCNT-PEGs) in neuronal PC12 cells at the biochemical, cellular, and gene expressional levels. SWCNTs elicited cytotoxicity in a concentration-dependent manner, and SWCNT-PEGs exhibited less cytotoxic potency than uncoated SWCNTs. Reactive oxygen species (ROS) were generated in both a concentration- and surface coating-dependent manner after exposure to these nanomaterials, indicating different oxidative stress mechanisms. More specifically, gene expression analysis showed that the genes involved in oxidoreductases and antioxidant activity, nucleic acid or lipid metabolism, and mitochondria dysfunction were highly represented. Interestingly, alteration of the genes is also surface coating-dependent with a good correlation with the biochemical data. These findings suggest that surface functionalization of SWCNTs decreases ROS-mediated toxicological response in vitro.

Small-interfering RNA (siRNA) has a high application potential for therapeutic silencing of pathologic or drug-resistance genes. However, although recent research has led to several nonviral nucleic acid delivery systems with encouraging transfection performance, there remains a substantial gap between these systems and an ideal siRNA carrier that can be safely and effectively used for the more complex delivery tasks such as cancer management. We hypothesized that by integrating the high transfection performance of linear polyethylenimine (PEI) with the controlled release properties of solid lipid components, and complementing the resulting lipid–PEI hybrid nanocarrier (LPN) with receptor-targeting capability, multiple limitations of the conventional siRNA carriers would be simultaneously overcome. Data comparing this new hybrid system with the conventional siRNA-PEI polyplexes showed 15 to 21% less loss of siRNA, higher selectivity for prostate cancer cells over noncancerous prostate cells, and significant reduction in both acute and delayed carrier toxicity especially to the noncancerous RWPE1 cells (e.g., 71.2% of LPN-treated cells preserved proliferative capacity versus ≤30.2% in other groups). We further demonstrated sustained intracellular siRNA release from LPNs, which was shown translatable into extended in vitro and in vivo RNA-interference effects for a minimum of one week. Our findings generally support the use of LPN technology to achieve a longer-acting, less toxic, more efficient, and cancer-specific form of siRNA therapy in an “all-in-one” manner. This brings the nonviral siRNA delivery approach one important step closer to its clinical application.

Single-molecule characterization is essential for ascertaining the structural and functional properties of bottom-up DNA nanostructures. Here we enlist three atomic force microscopy (AFM) techniques to examine tetrahedron-shaped DNA nanostructures that are functionally enhanced with small chemical tags. In line with their application for biomolecule immobilization in biosensing and biophysics, the tetrahedra feature three disulfide-modified vertices to achieve directed attachment to gold surfaces. The remaining corner carries a single bioligand that can capture and present individual cargo biomolecules at defined lateral nanoscale spacing. High-resolution AFM topographic imaging confirmed the directional surface attachment as well as the highly effective binding of individual receptor molecules to the exposed bioligands. Insight into the binding behavior at the single-molecule level was gained using molecular recognition force spectroscopy using an AFM cantilever tip with a tethered molecular receptor. Finally, simultaneous topographic and recognition imaging demonstrated the specific receptor–ligand interactions on individual tetrahedra. In summary, AFM characterization verified that the rationally designed DNA nanostructures feature characteristics to serve as valuable immobilization agents in biosensing, biophysics, and cell biology.

Color filters are indispensable in most color display applications. In most cases, they are chemical pigment-based filters, which produce a particular color by absorbing its complementary color, and the absorbed energy is totally wasted. If the absorbed and wasted energy can be utilized, e.g., to generate electricity, innovative energy-efficient electronic media could be envisioned. Here we show photonic nanostructures incorporated with photovoltaics capable of producing desirable colors in the visible band and utilize the absorbed light to simultaneously generate electrical powers. In contrast to the traditional colorant-based filters, these devices offer great advantages for electro-optic applications.

Three-dimensional microelectrodes were fabricated using glassy carbon electrodes combined with vertically aligned carbon nanotubes (VACNTs). VACNTs were grown on various conducting electrode patterns including a carbon electrode fabricated by pyrolysis of a negative photoresist, with plasma-enhanced chemical vapor deposition using a bilayer Fe/Al catalyst. VACNT electrodes grown on the glassy carbon showed excellent electrochemical behavior, whereas VACNT electrodes grown on Pt showed poor electrochemical performance, presumably due to the poor contact between VACNTs and the Pt electrode. Electron microscopy showed that the VACNT layer was strongly bound to the carbon electrode, while that on Pt tended to peel away. The versatility of the all-carbon microelectrodes was also tested by using them for interfacing stem cells. Their superior mechanical properties and the electrical connectivity between the carbon electrode and the VACNTs, along with the simple fabrication process, suggest that glassy carbon may be a good conducting substrate for VACNT electrodes.

Physically responsive field-effect transistors (physi-FETs) that are sensitive to physical stimuli have been studied for decades. The important issue for separating the responses of sensing materials from interference by other subcomponents in a FET transducer under global physical stimuli has not been completely resolved. In addition, challenges remain with regard to the design and employment of smart materials for flexible physi-FETs with a large electro-physical coupling effect. In this article, we propose the direct integration of nanocomposite (NC) gate dielectrics of barium titanate (BT) nanoparticles (NPs) and highly crystalline poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) into flexible organic FETs to achieve a large electro-physical coupling effect. Additionally, a new alternating current biasing method is proposed for precise extraction and quantification of tiny variations in the remnant polarization of NCs caused by mechanical stimuli. An investigation of physi-FETs under static mechanical stimuli revealed the first ever reported giant, positive piezoelectric coefficients of d₃₃ up to 960 pC/N in the NCs. The large coefficients are presumably due to the significant contributions of the intrinsic positive piezoelectricity of the BT NPs and P(VDF-TrFE) crystallites.

We describe novel composite nanoparticles consisting of a gold–silver nanocage core and a mesoporous silica shell functionalized with the photodynamic sensitizer Yb–2,4-dimethoxyhematoporphyrin (Yb–HP). In addition to the long-wavelength plasmon resonance near 750–800 nm, the composite particles exhibited a 400-nm absorbance peak and two fluorescence peaks, near 580 and 630 nm, corresponding to bound Yb–HP. The fabricated nanocomposites generated singlet oxygen under 630-nm excitation and produced heat under laser irradiation at the plasmon resonance wavelength (750–800 nm). In particular, we observed enhanced killing of HeLa cells incubated with nanocomposites and irradiated by 630-nm light. Furthermore, an additional advantage of fabricated conjugates was an IR-luminescence band (900–1060 nm), originating from Yb³⁺ ions of bound Yb–HP and located in the long-wavelength part of the tissue transparency window. This modality was used to control the accumulation and biodistribution of composite particles in mice bearing Ehrlich carcinoma tumors in a comparative study with intravenously injected free Yb–HP molecules. Thus, these multifunctional nanocomposites seem an attractive theranostic platform for simultaneous IR-luminescence diagnostic and photodynamic therapy owing to Yb–HP and for plasmonic photothermal therapy owing to Au–Ag nanocages.

We show, by complementary spectroscopic and STM analysis, that Cr₇Ni derivatives are suitable to be sublimed in UHV conditions. Cr₇Ni-bu weakly bonds to gold surface and can diffuse relatively freely on it, forming monolayers with hexagonal 2D packing. Conversely, by adding a functional thiol group to the central dibutylamine, a covalent bond between the molecule and surface gold adatoms is promoted, leading to a strong molecular grafting and the formation of a disordered monolayer. These two examples demonstrate the possibility to control the assembly of a large molecular complex, as rationalized by DFT calculations that establish different energy scales in the deposition processes. Moreover, low-temperature XMCD sprectra show that the magnetic features of Cr₇Ni rings deposited in UHV on gold remain unchanged with respect to those of the corresponding bulk sample.

Self-assembled hierarchical MoO₂/graphene nanoarchitectures have been fabricated on a large scale through a facile solution-phase process and subsequent reduction of the Mo-precursor/graphene composite. The as-formed MoO₂/graphene nanohybrid as an anode material for lithium-ion batteries exhibits not only a highly reversible capacity but also an excellent cycling performance as well as good rate capability. Results show that the hierarchical rods made of primary MoO₂ nanocrystals are uniformly encapsulated within the graphene sheets. The synergistic effect of the hierarchical nanoarchitecture and the conducting graphene support may contribute to the enhanced electrochemical performances of the hybrid MoO₂/graphene electrode. This work presents a facile synthetic strategy that is potentially competitive for scaling-up industrial production. Besides, the MoO₂/graphene hybrids with a well-defined hierarchical topology not only provide flexible building blocks for advanced functional devices, but are also ideal candidates for studying their nanoarchitecture-dependent performances in catalytic and electronic applications.

We have investigated the effects of localized surface plasmons (LSPs) on the performance of dye-sensitized solar cells (DSSCs). The LSPs from Ag nanoparticles (NPs) increase the absorption of the dye molecules, allowing us to decrease the thickness of photoanodes, which improves electron collection and device performance. The plasmon-enhanced DSSCs became feasible through incorporating core–shell Ag@TiO₂ NPs into conventional TiO₂ photoanodes. The thin shell keeps the photoelectrons from recombining on the surface of metal NPs with dye and electrolyte and improves the stability of metal NPs. With 0.6 wt % Ag@TiO₂ NPs, the power conversion efficiency of DSSCs with thin photoanodes (1.5 μm) increases from 3.1% to 4.4%. Moreover, a small amount of Ag@TiO₂ NPs (0.1 wt %) improves efficiency from 7.8% to 9.0% while decreasing photoanode thickness by 25% for improved electron collection. In addition, plasmon-enhanced DSSCs require 62% less material to maintain the same efficiency as conventional DSSCs.

We report on a technique enabling electrical control of the contact silicidation process in silicon nanowire devices. Undoped silicon nanowires were contacted by pairs of nickel electrodes, and each contact was selectively silicided by means of the Joule effect. By a real-time monitoring of the nanowire electrical resistance during the contact silicidation process we were able to fabricate nickel-silicide/silicon/nickel-silicide devices with controlled silicon channel length down to 8 nm.

It is currently believed that magnetic nanoparticle heaters (MNHs) can kill cancer cells only when the temperature is raised above 43 °C due to energy dissipation in an alternating magnetic field. On the other hand, simple heat conduction arguments indicate that in small tumors or single cells the relative rates of energy dissipation and heat conduction result in a negligible temperature rise, thus limiting the potential of MNHs in treating small tumors and metastatic cancer. Here we demonstrate that internalized MNHs conjugated to epidermal growth factor (EGF) and which target the epidermal growth factor receptor (EGFR) do result in a significant (up to 99.9%) reduction in cell viability and clonogenic survival in a thermal heat dose dependent manner, without the need for a perceptible temperature rise. The effect appears to be cell type specific and indicates that magnetic nanoparticles in alternating magnetic fields may effectively kill cancer cells under conditions previously considered as not possible.

Controlling the movement of nanoscale objects is a significant goal of nanotechnology. Dewetting-induced ejection of nanodroplets could provide another means of achieving that goal. Molecular dynamics simulations were used to investigate the dewetting-induced ejection of nanoscale liquid copper nanostructures that were deposited on a graphitic substrate. Nanostructures in the shape of a circle, square, equilateral, and isosceles triangle dewet and form nanodroplets that are ejected from the substrate with a velocity that depends on the initial shape and temperature. The dependence of the ejected velocity on shape is ascribed to the temporal asymmetry of the mass coalescence during the droplet formation; the dependence on temperature is ascribed to changes in the density and viscosity. The results suggest that dewetting induced by nanosecond laser pulses could be used to control the velocity of ejected nanodroplets.

High-sensitivity strain gauges based on single wires of close-packed 14 nm colloidal gold nanoparticles are obtained by a novel variant of convective self-assembly (CSA). This CSA mode named stop-and-go CSA enables the fabrication of nanoparticle wires only a few micrometers wide, separated by distances that can be easily tuned over tens to hundreds of micrometers. Nanoparticle wires are obtained in a single step by direct deposition of nanoparticles from suspensions onto flexible polyethylene terephthalate films, without any lithographic prepatterning. When connected between two electrodes, such single nanoparticle wires function as miniature resistive strain gauges. The high sensitivity, repeatability, and robustness demonstrated by these single-wire strain gauges make them extremely promising for integration into micro-electromechanical systems or for high-resolution strain mapping.

Diamond is an electrical insulator in its natural form. However, when doped with boron above a critical level (∼0.25 atom %) it can be rendered superconducting at low temperatures with high critical fields. Here we present the realization of a micrometer-scale superconducting quantum interference device (μ-SQUID) made from nanocrystalline boron-doped diamond (BDD) films. Our results demonstrate that μ-SQUIDs made from superconducting diamond can be operated in magnetic fields as large as 4 T independent of the field direction. This is a decisive step toward the detection of quantum motion in a diamond-based nanomechanical oscillator.

For the first time, large-area CVD-grown graphene films transferred onto flexible PET substrates were used as transparent conductive electrodes in alternating current electroluminescence (ACEL) devices. The flexible ACEL device based on a single-layer graphene electrode has a turn-on voltage of 80 V; at 480 V (16 kHz), the luminance and luminous efficiency are 1140 cd/m² and 5.0 lm/W, respectively. The turn-on voltage increases and the luminance decreases with increasing stacked layers of graphene, which means the single-layer graphene is the best optimal choice as the transparent conductive electrode. Furthermore, it demonstrates that the graphene-based ACEL device is highly flexible and can work very well even under a very large strain of 5.4%, suggesting great potential applications in flexible optoelectronics.

In biological fluids, proteins associate with nanoparticles, leading to a protein “corona” defining the biological identity of the particle. However, a comprehensive knowledge of particle-guided protein fingerprints and their dependence on nanomaterial properties is incomplete. We studied the long-lived (“hard”) blood plasma derived corona on monodispersed amorphous silica nanoparticles differing in size (20, 30, and 100 nm). Employing label-free liquid chromatography mass spectrometry, one- and two-dimensional gel electrophoresis, and immunoblotting the composition of the protein corona was analyzed not only qualitatively but also quantitatively. Detected proteins were bioinformatically classified according to their physicochemical and biological properties. Binding of the 125 identified proteins did not simply reflect their relative abundance in the plasma but revealed an enrichment of specific lipoproteins as well as proteins involved in coagulation and the complement pathway. In contrast, immunoglobulins and acute phase response proteins displayed a lower affinity for the particles. Protein decoration of the negatively charged particles did not correlate with protein size or charge, demonstrating that electrostatic effects alone are not the major driving force regulating the nanoparticle–protein interaction. Remarkably, even differences in particle size of only 10 nm significantly determined the nanoparticle corona, although no clear correlation with particle surface volume, protein size, or charge was evident. Particle size quantitatively influenced the particle’s decoration with 37% of all identified proteins, including (patho)biologically relevant candidates. We demonstrate the complexity of the plasma corona and its still unresolved physicochemical regulation, which need to be considered in nanobioscience in the future.

Nanoscale self-assembly dynamics of submonolayer bimetallic films was studied through simulation of a coarse-grained mesoscopic model. Simulations predict a phase transition sequence (hexagonal→stripe→inverse hexagonal) consistent with experimental observations of Pb/Cu(111) heteroepitaxial growth. Post-transition ordering dynamics of hexagonal and inverse hexagonal patterns was simulated and quantified in order to predict pattern quality and evolution mechanisms. Correlation length scaling laws and nanoscale evolution mechanisms were predicted through simulation of experimentally relevant length (≈1 μm²) and time scales, with findings supporting evidence of universal pattern behavior with other hexagonal systems. Results provide detailed dynamics and structure of this novel self-assembly process applicable to the design and optimization of functional bimetallic materials, such as bimetallic catalysts.

Octapod-shaped colloidal nanocrystals composed of a central “core” region of cubic sphalerite CdSe and pods of hexagonal wurtzite CdS are subject to a cation exchange reaction in which Cd²⁺ ions are progressively exchanged by Cu⁺ ions. The reaction starts from the tip regions of the CdS pods and proceeds toward the center of the nanocrystals. It preserves both the shape and the anionic lattices of the heterostructures. During the exchange, the hexagonal wurtzite CdS pods are converted gradually into pods of hexagonal Cu₂S chalcocite. Therefore, the partial cation exchange reactions lead to the formation of a ternary nanostructure, consisting of an octapod in which the central core is still CdSe, while the pods have a segmented CdS/Cu₂S composition. When the cation exchange reaches the core, the cubic sphalerite CdSe core is converted into a core of cubic Cu_2–xSe berzelianite phase. Therefore fully exchanged octapods are composed of a core of Cu_2–xSe and eight pods of Cu₂S. All these structures are stable, and the epitaxial interfaces between the various domains are characterized by low lattice mismatch. The Cu_2–xSe(core)/Cu₂S(pods) octapod represents another example of a nanostructure in which branching is achieved by proper organization of cubic and hexagonal domains in a single nanocrystal.

As luminescent surface-functionalized gold nanoparticles emerged as potential powerful analytical tools in the biomedical fields, understanding the interaction of such systems with proteins has become crucial. In the present study, the interaction of luminescent water-soluble gold nanoparticles (AuNP-1·Eu-nta), obtained through the self-assembly of a naphthalene β-diketone antenna with a Eu(III) cyclen complex tethered to the gold surface via a C₁₂ alkyl thiol spacer, with bovine serum albumin (BSA) was investigated. The changes in the UV–visible absorption and fluorescence spectra of both the antenna and protein, as well as in the time-resolved Eu(III)-centered emission, of the resulting self-assembly were monitored, at physiological pH, as a function of the BSA concentration. We demonstrate that the Eu(III) emission arising from the self-assembly on the AuNP surface is almost completely quenched upon addition of BSA. Binding constant determination clearly showed that the sensitizing antenna was not displaced and that the quenching was the result of the interaction between the antenna and BSA. Detailed spectroscopic studies performed on the nta–BSA system brought a better insight in the strength of such interaction as well as its effect on the protein secondary structure. Finally, the information gathered on each system resulted in applying AuNP-1·Eu-nta–BSA for the luminescent detection of drugs via the perturbation of the nta–BSA interaction. Competitive titrations using ibuprofen and warfarin showed that nta was located in the binding site II of BSA and that the presence of warfarin, a site I drug, did not interfere with the detection of site II ibuprofen.

We demonstrate the synthesis of large-area graphene on Co, a complementary metal-oxide-semiconductor (CMOS)-compatible metal, using acetylene (C₂H₂) as a precursor in a chemical vapor deposition (CVD)-based method. Cobalt films were deposited on SiO₂/Si, and the influence of Co film thickness on monolayer graphene growth was studied, based on the solubility of C in Co. The surface area coverage of monolayer graphene was observed to increase with decreasing Co film thickness. A thorough Raman spectroscopic analysis reveals that graphene films, grown on an optimized Co film thickness, are principally composed of monolayer graphene. Transport properties of monolayer graphene films were investigated by fabrication of back-gated graphene field-effect transistors (GFETs), which exhibited high hole and electron mobility of ∼1600 cm²/V s and ∼1000 cm²/V s, respectively, and a low trap density of ∼1.2 × 10¹¹ cm^–2.

The realization of highly flexible and all-solid-state energy-storage devices strongly depends on both the electrical properties and mechanical integrity of the constitutive materials and the controlled assembly of electrode and solid electrolyte. Herein we report the preparation of all-solid-state flexible supercapacitors (SCs) through the easy assembly of functionalized reduced graphene oxide (f-RGO) thin films (as electrode) and solvent-cast Nafion electrolyte membranes (as electrolyte and separator). In particular, the f-RGO-based SCs (f-RGO-SCs) showed a 2-fold higher specific capacitance (118.5 F/g at 1 A/g) and rate capability (90% retention at 30 A/g) compared to those of all-solid-state graphene SCs (62.3 F/g at 1A/g and 48% retention at 30 A/g). As proven by the 4-fold faster relaxation of the f-RGO-SCs than that of the RGO-SCs and more capacitive behavior of the former at the low-frequency region, these results were attributed to the facilitated ionic transport at the electrical double layer by means of the interfacial engineering of RGO by Nafion. Moreover, the superiority of all-solid-state flexible f-RGO-SCs was demonstrated by the good performance durability under the 1000 cycles of charging and discharging due to the mechanical integrity as a consequence of the interconnected networking structures. Therefore, this research provides new insight into the rational design and fabrication of all-solid-state flexible energy-storage devices as well as the fundamental understanding of ion and charge transport at the interface.

The work investigates the source of toxicity of copper oxide nanoparticles (CuO NPs) with respect to its leaching characteristic and speciation. Complexation-mediated leaching of CuO NPs by amino acids was identified as the source of toxicity toward Escherichia coli, the model microorganism used in the current study. The leached copper–peptide complex induces a multiple-fold increase in intracellular reactive oxygen species generation and reduces the fractions of viable cells, resulting in the overall inhibition of biomass growth. The cytotoxicity of the complex leachate is however different from that of equivalent soluble copper salts (nitrates and sulfates). A pH-dependent copper speciation during the addition of copper salts gives rise to uncoordinated copper ions, which in turn result in greater toxicity and cell lysis, the latter of which was not observed for CuO NPs even at comparable pH. Since leaching did not occur with micrometer-sized CuO, no cytotoxicty effect was observed, thus highlighting the prominence of materials toxicity at the nanoscale.

Eight fascinating sp²- and sp³-hybridized carbon allotropes have been uncovered using a newly developed ab initio particle-swarm optimization methodology for crystal structure prediction. These crystalline allotropes can be viewed respectively as three-dimensional (3D) polymers of (4,0), (5,0), (7,0), (8,0), (9,0), (3,3), (4,4), and (6,6) carbon nanotubes, termed 3D-(n, 0) or 3D-(n, n) carbons. The ground-state energy calculations show that the carbons all have lower energies than C₆₀ fullerene, and some are energetically more stable than the van der Waals packing configurations of their nanotube parents. Owing to their unique configurations, they have distinctive electronic properties, high Young’s moduli, high tensile strength, ultrahigh hardness, good ductility, and low density, and may be potentially applied to a variety of needs.

A reverse microemulsion synthesis was used to prepare amine-functionalized silica nanoparticles of three distinct sizes (i.e., 50, 100, and 200 nm) with similar amine content. The resulting hybrid nanoparticles, consisting of N-(6-aminohexyl)aminopropyltrimethoxysilane and tetraethoxysilane, were highly monodisperse in size. N-Diazeniumdiolate nitric oxide (NO) donors were subsequently formed on secondary amines while controlling reaction conditions to keep the total amount of NO released constant for each particle size. The bactericidal efficacy of the NO-releasing nanoparticles against Pseudomonas aeruginosa increased with decreasing particle size. Additionally, smaller diameter nanoparticles were found to associate with the bacteria at a faster rate and to a greater extent than larger particles. Neither control (non-NO-releasing) nor NO-releasing particles exhibited toxicity toward L929 mouse fibroblasts at concentrations above their respective minimum bactericidal concentrations. This study represents the first investigation of the bactericidal efficacy of NO-releasing silica nanoparticles as a function of particle size.

Lithiation of individual multiwalled carbon nanotubes (MWCNTs) was conducted in situ inside a transmission electron microscope. Upon lithiation, the intertube spacing increased from 3.4 to 3.6 Å, corresponding to about 5.9% radial and circumferential expansions and ∼50 GPa tensile hoop stress on the outermost tube wall. The straight tube walls became distorted after lithiation. In situ compression and tension tests show that the lithiated MWCNTs were brittle with sharp fracture edges. Such a failure mode is in stark contrast with that of the pristine MWCNTs which are extremely flexible and fail in a “sword-in-sheath” manner upon tension. The lithiation-induced embrittlement is attributed to the mechanical effect of a “point-force” action posed by the intertubular lithium that induces the stretch of carbon–carbon bonds in addition to that by applied strain, as well as the chemical effect of electron transfer from lithium to the antibonding π orbital that weakens the carbon–carbon bond. The combined mechanical and chemical weakening leads to a considerable decrease of the fracture strain in lithiated MWCNTs. Our results provide direct evidence and understanding of the degradation mechanism of carbonaceous anodes in lithium ion batteries.

As optical frequency nanoantennas, reduced-symmetry plasmonic nanoparticles have light-scattering properties that depend strongly on geometry, orientation, and variations in dielectric environment. Here we investigate how these factors influence the spectral and angular dependence of light scattered by Au nanocups. A simple dielectric substrate causes the axial, electric dipole mode of the nanocup to deviate substantially from its characteristic cos² θ free space scattering profile, while the transverse, magnetic dipole mode remains remarkably insensitive to the presence of the substrate. Nanoscale irregularities of the nanocup rim and the local substrate permittivity have a surprisingly large effect on the spectral- and angle-dependent light-scattering properties of these structures.

In the last few decades, nanoparticles (NPs) have been recognized as promising candidates for starting a new revolution in science and technology due to their unusual properties, attracting the attention of physicists, chemists, biologists, and engineers. The aim of this study is to evaluate the toxicities (at both cellular and molecular levels) of three forms of superparamagnetic iron oxide nanoparticles (SPIONs) of various surface chemistries (COOH, plain, and NH₂) through the comparison with gene expression patterns of three cell types (i.e., human heart, brain, and kidney). For this purpose, both an MTT assay and a DNA microarray analysis were applied in three human cell lines—HCM (heart), BE-2-C (brain), and 293T (kidney)—under the exposure to SPIONs-COOH, SPIONs-NH₂, and bare SPIONs. The specific gene alteration and hierarchical clustering revealed that SPIONs-COOH altered genes associated with cell proliferative responses due to their reactive oxygen species (ROS) properties. It was also found that the cell type can have quite a significant role in the definition of suitable pathways for detoxification of NPs, which has deep implications for the safe and high yield design of NPs for biomedical applications and will require serious consideration in the future.

Fluid flow inside carbon nanotubes is remarkable: transport of water and gases is nearly frictionless, and the small channel size results in selective transport of ions. Very recently, devices have been fabricated in which one narrow single-walled carbon nanotube spans a barrier separating electrolyte reservoirs. Ion current through these devices is about 2 orders of magnitude larger than predicted from the bulk resistivity of the electrolyte. Electroosmosis can drive these large excess currents if the tube both is charged and transports anions or cations preferentially. By building a nanofluidic field-effect transistor with a gate electrode embedded in the fluid barrier, we show that the tube carries a negative charge and the excess current is carried by cations. The magnitude of the excess current and its control by a gate electrode are correctly predicted by the Poisson–Nernst–Planck–Stokes equations.

Zebrafish is an aquatic organism that can be used for high content safety screening of engineered nanomaterials (ENMs). We demonstrate, for the first time, the use of high content bright-field and fluorescence-based imaging to compare the toxicological effect of transition metal oxide (CuO, ZnO, NiO, and Co₃O₄) nanoparticles in zebrafish embryos and larvae. High content bright-field imaging demonstrated potent and dose-dependent hatching interference in the embryos, with the exception of Co₃O₄ which was relatively inert. We propose that the hatching interference was due to the shedding of Cu and Ni ions, compromising the activity of the hatching enzyme, ZHE1, similar to what we previously proposed for Zn²⁺. This hypothesis is based on the presence of metal-sensitive histidines in the catalytic center of this enzyme. Co-introduction of a metal ion chelator, diethylene triamine pentaacetic acid (DTPA), reversed the hatching interference of Cu, Zn, and Ni. While neither the embryos nor larvae demonstrated morphological abnormalities, high content fluorescence-based imaging demonstrated that CuO, ZnO, and NiO could induce increased expression of the heat shock protein 70:enhanced green fluorescence protein (hsp70:eGFP) in transgenic zebrafish larvae. Induction of this response by CuO required a higher nanoparticle dose than the amount leading to hatching interference. This response was also DTPA-sensitive. We demonstrate that high content imaging of embryo development, morphological abnormalities, and HSP70 expression can be used for hazard ranking and determining the dose–response relationships leading to ENM effects on the development of the zebrafish embryo.

The photoluminescence (PL) of well dispersed molecules of a conjugated polymer, poly[2-methoxy-5-((2′-ethylhexyl)oxy)-1,4-phenylene-vinylene] (MEH-PPV), in an optically inert matrix manifested dramatic increases when the individual molecular strands were fully stretched. The PL increase rose with stretching and may reach several folds when the mechanical strain of the matrix polymer went beyond 550%. Strong polarization effects indicate that stretching individual polymer chains was responsible for the PL enhancement. This effect was attributed to suppression of electron–phonon interactions in the stress-rigidified polymer chain segments and may be useful for efficiency-enhanced polymer-based optoelectronic devices.

The growth of large-area hexagonal boron nitride (h-BN) monolayers on catalytic metal substrates is a topic of scientific and technological interest. We have used real-time microscopy during the growth process to study h-BN chemical vapor deposition (CVD) from borazine on Ru(0001) single crystals and thin films. At low borazine pressures, individual h-BN domains nucleate sparsely, grow to macroscopic dimensions, and coalescence to form a closed monolayer film. A quantitative analysis shows borazine adsorption and dissociation predominantly on Ru, with the h-BN covered areas being at least 100 times less reactive. We establish strong effects of hydrogen added to the CVD precursor gas in controlling the in-plane expansion and morphology of the growing h-BN domains. High-temperature exposure of h-BN/Ru to pure hydrogen causes the controlled edge detachment of B and N and can be used as a clean etching process for h-BN on metals.

Deterministic organization of nanostructures into microscale geometries is essential for the development of materials with novel mechanical, optical, and surface properties. We demonstrate scalable fabrication of 3D corrugated carbon nanotube (CNT) microstructures, via an iterative sequence of vertically aligned CNT growth and capillary self-assembly. Vertical microbellows and tilted microcantilevers are created over large areas, and these structures can have thin walls with aspect ratios exceeding 100:1. We show these structures can be used as out-of-plane microsprings with compliance determined by the wall thickness and number of folds.

We present calculations of impact ionization rates, carrier multiplication yields, and solar-power conversion efficiencies in solar cells based on quantum dots (QDs) of a semimetal, α-Sn. Using these results and previous ones on PbSe and PbS QDs, we discuss a strategy to select QDs with the highest carrier multiplication rate for more efficient solar cells. We suggest using QDs of materials with a close to zero band gap and a high multiplicity of the bands in order to favor the relaxation of photoexcited carriers by impact ionization. Even in that case, the improvement of the maximum solar-power conversion efficiency appears to be a challenging task.

Virus life stages often constitute a complex chain of events, difficult to track in vivo and in real-time. Challenges are associated with spatial and time limitations of current probes: most viruses are smaller than the diffraction limit of optical microscopes while the entire time scale of virus dynamics spans over 8 orders of magnitude. Thus, virus processes such as entry, disassembly, and egress have generally remained poorly understood. Here we discuss photothermal heterodyne imaging (PHI) as a possible alternative to fluorescence microscopy in the study of single virus-like nanoparticle (VNP) dynamics, with relevance in particular to virus uncoating. Being based on optical absorption rather than emission, PHI could potentially surpass some of the current limitations associated with fluorescent labels. As proof-of-principle, single VNPs self-assembled from 60 nm DNA-functionalized gold nanoparticles (DNA-Au NPs) encapsulated in a Gag protein shell of the human immunodeficiency virus (HIV-1) were imaged, and their photothermal response was compared with DNA-Au NPs. For the first time, the protein stoichiometry of a single virus-like particle was estimated by a method other than electron microscopy.

The culture of bone marrow derived mesenchymal stem cells (MSCs), as well as the control of its differentiation toward different tissue lineage, is a very important part of tissue engineering, where cells are combined with artificial scaffold to regenerate tissues. Graphene (G) and graphene oxide (GO) sheets are soft membranes with high in-plane stiffness and can potentially serve as a biocompatible, transferable, and implantable platform for stem cell culture. While the healthy proliferation of stem cells on various carbon platforms has been demonstrated, the chemical role of G and GO, if any, in guiding uncommitted stem cells toward differentiated cells is not known. Herein, we report that the strong noncovalent binding abilities of G allow it to act as a preconcentration platform for osteogenic inducers, which accelerate MSCs growing on it toward the osteogenic lineage. The molecular origin of accelerated differentation is investigated by studying the binding abilities of G and GO toward different growth agents. Interestingly, differentiation to adipocytes is greatly suppressed on G because insulin, which is a key regulator for the synthesis of fatty acids, is denatured upon π–π adsorption on G; in contrast, GO does not interfere with adipogenesis due to electrostatic binding with insulin. The different binding interactions and their subsequent influence on stem cell growth and differentiation are ascribed to different degrees of π–π stacking and electrostatic and hydrogen bonding mediated by G and GO.

It is commonly believed that nanomaterials cause nonspecific oxidative damage. Our mass spectrometry-based oxidative lipidomics analysis of all major phospholipid classes revealed highly selective patterns of pulmonary peroxidation after inhalation exposure of mice to single-walled carbon nanotubes. No oxidized molecular species were found in the two most abundant phospholipid classes: phosphatidylcholine and phosphatidylethanolamine. Peroxidation products were identified in three relatively minor classes of anionic phospholipids, cardiolipin, phosphatidylserine, and phosphatidylinositol, whereby oxygenation of polyunsaturated fatty acid residues also showed unusual substrate specificity. This nonrandom peroxidation coincided with the accumulation of apoptotic cells in the lung. A similar selective phospholipid peroxidation profile was detected upon incubation of a mixture of total lung lipids with H₂O₂/cytochrome c known to catalyze cardiolipin and phosphatidylserine peroxidation in apoptotic cells. The characterized specific phospholipid peroxidation signaling pathways indicate new approaches to the development of mitochondria-targeted regulators of cardiolipin peroxidation to protect against deleterious effects of pro-apoptotic effects of single-walled carbon nanotubes in the lung.

Laser cooling the center-of-mass motion of systems that exhibit Fano resonances is discussed. We find that cooling occurs for red or blue detuning of the laser frequency from resonance depending on the Fano factor associated with the resonance. The combination of the Doppler effect with the radiation cross-section quenching typical of quantum interference yields temperatures below the conventional Doppler limit. This scheme opens perspectives for controlling the motion of mesoscopic systems such as hybrid nanostructures at the quantum regime and the exploration of motional nonclassical states at the nanoscale.

Understanding the influence of interfacial structures on the nanoarchitecture mechanical properties is of particular importance for its mechanical applications. Due to a small size of constituting nanostructural units and a consequently high volume ratio of such interfacial regions, this question becomes crucial for the overall mechanical performance. Boron nitride bamboo-like nanotubes, called hereafter boron nitride nanobamboos (BNNBs), are composed of short BN nanotubular segments with specific interfaces at the bamboo-shaped joints. In this work, the mechanical properties of such structures are investigated by using direct in situ transmission electron microscopy tensile tests and molecular dynamics simulations. The mechanical properties and deformation behaviors are correlated with the interfacial structure under atomic resolution, and a geometry strengthening effect is clearly demonstrated. Due to the interlocked joint interfacial structures and compressive interfacial stresses, the deformation mechanism is switched from an interplanar sliding mode to an in-plane tensile elongation mode. As a result of such a specific geometry strengthening effect, the BNNBs show high tensile fracture strength and Young’s modulus up to 8.0 and 225 GPa, respectively.

UV irradiation of TiO₂ nanoparticles in the presence of Ag⁺ ions results in the quantitative reduction and deposition of silver on its surface. Continued UV irradiation following the deposition of Ag on the TiO₂ surface causes a blue shift in the surface plasmon peak from 430 to 415 nm as these particles become charged with excess electrons. Under UV irradiation, both the charging and discharging of electrons occur at different rates, thus allowing the system to attain a steady state. Upon stopping the UV irradiation, a fraction of these electrons remain stored. The electron storage is dependent on the amount of Ag deposited on TiO₂ nanoparticles with maximum capacity seen at 8.6 μM of Ag in a suspension containing 5.8 mM of TiO₂. Such electron charging and discharging processes in semiconductor–metal composites need to be taken into account while evaluating the plasmon resonance induced effects in photocatalysis and photoelectrochemistry.

We propose and demonstrate a hybrid lithographic technique capable of nanopatterning surfaces by optothermal decomposition of a polymeric film induced by a single metal nanoparticle. A tightly focused laser beam exerting a strong optical force onto the nanoparticle is used to move it inside the polymer film. Due to efficient plasmonic absorption of the laser light, the nanoparticle is heated up to temperatures of several hundred degrees, causing melting or even thermal decomposition of the polymer film. By this method, grooves less than 100 nm wide and tens of micrometers long can be directly milled in a polymer layer.

Carbon nanotube (CNT) networks on solid substrates have recently drawn attention as a means to direct the growth and differentiation of stem cells. However, it is still not clear whether cells can recognize individual CNTs with a sub-2 nm diameter, and directional nanostructured substrates such as aligned CNT networks have not been utilized to control cell behaviors. Herein, we report that human mesenchymal stem cells (hMSCs) grown on CNT networks could recognize the arrangement of individual CNTs in the CNT networks, which allowed us to control the growth direction and differentiation of the hMSCs. We achieved the directional growth of hMSCs following the alignment direction of the individual CNTs. Furthermore, hMSCs on aligned CNT networks exhibited enhanced proliferation and osteogenic differentiation compared to those on randomly oriented CNT networks. As a plausible explanation for the enhanced proliferation and osteogenic differentiation, we proposed mechanotransduction pathways triggered by high cytoskeletal tension in the aligned hMSCs. Our findings provide new insights regarding the capability of cells to recognize nanostructures smaller than proteins and indicate their potential applications for regenerative tissue engineering.

The heat generation and dissipation of an individual optically excited metallic single-walled carbon nanotube is characterized using a thermal sensor thin film of Al_0.94Ga_0.06N embedded with Er³⁺. The absorption cross section from an individual SWCNT excited at 532 nm is revealed from the steady-state temperature of the thermal sensor film. A maximum temperature of 4.3 K is observed when the SWCNT is excited with parallel polarization and an average intensity of 7 × 10¹⁰ W/m². From this temperature measurement, we determine an absorption cross section for the SWCNT of 9.4 × 10^–17 m²/μm using parallel polarization and 2.4 × 10^–17 m²/μm for perpendicular polarization. We establish a temperature difference between the SWCNT and the substrate of 315 K by converting the G band shift of the SWCNT into the local SWCNT temperature and scaling the measured film temperature to the local non-resolution-limited temperature rise. From the temperature difference and heat flux, we deduce a value of 6.6 MW/m²·K for the thermal interfacial conductance of a SWCNT sitting on a thin film of amorphous Al_0.94Ga_0.06N.

Smart windows that can reversibly alternate between extreme optical characteristics via clicking counteranions of different hydration energies were developed on glass substrates through the facile spray-casting of poly[2-(methacryloyloxy)ethyltrimethylammonium chloride-co-3-(trimethoxysilyl)propyl methacrylate]. The optical transmittance was either 90.9% or 0% over the whole spectral range when alternately immersed in solutions containing thiocyanate (SCN^–) or bis(trifluoromethane)sulfonimide (TFSI^–) ions, respectively. The extreme optical transitions were attributed to formation of microporous structures via the molecular aggregation of polyelectrolyte chains bearing TFSI^– ions in methanol. Because the smart windows were either highly transparent toward or completely blocking of incident light upon direct counterion exchange, this kind of nanotechnology may provide a new platform for efficiently conserving on energy usage in the interior of buildings.

This paper reports the first direct measurements of static friction force and interfacial shear strength between silicon (Si) nanowires (NWs) and poly(dimethylsiloxane) (PDMS). A micromanipulator is used to manipulate and deform the NWs under a high-magnification optical microscope in real time. The static friction force is measured based on “the most-bent state” of the NWs. The static friction and interface shear strength are found to depend on the ultraviolet/ozone (UVO) treatment of PDMS. The shear strength starts at 0.30 MPa without UVO treatment, increases rapidly up to 10.57 MPa at 60 min of treatment and decreases for longer treatment. Water contact angle measurements suggest that the UVO-induced hydrophobic-to-hydrophilic conversion of PDMS surface is responsible for the increase in the static friction, while the hydrophobic recovery effect contributes to the decrease. The static friction between NWs and PDMS is of critical relevance to many device applications of NWs including NW-based flexible/stretchable electronics, NW assembly and nanocomposites (e.g., supercapacitors). Our results will enable quantitative interface design and control for such applications.

Silver nanoprisms of a predominantly hexagonal shape have been prepared using a ligand combination of a strongly binding thiol, captopril, and charge-stabilizing citrate together with hydrogen peroxide as an oxidative etching agent and a strong base that triggered nanoprism formation. The role of the reagents and their interplay in the nanoprism synthesis is discussed in detail. The beneficial role of chloride ions to attain a high degree of reproducibility and monodispersity of the nanoprisms is elucidated. Control over the nanoprism width, thickness, and, consequently, plasmon resonance in the system has been demonstrated. One of the crucial factors in the nanoprism synthesis was the slow, controlled aggregation of thiolate-stabilized silver nanoclusters as the intermediates. The resulting superior monodispersity (better than ca. 10% standard deviation in lateral size and ca. 15% standard deviation in thickness (<1 nm variation)) and charge stabilization of the produced silver nanoprisms enabled the exploration of the rich diversity of the self-assembled morphologies in the system. Regular columnar assemblies of the self-assembled nanoprisms spanning 2–3 μm in length have been observed. Notably, the helicity of the columnar phases was evident, which can be attributed to the chirality of the strongly binding thiol ligand. Finally, the enhancement of Raman scattering has been observed after oxidative removal of thiolate ligands from the AgNPR surface.

Increasing interest has been devoted to synthesizing graphene (GR)-semiconductor nanocomposites as photocatalysts for potential applications, which is very similar to its forebear carbon nanotube (CNT)-semiconductor photocatalysts. Unfortunately, a thoughtful and inevitable comparison between GR- and CNT-semiconductors as photocatalysts is often neglected in literature. This situation may give incomplete or exaggerated information on the contribution role of GR to enhance the semiconductor photocatalytic activity, as compared to CNT. Thus, our knowledge regarding the specific advantage of GR over CNT on how to design more efficient GR-semiconductor nanocomposites and understanding the origin of their enhanced photocatalytic performance is far from satisfactory. By taking the TiO₂ semiconductor as an example, we conceptually demonstrate how to synthesize a more efficient GR-TiO₂ nanocomposite as a visible light photocatalyst toward selective oxidation of alcohols under mild conditions. Comparison between GR-TiO₂ and CNT-TiO₂ discloses the prominent advantage of GR over CNT on both controlling the morphology of GR-TiO₂ nanocomposite and enhancing the photocatalytic activity of TiO₂. This work clearly highlights the importance and necessity for a comparison investigation between GR- and CNT-semiconductors as photocatalysts, which will promote our in-depth fundamental understanding on the analogy and difference between GR and CNT on controlling the morphology of GR (or CNT)-semiconductor nanocomposites and enhancing the photocatalytic performance. Therefore, we appeal the photocatalysis community to pay attention to this respect rather than separately imposing hype on the miracle of GR in much the same way as its carbon forebears, which could significantly advance our rational fabrication of smart GR-semiconductor nanocomposites for artificial photosynthesis.

Detection and analysis of magnetic nanoobjects is a crucial task in modern diagnostic and therapeutic techniques applied to medicine and biology. Accomplishment of this task calls for the development and implementation of electronic elements directly in fluidic channels, which still remains an open and nontrivial issue. Here, we present a novel concept based on rolled-up nanotechnology for fabrication of multifunctional devices, which can be straightforwardly integrated into existing fluidic architectures. We apply strain engineering to roll-up a functional nanomembrane consisting of a magnetic sensor element based on [Py/Cu]₃₀ multilayers, revealing giant magnetoresistance (GMR). The comparison of the sensor’s characteristics before and after the roll-up process is found to be similar, allowing for a reliable and predictable method to fabricate high-quality ultracompact GMR devices. The performance of the rolled-up magnetic sensor was optimized to achieve high sensitivity to weak magnetic fields. We demonstrate that the rolled-up tube itself can be efficiently used as a fluidic channel, while the integrated magnetic sensor provides an important functionality to detect and respond to a magnetic field. The performance of the rolled-up magnetic sensor for the in-flow detection of ferromagnetic CrO₂ nanoparticles embedded in a biocompatible polymeric hydrogel shell is highlighted.

The newly developed hydrogen sensor, based on a network of ultrasmall pure palladium nanowires sputter-deposited on a filtration membrane, takes advantage of single palladium nanowires’ characteristics of high speed and sensitivity while eliminating their nanofabrication obstacles. However, this new type of sensor, like the single palladium nanowires, cannot distinguish hydrogen concentrations above 3%, thus limiting the potential applications of the sensor. This study reports hydrogen sensors based on a network of ultrasmall Cr-buffered Pd (Pd/Cr) nanowires on a filtration membrane. These sensors not only are able to outperform their pure Pd counterparts in speed and durability but also allow hydrogen detection at concentrations up to 100%. The new networks consist of a thin layer of palladium deposited on top of a Cr adhesion layer 1–3 nm thick. Although the Cr layer is insensitive to hydrogen, it enables the formation of a network of continuous Pd/Cr nanowires with thicknesses of the Pd layer as thin as 2 nm. The improved performance of the Pd/Cr sensors can be attributed to the increased surface area to volume ratio and to the confinement-induced suppression of the phase transition from Pd/H solid solution (α-phase) to Pd hydride (β-phase).

Hydrophobicity is a fundamental property that is responsible for numerous physical and biophysical aspects of molecular interactions in water. Peculiar behavior is expected for water in the vicinity of hydrophobic structures, such as nanopores. Indeed, hydrophobic nanopores can be found in two distinct states, dry and wet, even though the latter is thermodynamically unstable. Transitions between these two states are kinetically hindered in long pores but can be much faster in shorter pores. As it is demonstrated for the first time in this paper, these transitions can be induced by applying a voltage across a membrane with a single hydrophobic nanopore. Such voltage-induced gating in single nanopores can be realized in a reversible manner through electrowetting of inner walls of the nanopores. The resulting I–V curves of such artificial hydrophobic nanopores mimic biological voltage-gated channels.

Low targeting efficiency is one of the biggest limitations for nanoparticulate drug delivery system-based cancer therapy. In this study, an efficient approach for tumor-targeted drug delivery was developed with mesenchymal stem cells as the targeting vehicle and a silica nanorattle as the drug carrier. A silica nanorattle–doxorubicin drug delivery system was efficiently anchored to mesenchymal stem cells (MSCs) by specific antibody–antigen recognitions at the cytomembrane interface without any cell preconditioning. Up to 1500 nanoparticles were uploaded to each MSC cell with high cell viability and tumor-tropic ability. The intracellular retention time of the silica nanorattle was no less than 48 h, which is sufficient for cell-directed tumor-tropic delivery. In vivo experiments proved that the burdened MSCs can track down the U251 glioma tumor cells more efficiently and deliver doxorubicin with wider distribution and longer retention lifetime in tumor tissues compared with free DOX and silica nanorattle-encapsulated DOX. The increased and prolonged DOX intratumoral distribution further contributed to significantly enhanced tumor-cell apoptosis. This strategy has potential to be developed as a robust and generalizable method for targeted tumor therapy with high efficiency and low systematic toxicity.

In this report, we utilize the U-tube double diffusion device as a reliable, environmentally friendly method for the size-controlled synthesis of high-quality, single crystalline Pd nanowires. The nanowires grown in 200 and 15 nm polycarbonate template pores maintain diameters of 270 ± 45 nm and 45 ± 9 nm, respectively, and could be isolated either as individual nanowires or as ordered free-standing arrays. The growth mechanism of these nanowires has been extensively explored, and we have carried out characterization of the isolated nanowires, free-standing nanowire arrays, and cross sections of the filled template in order to determine that a unique two-step growth process predominates within the template pores. Moreover, as-prepared submicrometer and nanosized wires were studied by comparison with ultrathin 2 nm Pd nanowires in order to elucidate the size-dependent trend in oxygen reduction reaction (ORR) electrocatalysis. Subsequently, the desired platinum monolayer overcoating was reliably deposited onto the surface of the Pd nanowires by Cu underpotential deposition (UPD) followed by galvanic displacement of the Cu adatoms. The specific and platinum mass activity of the core–shell catalysts was found to increase from 0.40 mA/cm² and 1.01 A/mg to 0.74 mA/cm² and 1.74 A/mg as the diameter was decreased from the submicrometer size regime to the ultrathin nanometer range.

Vertical stacks of electrically confined quantum wires were demonstrated in devices with large areas. Multiple current plateaus and strong differential conductance oscillations were observed at above liquid nitrogen temperatures because of interlevel cascade transition of carriers. Our simulation results for charge transport, as well as interlevel infrared photoresponse red-shift, due to lateral electric field confinement show good agreement with experimental data.

Outstanding mechanical and optical properties of diamond nanoparticles in combination with their biocompatibility have recently attracted much attention. Modification of the surface chemistry and incorporation into a polymer is required in many applications of the nanodiamond. Nanodiamond powder with reactive amino groups (∼20% of the number of surface carbon atoms in each 5 nm particle) was produced in this work by covalent linking of ethylenediamine to the surface carboxyl groups via amide bonds. The synthesized material was reacted with epoxy resin, yielding a composite, in which nanodiamond particles are covalently incorporated into the polymer matrix. The effect of amino groups grafted on the nanodiamond on the curing chemistry of the epoxy resin was analyzed and taken into consideration. Covalently bonded nanodiamond–epoxy composites showed a three times higher hardness, 50% higher Young’s modulus, and two times lower creep compared to the composites in which the nanodiamond was not chemically linked to the matrix. Aminated nanodiamond produced and characterized in the present study may also find applications beyond the composites, for example, as a drug, protein, and gene delivery platform in biology and medicine, as a solid support in chromatography and separation science, and in solid state peptide synthesis.

The importance of the protein corona formed around nanoparticles upon entering a biological fluid has recently been highlighted. This corona is, when sufficiently long-lived, thought to govern the particles’ biological fate. However, even this long-lived “hard” corona evolves and re-equilibrates as particles pass from one biological fluid to another, and may be an important feature for long-term fate. Here we show the evolution of the protein corona as a result of transfer of nanoparticles from one biological fluid (plasma) into another (cytosolic fluid), a simple illustrative model for the uptake of nanoparticles into cells. While no direct comparison can be made to what would happen in, for example, the uptake pathway, the results confirm that significant evolution of the corona occurs in the second biological solution, but that the final corona contains a “fingerprint” of its history. This could be evolved to map the transport pathways utilized by nanoparticles, and eventually to predict nanoparticle fate and behavior.

We report the study of a novel linear magneto-resistance (MR) under perpendicular magnetic fields in Bi₂Se₃ nanoribbons. Through angular dependence magneto-transport experiments, we show that this linear MR is purely due to two-dimensional (2D) transport, in agreement with the recently discovered linear MR from 2D topological surface state in bulk Bi₂Te₃, and the linear MR of other gapless semiconductors and graphene. We further show that the linear MR of Bi₂Se₃ nanoribbons persists to room temperature, underscoring the potential of exploiting topological insulator nanomaterials for room-temperature magneto-electronic applications.

The opening of an electrical band gap in graphene is crucial for its application for logic circuits. Recent studies have shown that an energy gap in Bernal-stacked bilayer graphene can be generated by applying an electric displacement field. Molecular doping has also been proposed to open the electrical gap of bilayer graphene by breaking either in-plane symmetry or inversion symmetry; however, no direct observation of an electrical gap has been reported. Here we discover that the organic molecule triazine is able to form a uniform thin coating on the top surface of a bilayer graphene, which efficiently blocks the accessible doping sites and prevents ambient p-doping on the top layer. The charge distribution asymmetry between the top and bottom layers can then be enhanced simply by increasing the p-doping from oxygen/moisture to the bottom layer. The on/off current ratio for a bottom-gated bilayer transistor operated in ambient condition is improved by at least 1 order of magnitude. The estimated electrical band gap is up to ∼111 meV at room temperature. The observed electrical band gap dependence on the hole-carrier density increase agrees well with the recent density-functional theory calculations. This research provides a simple method to obtain a graphene bilayer transistor with a moderate on/off current ratio, which can be stably operated in air without the need to use an additional top gate.

A fabrication process for the monolithic integration of field-effect transistors based on individual carbon nanotubes and load resistors based on vacuum-evaporated carbon films into fast unipolar logic circuits on glass substrates is reported for the first time. The individual-carbon-nanotube transistors operate with relatively small gate-source and drain-source voltages of 1 V and combine large transconductance (up to 6 μS), large ON/OFF ratio (>10⁴), and short switching delay time constants (12 ns). The thin-film carbon load resistors provide linear current–voltage characteristics and resistances between 300 kΩ and 100 MΩ, depending on the layout of the resistors and the thickness of the vacuum-evaporated carbon films. Various combinational circuits (NAND, NOR, AND, OR gates) as well as a sequential circuit (S̅R̅ NAND latch) have been fabricated and characterized. Although these unipolar circuits cannot compete with optimized complementary circuits in terms of integration density and static power consumption, they offer the possibility of realizing air-stable, low-voltage integrated circuits with promising static and dynamic performance on unconventional substrates for large-area electronics applications, such as displays or sensors.