Optical Monitoring of Labile Zinc inside Metastatic Cells with Plasmonic ChemonanosensorsClick to copy article linkArticle link copied!
- Ting ZhouTing ZhouIntegrative Biomedical Materials and Nanomedicine Laboratory, Department of Medicine and Life Sciences, Universitat Pompeu Fabra, PRBB, Doctor Aiguader 88, Barcelona 08003, SpainMore by Ting Zhou
- Rubén VicenteRubén VicenteMolecular Physiology Laboratory, Department of Medicine and Life Sciences, Universitat Pompeu Fabra, PRBB, Carrer Doctor Aiguader 88, Barcelona 08003, SpainMore by Rubén Vicente
- Pilar Rivera-Gil*Pilar Rivera-Gil*Email: [email protected]Integrative Biomedical Materials and Nanomedicine Laboratory, Department of Medicine and Life Sciences, Universitat Pompeu Fabra, PRBB, Doctor Aiguader 88, Barcelona 08003, SpainMore by Pilar Rivera-Gil
Abstract
We report the development and characterization of an optical nanosensor for the detection of labile zinc in biological environments. The readout is based on surface-enhanced Raman scattering promoted by a Raman reporter conjugated to the inner plasmonic cavity of hollow silica nanocapsules. We quantify Zn2+ by obtaining the ratio between a Zn2+-sensitive band and a Zn2+-insensitive band. The Raman reporter measures within the range from 10–5 to 10–11 M and exhibits a limit of detection of 10–11.72 M. The nanosensor discriminates between intracellular and extracellular Zn2+ concentrations.
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Special Issue
Published as part of ACS Omega virtual special issue “Celebrating 50 Years of Surface Enhanced Spectroscopy”.
Introduction
Materials and Methods
Materials
Synthesis of Au@SiO2 Nanocapsules
Figure 1
Figure 1. Schematic representation of the working principle of our Raman probe for Zn2+.
Synthesis of the Zn2+-Nanosensor and Stability of Its Signal to pH
Physicochemical Characterization
Transmission Electron Microscopy
UV–Visible Spectroscopy
Dynamic Light Scattering
Surface-Enhanced Raman Spectroscopy
SERS Data Processing
Zn2+ Quantification in Solution and Calibration Curve
Calcium Measurements with NCs@TPY
Cell Culture
Zn2+ Measurements with Zinquin
Cellular Mapping of Zn2+ with SERS
Zn2+ Quantification with NCs@TPY in Metastatic vs Parental Cells
Results and Discussion
Synthesis and Characterization of the Nanosensor (NCs@TPY)
Figure 2
Figure 2. Synthesis and characterization of NCs@TPY. (A) UV–visible extinction profile of the NCs at different stages of the synthesis, i.e., PS template (blue), hollow with gold seeds (Auseeds@SiO2; red), and NCs after growing the gold seeds (Au@SiO2; black); (B) TEM image of Au@SiO2 NCs; and (C) Raman spectrum (red) of TPY in the powder form and SERS spectrum (blue) of the TPY attached to the plasmonic nanostructure of the NCs (NCs@TPY).
Calibration Curve between Zn2+ Concentration in Biological Media and Ratiometric SERS Sensing
Figure 3
Figure 3. Calibration curve between the Zn2+concentration in biological media and ratiometric SERS sensing. (A) SERS spectrum of NCs@TPY exposed to different Zn2+ concentrations (10–5, 10–6, 10–7, 10–8, 10–9, 10–10, 10–11, and 10–12 M and none) in ion-depleted cell growth medium. The Zn2+-sensitive (1034 cm–1) and insensitive (1021 cm–1) peaks are visible. Each spectrum is the average of 5 spectra. (B) The calibration curve is plotted based on the 1034–1021 cm–1 intensity ratio measured at each Zn2+ concentration.
Intracellular Zn2+ Sensing in Metastatic and Parental Breast Cancer Cells
Figure 4
Figure 4. Intracellular Zn2+ SERS mapping. MDA (A) and MDA-Zip4 (B) were incubated with NCs@TPY for 24 h and were exposed to different amounts of Zn2+ (0, 10, 50, and 100 μM) for 2 h. The measured area is 23 (l) × 21 (w) μm, and during each mapping, we acquired 56 spectra/area. Increasing values of the sensitive vs insensitive band ratio (I1034/I1021) correspond to an increase in the colored (red) area. A zoomed-in view of the scanned area is shown (scale bar 5 μm).
Figure 5
Figure 5. Zn2+quantification in metastatic and parental breast tumor cells. (A) Different breast cancer cells (MDA, MDA-Zip4, LM2, and BrM2 cells) were cultured in growth medium supplemented with different amounts of Zn2+ (10–5, 10–6, 10–7, 10–8, 10–9, 10–10, 10–11, and 10–12 M and none). NCs@TPY quantified the intracellular Zn2+ amount based on the intensity ratio of the sensitive (1034 cm–1) to insensitive (1021 cm–1) band.
Zn2+ (M) added | MDA | MDA-Zip4 | LM2 | BrM2 |
---|---|---|---|---|
0 | 10–14.42 | 10–13.74 | 10–10.52 | 10–10.48 |
10–5 | 10–8.67 | 10–5.98 | 10–2.56 | 10–2.31 |
10–6 | 10–9.28 | 10–7.49 | 10–4.36 | 10–3.99 |
10–7 | 10–10.04 | 10–7.81 | 10–5.47 | 10–4.90 |
10–8 | 10–10.11 | 10–8.43 | 10–6.30 | 10–5.47 |
10–9 | 10–10.80 | 10–9.70 | 10–6.85 | 10–6.13 |
10–10 | 10–11.81 | 10–10.21 | 10–7.56 | 10–7.97 |
10–11 | 10–13.20 | 10–11.63 | 10–8.53 | 10–8.91 |
10–12 | 10–14.54 | 10–12.52 | 10–12.74 | 10–11.86 |
LOD | 10–11.72 |
(cf., Table S1 for the extracellular values).
Figure 6
Figure 6. Differences of basal intracellular Zn2+ and Zn2+ acquisition capacity in different cells. (A) Different breast cancer cells (MDA, MDA-Zip4, LM2, and BrM2 cells) were cultured with NCs@TPY and exposed to ion-depleted GM without Zn2+ addition overnight. (B) Cells were also exposed to ion-depleted GM supplemented with different amounts of Zn2+ (10–5, 10–6, 10–7, 10–8, 10–9, 10–10, 10–11, and 10–12 M) overnight, and then, the basal level of Zn2+ was removed in each cell line. NCs@TPY quantified their intracellular Zn2+ amount based on the intensity ratio of the sensitive (1034 cm–1) to insensitive (1021 cm–1) band. (C) Quantitative values of the increment of Zn2+ from each cell line.
Conclusions
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.4c03631.
Additional results and methodology and additional information on all the sections of the article from the synthesis to the biological zinc quantification (PDF)
Terms & Conditions
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Acknowledgments
Pilar Rivera Gil acknowledges the Ministry of Science, Innovation and Universities (MICINN) and the AEI (AEI-PID2019-106755RB-I00 and PID2022-140423NB-I00) and the AGAUR (2021 SGR 00175 and 2021 PROD 00041) for financial support. T.Z. and Pilar Rivera Gil appreciate the financial support from the China Scholarship Council (CSC) by a State Scholarship Fund (NSCIS no. 202008350121). R.V. acknowledges AEI (PID2022-136511OB-I00) for financial support.
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- 21Tsoutsi, D.; Sanles-Sobrido, M.; Cabot, A.; Gil, P. R. Common Aspects Influencing the Translocation of SERS to Biomedicine. Curr. Med. Chem. 2018, 25 (35), 4638– 4652, DOI: 10.2174/0929867325666180105101841Google Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXisF2gsrrE&md5=c6b667f540f1bfca9dd47f32d9c35f1dCommon Aspects Influencing the Translocation of SERS to BiomedicineTsoutsi, Dionysia; Sanles-Sobrido, Marcos; Cabot, Andreu; Gil, Pilar-RiveraCurrent Medicinal Chemistry (2018), 25 (35), 4638-4652CODEN: CMCHE7; ISSN:0929-8673. (Bentham Science Publishers Ltd.)This review overviews the impact in biomedicine of surface enhanced. Raman scattering motivated by the great potential we believe this technique has. We present the advantages and limitations of this technique relevant to bioanal. in vitro and in vivo and how this technique goes beyond the state of the art of traditional anal., labeling and healthcare diagnostic technologies.
- 22Nyamekye, C. K. A.; Weibel, S. C.; Smith, E. A. Directional Raman scattering spectra of metal-sulfur bonds at smooth gold and silver substrates. J. Raman Spectrosc. 2021, 52 (7), 1246– 1255, DOI: 10.1002/jrs.6124Google ScholarThere is no corresponding record for this reference.
- 23Osterloh, F.; Hiramatsu, H.; Porter, R.; Guo, T. Alkanethiol-Induced Structural Rearrangements in Silica–Gold Core–Shell-type Nanoparticle Clusters: An Opportunity for Chemical Sensor Engineering. Langmuir 2004, 20, 5553– 5558, DOI: 10.1021/la0348719Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXktlWgsrs%253D&md5=f0884f31b60aeb4e70b7b8b5d090392dAlkanethiol-Induced Structural Rearrangements in Silica-Gold Core-Shell-type Nanoparticle Clusters: An Opportunity for Chemical Sensor EngineeringOsterloh, Frank; Hiramatsu, Hiroki; Porter, Rhiannon; Guo, TingLangmuir (2004), 20 (13), 5553-5558CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)Electrostatically bonded SiO2·Au nanoparticle clusters form by reaction of 3-aminopropylsilane-modified SiO2 spheres (470 nm) with citrate-coated gold nanoparticles (9.7 nm) in water. Reaction of the clusters with 0.01M KBr or HCl soln. induces desorption of the gold nanoparticles within minutes. Reaction of the clusters with alkanethiols CnH2n+1SH (n = 2-18) at 80° causes the gold nanoparticles to form stringlike gold nanoparticle structures for thiols with short alkane groups (n = 2, 3, 4) and hexagonally packed arrays of gold nanoparticles for thiols with long alkane groups (n = 5-18) on the silica surfaces. The structural changes indicate that the bonding between Au and SiO2 nanoparticles has changed from electrostatic to van der Waals. Elemental analyses show that the reaction with hexanethiol does not affect the Au/Si/O compn. of the SiO2·Au cluster, and Raman spectra on the hexanethiol-reacted cluster indicate the formation of a thiol SAM on the gold nanoparticles. The thiol-reacted SiO2·Au clusters display characteristic shifts of the absorption maxima in the visible spectra, and there is an inverse relation between these shifts and the lengths of the alkyl groups in the thiols. This relation can be understood in terms of the free electron model for metals. The use of SiO2·Au nanoparticle clusters as coulometric sensors for the qual. detection of thiols is discussed.
- 24Zhao, Y.; Newton, J. N.; Liu, J.; Wei, A. Dithiocarbamate-coated SERS substrates: sensitivity gain by partial surface passivation. Langmuir 2009, 25 (24), 13833– 13839, DOI: 10.1021/la902087eGoogle Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhtVSgt7nE&md5=86e589d11c53db79c8b94f04768c4614Dithiocarbamate-coated SERS substrates: sensitivity gain by partial surface passivationZhao, Yan; Newton, James N.; Liu, Jie; Wei, AlexanderLangmuir (2009), 25 (24), 13833-13839CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)The surface-enhanced Raman scattering (SERS) activity of nanoporous gold (NPG) can be boosted by controlled surface passivation. The SERS activities of unfunctionalized NPG were 1st optimized by etching substrates with NaI/I2 (triiodide) and using 2-mercaptopyridine (2-MP) as the probing analyte. Gains in analyte sensitivity were then achieved by passivating the superficial regions of the NPG substrates with dimethyldithiocarbamate (Me2DTC) while leaving the more recessed hot spots available for SERS detection. Partial surface passivation with DTCs increased the substrate sensitivity to chemisorptive analytes such as 2-MP by an order of magnitude, whereas surface satn. lowered the sensitivity by an order of magnitude. The partially passivated NPG films can also be functionalized with supramol. receptors for chemoselective SERS. Installation of a DTC-anchored terpyridine enabled the detection of divalent metal ions at trace levels, as detd. by the complexation-induced shift of a characteristic Raman peak of the metal ion receptor.
- 25Wright, D.; Lin, Q.; Berta, D.; Földes, T.; Wagner, A.; Griffiths, J.; Readman, C.; Rosta, E.; Reisner, E.; Baumberg, J. J. Mechanistic study of an immobilized molecular electrocatalyst by in situ gap-plasmon-assisted spectro-electrochemistry. Nature Catalysis 2021, 4 (2), 157– 163, DOI: 10.1038/s41929-020-00566-xGoogle Scholar25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXht1eqtbbP&md5=248c90dc521668f3b6106f7630a6c360Mechanistic study of an immobilized molecular electrocatalyst by in situ gap-plasmon-assisted spectro-electrochemistryWright, Demelza; Lin, Qianqi; Berta, Denes; Foldes, Tamas; Wagner, Andreas; Griffiths, Jack; Readman, Charlie; Rosta, Edina; Reisner, Erwin; Baumberg, Jeremy J.Nature Catalysis (2021), 4 (2), 157-163CODEN: NCAACP; ISSN:2520-1158. (Nature Research)Immobilized first-row transition metal complexes are potential low-cost electrocatalysts for selective CO2 conversion in the prodn. of renewable fuels. Mechanistic understanding of their function is vital for the development of next-generation catalysts, although the poor surface sensitivity of many techniques makes this challenging. Here, a nickel bis(terpyridine) complex is introduced as a CO2 redn. electrocatalyst in a unique electrode geometry, sandwiched by thiol-anchoring moieties between two gold surfaces. Gap-plasmon-assisted surface-enhanced Raman scattering spectroscopy coupled with d. functional theory calcns. reveals that the nature of the anchoring group plays a pivotal role in the catalytic mechanism. Our in situ spectro-electrochem. measurement enables the detection of as few as eight mols. undergoing redox transformations in individual plasmonic hotspots, together with the calibration of elec. fields via vibrational Stark effects. This advance allows rapid exploration of non-resonant redox reactions at the few-mol. level and provides scope for future mechanistic studies of single mols. [graphic not available: see fulltext].
- 26Hühn, D.; Kantner, K.; Geidel, C.; Brandholt, S.; De Cock, I.; Soenen, S. J. H.; Rivera_Gil, P.; Montenegro, J. M.; Braeckmans, K.; Müllen, K.; Nienhaus, G. U.; Klapper, M. Polymer-Coated NanoparticlesInteracting with Proteins and Cells:Focusing on the Sign of the Net Charge. ACS Nano 2013, 7 (4), 3253– 3263, DOI: 10.1021/nn3059295Google Scholar26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC3srjt12juw%253D%253D&md5=632e347ce062315a6488277e97a9a2c6Polymer-coated nanoparticles interacting with proteins and cells: focusing on the sign of the net chargeHuhn Dominik; Kantner Karsten; Geidel Christian; Brandholt Stefan; De Cock Ine; Soenen Stefaan J H; Rivera Gil Pilar; Montenegro Jose-Maria; Braeckmans Kevin; Mullen Klaus; Nienhaus G Ulrich; Klapper Markus; Parak Wolfgang JACS nano (2013), 7 (4), 3253-63 ISSN:.To study charge-dependent interactions of nanoparticles (NPs) with biological media and NP uptake by cells, colloidal gold nanoparticles were modified with amphiphilic polymers to obtain NPs with identical physical properties except for the sign of the charge (negative/positive). This strategy enabled us to solely assess the influence of charge on the interactions of the NPs with proteins and cells, without interference by other effects such as different size and colloidal stability. Our study shows that the number of adsorbed human serum albumin molecules per NP was not influenced by their surface charge. Positively charged NPs were incorporated by cells to a larger extent than negatively charged ones, both in serum-free and serum-containing media. Consequently, with and without protein corona (i.e., in serum-free medium) present, NP internalization depends on the sign of charge. The uptake rate of NPs by cells was higher for positively than for negatively charged NPs. Furthermore, cytotoxicity assays revealed a higher cytotoxicity for positively charged NPs, associated with their enhanced uptake.
- 27Jiang, X.; Valdeperez, D.; Nazarenus, M.; Wang, Z.; Stellacci, F.; Parak, W. J.; del Pino, P. Future Perspectives Towards the Use of Nanomaterials for Smart Food Packaging and Quality Control. Particle & Particle Systems Characterization 2015, 32 (4), 408– 416, DOI: 10.1002/ppsc.201400192Google ScholarThere is no corresponding record for this reference.
- 28Abhijnakrishna, R.; Magesh, K.; Ayushi, A.; Velmathi, S. Advances in the Biological Studies of Metal-Terpyridine Complexes: An Overview From 2012 to 2022. Coord. Chem. Rev. 2023, 496, 215380, DOI: 10.1016/j.ccr.2023.215380Google ScholarThere is no corresponding record for this reference.
- 29Sant’Ana, A. C.; Alves, W. A.; Santos, R. H. A.; Ferreira, A. M. D.; Temperini, M. L. A. The adsorption of 2,2′:6′,2″-terpyridine, 4′-(5-mercaptopentyl)-2,2′:6′,2″-terpyridinyl, and perchlorate on silver and copper surfaces monitored by SERS. Polyhedron 2003, 22 (13), 1673– 1682, DOI: 10.1016/S0277-5387(03)00325-5Google ScholarThere is no corresponding record for this reference.
- 30Carregal-Romero, S.; Montenegro, J. M.; Parak, W. J.; Rivera_Gil, P. Subcellular carrier-based optical ion-selective nanosensors. Front. Pharmacol 2012, 3, 70, DOI: 10.3389/fphar.2012.00070Google Scholar30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC38ngsVWksw%253D%253D&md5=cd1118809fb9f476d8eb7ac7b33779b6Subcellular carrier-based optical ion-selective nanosensorsCarregal-Romero Susana; Montenegro Jose-Maria; Parak Wolfgang J; Rivera Gil PilarFrontiers in pharmacology (2012), 3 (), 70 ISSN:.In this review, two carrier systems based on nanotechnology for real-time sensing of biologically relevant analytes (ions or other biological molecules) inside cells in a non-invasive way are discussed. One system is based on inorganic nanoparticles with an organic coating, whereas the second system is based on organic microcapsules. The sensor molecules presented within this work use an optical read-out. Due to the different physicochemical properties, both sensors show distinctive geometries that directly affect their internalization patterns. The nanoparticles carry the sensor molecule attached to their surfaces whereas the microcapsules encapsulate the sensor within their cavities. Their different size (nano and micro) enable each sensors to locate in different cellular regions. For example, the nanoparticles are mostly found in endolysosomal compartments but the microcapsules are rather found in phagolysosomal vesicles. Thus, allowing creating a tool of sensors that sense differently. Both sensor systems enable to measure ratiometrically however, only the microcapsules have the unique ability of multiplexing. At the end, an outlook on how more sophisticated sensors can be created by confining the nano-scaled sensors within the microcapsules will be given.
- 31Peana, M.; Pelucelli, A.; Chasapis, C. T.; Perlepes, S. P.; Bekiari, V.; Medici, S.; Zoroddu, M. A. Biological Effects of Human Exposure to Environmental Cadmium. Biomolecules 2022, 13 (1), 36, DOI: 10.3390/biom13010036Google ScholarThere is no corresponding record for this reference.
- 32Jin, L.; She, G.; Mu, L.; Shi, W. Highly uniform indicator-mediated SERS sensor platform for the detection of Zn2+. RSC Adv. 2016, 6 (20), 16555– 16560, DOI: 10.1039/C5RA28041AGoogle ScholarThere is no corresponding record for this reference.
- 33Lee, N.; Ly, N. H.; Kim, J. S.; Jung, H. S.; Joo, S.-W. A selective triarylmethine-based spectroscopic probe for Zn2+ ion monitoring. Dyes Pigm. 2019, 171, 107721, DOI: 10.1016/j.dyepig.2019.107721Google ScholarThere is no corresponding record for this reference.
- 34Li, D.; Ma, Y.; Duan, H.; Jiang, F.; Deng, W.; Ren, X. Fluorescent/SERS dual-sensing and imaging of intracellular Zn2+. Anal. Chim. Acta 2018, 1038, 148– 156, DOI: 10.1016/j.aca.2018.07.020Google Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtlOisb7F&md5=a06c154304f3b6fc2281fc08647d69cdFluorescent/SERS dual-sensing and imaging of intracellular Zn2+Li, Dan; Ma, Yadan; Duan, Huazhen; Jiang, Fei; Deng, Wei; Ren, XingangAnalytica Chimica Acta (2018), 1038 (), 148-156CODEN: ACACAM; ISSN:0003-2670. (Elsevier B.V.)A fluorescent and surface-enhanced Raman spectroscopy (SERS) dual-mode probe is developed for imaging of intracellular Zn2+ based on N-(2-(bis(pyridine-2-ylmethyl)amino)ethyl)-2-mercaptoacetamide (MDPA) modified gold nanoparticles (MDPA-GNPs). Benefiting from the chelation-enhanced fluorescence (CHEF) between MDPA-GNPs and Zn2+, the fluorescent intensities of MDPA-GNPs are substantially enhanced with the increment of Zn2+ concns., which can be clearly obsd. by the naked eye. Under physiol. conditions, the probe exhibits a stable response for Zn2+ from 1 μM to 120 μM, with a detection limit of 0.32 μM in aq. solns. The resultant MDPA-GNPs can be used for ultrasensitive SERS detection of Zn2+ because of the strong interparticle plasmonic coupling generated in the process of Zn2+-triggered MDPA-GNPs self-aggregation, with a low detection limit of 0.28 pM, which is eight order of magnitude lower than the United States Environmental Protection Agency (US EPA)-defined limit (76 μM) in drinkable water. More importantly, the proposed probe can be applied for efficient detection of intracellular Zn2+ with excellent biocompatibility and cellular imaging capability. Therefore, a highly sensitive and selective nanosensor has been demonstrated for both reliable quant. detection of Zn2+ in aq. soln. and real-time imaging of intracellular Zn2+, suggesting its significant potential utility in bioanal. and biomedical detection in the future.
- 35Zhu, L.; Yuan, Z.; Simmons, J. T.; Sreenath, K. Zn(II)-coordination modulated ligand photophysical processes - the development of fluorescent indicators for imaging biological Zn(II) ions. RSC Adv. 2014, 4 (39), 20398– 20440, DOI: 10.1039/C4RA00354CGoogle ScholarThere is no corresponding record for this reference.
- 36Hancock, R. D.; Martell, A. E. Ligand design for selective complexation of metal ions in aqueous solution. Chem. Rev. 1989, 89 (8), 1875– 1914, DOI: 10.1021/cr00098a011Google Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL1MXmsVWiurY%253D&md5=22b2ce07e68c61d4db06b2c2f0bd164fLigand design for selective complexation of metal ions in aqueous solutionHancock, Robert D.; Martell, Arthur E.Chemical Reviews (Washington, DC, United States) (1989), 89 (8), 1875-914CODEN: CHREAY; ISSN:0009-2665.A review on the role of steric strain in ligand design for size-match selectivity of macrocycles toward metal ions. About 155 res.
- 37Hancock, R. D. Molecular mechanics calculations and metal ion recognition. Acc. Chem. Res. 1990, 23 (8), 253– 257, DOI: 10.1021/ar00176a003Google Scholar37https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3cXkvVCqtbg%253D&md5=f767ffc78196895ff33f9e285601b7a8Molecular mechanics calculations and metal ion recognitionHancock, Robert D.Accounts of Chemical Research (1990), 23 (8), 253-7CODEN: ACHRE4; ISSN:0001-4842.A review with 39 refs. The results of authors studies on the relation between the cations size and the stability of a complex with a tetraaza microcycle were examd. and compared with results of mol. mechanics calcns.
- 38Ejarque, D.; Calvet, T.; Font-Bardia, M.; Pons, J. Steric crowding of a series of pyridine based ligands influencing the photophysical properties of Zn(II) complexes. CrystEngComm 2021, 23 (35), 6199– 6213, DOI: 10.1039/d1ce00833aGoogle ScholarThere is no corresponding record for this reference.
- 39Pearson, R. G. Hard and Soft Acids and Bases. J. Chem. Educ. 1968, 45 (9), 581, DOI: 10.1021/ed045p581Google Scholar39https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaF1cXltVShs74%253D&md5=d8780153780b30b62dae6309891fb283Hard and soft acids and bases (HSAB). I. Fundamental principlesPearson, Ralph G.Journal of Chemical Education (1968), 45 (9), 581-7CODEN: JCEDA8; ISSN:0021-9584."The principle of hard and soft acids and bases," which classified acids and bases as hard, soft, or borderline, is discussed. The rule states that hard acids prefer to bind to hard bases and soft acids prefer to bind to soft bases. The use of the rule for predicting chem. behavior, and in correlating the vast amt. of chem. information at hand is discussed.
- 40Pearson, R. G. Hard and soft acids and bases, HSAB, part 1: Fundamental principles. J. Chem. Educ. 1968, 45 (9), 581, DOI: 10.1021/ed045p581Google Scholar40https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaF1cXltVShs74%253D&md5=d8780153780b30b62dae6309891fb283Hard and soft acids and bases (HSAB). I. Fundamental principlesPearson, Ralph G.Journal of Chemical Education (1968), 45 (9), 581-7CODEN: JCEDA8; ISSN:0021-9584."The principle of hard and soft acids and bases," which classified acids and bases as hard, soft, or borderline, is discussed. The rule states that hard acids prefer to bind to hard bases and soft acids prefer to bind to soft bases. The use of the rule for predicting chem. behavior, and in correlating the vast amt. of chem. information at hand is discussed.
- 41Wang, S.; Cao, J.; Jia, W.; Guo, W.; Yan, S.; Wang, Y.; Zhang, P.; Chen, H. Y.; Huang, S. Single molecule observation of hard-soft-acid-base (HSAB) interaction in engineered Mycobacterium smegmatis porin A (MspA) nanopores. Chem. Sci. 2020, 11 (3), 879– 887, DOI: 10.1039/C9SC05260GGoogle Scholar41https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitlGgsrjE&md5=d26bcf0b5af36e0b047ca98d385684fdSingle molecule observation of hard-soft-acid-base (HSAB) interaction in engineered Mycobacterium smegmatis porin A (MspA) nanoporesWang, Sha; Cao, Jiao; Jia, Wendong; Guo, Weiming; Yan, Shuanghong; Wang, Yuqin; Zhang, Panke; Chen, Hong-Yuan; Huang, ShuoChemical Science (2020), 11 (3), 879-887CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)In the formation of coordination interactions between metal ions and amino acids in natural metalloproteins, the bound metal ion is crit. either for the stabilization of the protein structure or as an enzyme co-factor. Though extremely small in size, metal ions, when bound to the restricted environment of an engineered biol. nanopore, result in detectable perturbations during single channel recordings. All reported work of this kind was performed with engineered α-hemolysin nanopores and the obsd. events appear to be extremely small in amplitude (∼1-3 pA). We speculate that the cylindrical pore restriction of a-hemolysin may not be optimal for probing extremely small analytes. Mycobacterium smegmatis porin A (MspA), a conical shaped nanopore, was engineered to interact with Ca2+, Mn2+, Co2+, Ni2+, Zn2+, Pb2+ and Cd2+ and a systematically larger event amplitude (up to 10 pA) was obsd. The measured rate const. suggests that the coordination of a single ion with an amino acid follows hard-soft-acid-base theory, which has never been systematically validated in the case of a single mol. By adjusting the measurement pH from 6.8 to 8.0, the duration of a single ion binding event could be modified with a ∼46-fold time extension. The phenomena reported suggest MspA to be a superior engineering template for probing a variety of extremely small analytes, such as monat. and polyat. ions, small mols. or chem. intermediates, and the principle of hard-soft-acid-base interaction may be instructive in the pore design.
- 42Vogel-Gonzalez, M.; Musa-Afaneh, D.; Rivera Gil, P.; Vicente, R. Zinc Favors Triple-Negative Breast Cancer’s Microenvironment Modulation and Cell Plasticity. Int. J. Mol. Sci. 2021, 22 (17), 9188, DOI: 10.3390/ijms22179188Google ScholarThere is no corresponding record for this reference.
- 43Nowakowski, A. B.; Petering, D. H. Reactions of the fluorescent sensor, Zinquin, with the zinc-proteome: adduct formation and ligand substitution. Inorg. Chem. 2011, 50 (20), 10124– 10133, DOI: 10.1021/ic201076wGoogle ScholarThere is no corresponding record for this reference.
- 44Zalewski, P. D.; Forbes, I. J.; Betts, W. H. Correlation of apoptosis with change in intracellular labile Zn(II) using Zinquin [(2-methyl-8-p-toluenesulphonamido-6-quinolyloxy)acetic acid], a new specific fluorescent probe for Zn(II). Biochem. J. 1993, 296, 403– 408, DOI: 10.1042/bj2960403Google Scholar44https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2cXjvVer&md5=8ccb1d326f48b1cefce05f36611b2990Correlation of apoptosis with change in intracellular labile zinc(II) using zinquin [(2-methyl-8-p-toluenesulfonamido-6-quinolyloxy)acetic acid], a new specific fluorescent probe for zinc(II)Zalewski, Peter D.; Forbes, Ian J.; Betts, W. HenryBiochemical Journal (1993), 296 (2), 403-8CODEN: BIJOAK; ISSN:0264-6021.Zinquin, a membrane-permeant fluorophore specific for Zn(II), was used with spectrofluorometry and video image anal. to reveal and quantify labile intracellular Zn. Zinquin labeled human chronic-lymphocytic-leukemia lymphocytes, rat splenocytes and thymocytes with a weak diffuse fluorescence that was quenched when intracellular Zn was chelated with N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN) and was greatly intensified by pretreatment of cells with the Zn ionophore pyrithione and exogenous Zn. There was substantial heterogeneity of labile Zn among ionophore-treated cells, and fluorescence was largely extranuclear. The av. contents of labile Zn in human leukemic lymphocytes, rat splenocytes and rat thymocytes were approx. 20, 31 and 14 pmol/106 cells resp. Morphol. changes and internucleosomal DNA fragmentation indicated substantial apoptosis in these cells when the level of intracellular labile Zn was decreased by treatment with TPEN. Conversely, increasing labile Zn by pretreatment with Zn plus pyrithione suppressed both spontaneous DNA fragmentation and that induced by the potent apoptosis-induced agents colchicine and dexamethasone. These results suggest that prevention of apoptosis is a function of labile Zn, and that a redn. below a threshold concn. in this Zn pool induces apoptosis.
- 45Chen, Q. G.; Zhang, Z.; Yang, Q.; Shan, G. Y.; Yu, X. Y.; Kong, C. Z. The role of zinc transporter ZIP4 in prostate carcinoma. Urol Oncol 2012, 30 (6), 906– 911, DOI: 10.1016/j.urolonc.2010.11.010Google ScholarThere is no corresponding record for this reference.
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Abstract
Figure 1
Figure 1. Schematic representation of the working principle of our Raman probe for Zn2+.
Figure 2
Figure 2. Synthesis and characterization of NCs@TPY. (A) UV–visible extinction profile of the NCs at different stages of the synthesis, i.e., PS template (blue), hollow with gold seeds (Auseeds@SiO2; red), and NCs after growing the gold seeds (Au@SiO2; black); (B) TEM image of Au@SiO2 NCs; and (C) Raman spectrum (red) of TPY in the powder form and SERS spectrum (blue) of the TPY attached to the plasmonic nanostructure of the NCs (NCs@TPY).
Figure 3
Figure 3. Calibration curve between the Zn2+concentration in biological media and ratiometric SERS sensing. (A) SERS spectrum of NCs@TPY exposed to different Zn2+ concentrations (10–5, 10–6, 10–7, 10–8, 10–9, 10–10, 10–11, and 10–12 M and none) in ion-depleted cell growth medium. The Zn2+-sensitive (1034 cm–1) and insensitive (1021 cm–1) peaks are visible. Each spectrum is the average of 5 spectra. (B) The calibration curve is plotted based on the 1034–1021 cm–1 intensity ratio measured at each Zn2+ concentration.
Figure 4
Figure 4. Intracellular Zn2+ SERS mapping. MDA (A) and MDA-Zip4 (B) were incubated with NCs@TPY for 24 h and were exposed to different amounts of Zn2+ (0, 10, 50, and 100 μM) for 2 h. The measured area is 23 (l) × 21 (w) μm, and during each mapping, we acquired 56 spectra/area. Increasing values of the sensitive vs insensitive band ratio (I1034/I1021) correspond to an increase in the colored (red) area. A zoomed-in view of the scanned area is shown (scale bar 5 μm).
Figure 5
Figure 5. Zn2+quantification in metastatic and parental breast tumor cells. (A) Different breast cancer cells (MDA, MDA-Zip4, LM2, and BrM2 cells) were cultured in growth medium supplemented with different amounts of Zn2+ (10–5, 10–6, 10–7, 10–8, 10–9, 10–10, 10–11, and 10–12 M and none). NCs@TPY quantified the intracellular Zn2+ amount based on the intensity ratio of the sensitive (1034 cm–1) to insensitive (1021 cm–1) band.
Figure 6
Figure 6. Differences of basal intracellular Zn2+ and Zn2+ acquisition capacity in different cells. (A) Different breast cancer cells (MDA, MDA-Zip4, LM2, and BrM2 cells) were cultured with NCs@TPY and exposed to ion-depleted GM without Zn2+ addition overnight. (B) Cells were also exposed to ion-depleted GM supplemented with different amounts of Zn2+ (10–5, 10–6, 10–7, 10–8, 10–9, 10–10, 10–11, and 10–12 M) overnight, and then, the basal level of Zn2+ was removed in each cell line. NCs@TPY quantified their intracellular Zn2+ amount based on the intensity ratio of the sensitive (1034 cm–1) to insensitive (1021 cm–1) band. (C) Quantitative values of the increment of Zn2+ from each cell line.
References
This article references 45 other publications.
- 1Zhang, X.-a.; Lovejoy, K. S.; Jasanoff, A.; Lippard, S. J. Water-soluble porphyrins as a dual-function molecular imaging platform for MRI and fluorescence zinc sensing. Proc. Natl. Acad. Sci. U.S.A. 2007, 104 (26), 10780– 10785, DOI: 10.1073/pnas.07023931041https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXnsV2ltb4%253D&md5=767696789f3fdeb1241d1af1eec97aeeWater-soluble porphyrins as a dual-function molecular imaging platform for MRI and fluorescence zinc sensingZhang, Xiao-an; Lovejoy, Katherine S.; Jasanoff, Alan; Lippard, Stephen J.Proceedings of the National Academy of Sciences of the United States of America (2007), 104 (26), 10780-10785CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)We report a mol. platform for dual-function fluorescence/MRI sensing of mobile zinc. Zinc-selective binding units were strategically attached to a water-sol. porphyrin template. The synthetic strategy for achieving the designed target ligand is flexible and convenient, and the key intermediates can be applied as general building blocks for the construction of other metal sensors based on a similar mechanism. The metal-free form, (DPA-C2)2-TPPS3 (1), where DPA is dipicolylamine and TPPS3 is 5-phenyl-10,15,20-tris(4-sulfonatophenyl)porphine, is an excellent fluorescent sensor for zinc. It has certain superior phys. properties compared with earlier-generation zinc sensors including emission in the red and near-IR regions [λem = 645 nm (s) and 715 nm (m)], with a large Stokes shift of >230 nm. The fluorescence intensity of 1 increases by >10-fold upon zinc binding. The fluorescence "turn-on" is highly selective for zinc vs. other divalent metal ions and is relatively pH-insensitive within the biol. relevant pH window. The manganese deriv., [(DPA-C2)2-TPPS3Mn(III)] (2), switches the function of the mol. to generate an MRI contrast agent. In the presence of zinc, the relaxivity of 2 in aq. soln. is significantly altered, which makes it a promising zinc MRI sensor. Both metal-free and Mn(III)-inserted forms are efficiently taken up by live cells, and the intracellular zinc can be imaged by either fluorescence or MR, resp. We anticipate that in vivo applications of the probes will facilitate a deeper understanding of the physiol. roles of zinc and allow detection of abnormal zinc homeostasis for pathol. diagnoses.
- 2Hambidge, M. Human zinc deficiency. J. Nutr. 2000, 130 (5), 1344S– 1349S, DOI: 10.1093/jn/130.5.1344S2https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3cXivFKnu7g%253D&md5=68d17bd0a73ea3bd48e1653592ca0bbaHuman zinc deficiencyHambidge, MichaelJournal of Nutrition (2000), 130 (5S), 1344S-1349SCODEN: JONUAI; ISSN:0022-3166. (American Society for Nutritional Sciences)A review with 52 refs. The topics include the biochem. and biol. role of zinc in human nutrition, history of human zinc deficiency research, clin. symptoms of zinc deficiency (growth delay, diarrhea, pneumonia, infections, disturbed neuropsychol. performance, abnormalities of fetal development), biomarkers for mild zinc deficiency, public health significance of zinc deficiency in the developing world, and status of zinc nutriture in the US. There is a need for better understanding of human zinc metab. and homeostasis at mol., cellular, organ-system, and whole body levels and of factors that affect zinc bioavailability. Potential strategies for the prevention and management of human zinc deficiency are outlined.
- 3Craddock, T. J.; Tuszynski, J. A.; Chopra, D.; Casey, N.; Goldstein, L. E.; Hameroff, S. R.; Tanzi, R. E. The zinc dyshomeostasis hypothesis of Alzheimer’s disease. PLoS One 2012, 7 (3), e33552 DOI: 10.1371/journal.pone.0033552There is no corresponding record for this reference.
- 4Yan, X.; Kim, J. J.; Jeong, H. S.; Moon, Y. K.; Cho, Y. K.; Ahn, S.; Jun, S. B.; Kim, H.; You, Y. Low-Affinity Zinc Sensor Showing Fluorescence Responses with Minimal Artifacts. Inorg. Chem. 2017, 56 (8), 4332– 4346, DOI: 10.1021/acs.inorgchem.6b027864https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXlsFSlsLc%253D&md5=f9010a2f3f6f7ce9d29600504f688309Low-Affinity Zinc Sensor Showing Fluorescence Responses with Minimal ArtifactsYan, Xinhao; Kim, Jin Ju; Jeong, Hye Sun; Moon, Yu Kyung; Cho, Yoon Kyung; Ahn, Soyeon; Jun, Sang Beom; Kim, Hakwon; You, YoungminInorganic Chemistry (2017), 56 (8), 4332-4346CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)The study of the zinc biol. requires mol. probes with proper zinc affinity. The authors developed a low-affinity zinc probe (HBO-ACR) based on an azacrown ether (ACR) and an 2-(2-hydroxyphenyl)benzoxazole (HBO) fluorophore. This probe design imposed pos. charge in the vicinity of a zinc coordination center, which enabled fluorescence turn-on responses to high levels of zinc without being affected by the pH and the presence of other transition-metal ions. Steady-state and transient photophys. studies suggested that such a high tolerance benefits from orchestrated actions of proton-induced nonradiative and zinc-induced radiative control. The zinc bioimaging utility of HBO-ACR has been fully demonstrated using human pancreas epidermoid carcinoma, PANC-1 cells, and rodent hippocampal neurons from cultures and acute brain slices. The results obtained through the authors' studies established the validity of incorporating pos. charged ionophores for the creation of low-affinity probes for the visualization of biometals.
- 5Frederickson, C. J.; Suh, S. W.; Silva, D.; Frederickson, C. J.; Thompson, R. B. Importance of zinc in the central nervous system: the zinc-containing neuron. J. Nutr. 2000, 130 (5), 1471S– 1483S, DOI: 10.1093/jn/130.5.1471S5https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3cXivFKms7k%253D&md5=7f849c8bc1bb364de55afba33e7b07b5Importance of zinc in the central nervous system: the zinc-containing neuronFrederickson, Christopher J.; Suh, Sang Won; Silva, David; Frederickson, Cathy J.; Thompson, Richard B.Journal of Nutrition (2000), 130 (5S), 1471S-1483SCODEN: JONUAI; ISSN:0022-3166. (American Society for Nutritional Sciences)A review with 111 refs. Zinc is essential to the structure and function of myriad proteins, including regulatory, structural and enzymic. It is estd. that up to 1% of the human genome codes for zinc finger proteins. In the central nervous system, zinc has an addnl. role as a neurosecretory product or cofactor. In this role, zinc is highly concd. in the synaptic vesicles of a specific contingent of neurons, called "zinc-contg." neurons. Zinc-contg. neurons are a subset of glutamatergic neurons. The zinc in the vesicles probably exceeds 1 mmol/L in concn. and is only weakly coordinated with any endogenous ligand. Zinc-contg. neurons are found almost exclusively in the forebrain, where in mammals they have evolved into a complex and elaborate associational network that interconnects most of the cerebral cortices and limbic structures. Indeed, one of the intriguing aspects of these neurons is that they compose somewhat of a chemospecific "private line" of the mammalian cerebral cortex. The present review outlines (1) the methods used to discover, define and describe zinc-contg. neurons; (2) the neuroarchitecture and synaptol. of zinc-contg. neural circuits; (3) the physiol. of regulated vesicular zinc release; (4) the "life cycle" and mol. biol. of vesicular zinc; (5) the importance of synaptically released zinc in the normal and pathol. processes of the cerebral cortex; and (6) the role of specific and nonspecific stressors in the release of zinc.
- 6Kim, J. W.; Byun, M. S.; Yi, D.; Lee, J. H.; Kim, M. J.; Jung, G.; Lee, J. Y.; Kang, K. M.; Sohn, C. H.; Lee, Y. S. Serum zinc levels and in vivo beta-amyloid deposition in the human brain. Alzheimers Res. Ther 2021, 13 (1), 190, DOI: 10.1186/s13195-021-00931-3There is no corresponding record for this reference.
- 7Fukunaka, A.; Fujitani, Y. Role of Zinc Homeostasis in the Pathogenesis of Diabetes and Obesity. Int. J. Mol. Sci. 2018, 19 (2), 476, DOI: 10.3390/ijms190204767https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXit1Squ7zP&md5=0e984afaab5627f4b9de9e13e7ec1176Role of zinc homeostasis in the pathogenesis of diabetes and obesityFukunaka, Ayako; Fujitani, YoshioInternational Journal of Molecular Sciences (2018), 19 (2), 476/1-476/14CODEN: IJMCFK; ISSN:1422-0067. (MDPI AG)Zinc deficiency is a risk factor for obesity and diabetes. However, until recently, the underlying mol. mechanisms remained unclear. The breakthrough discovery that the common polymorphism in zinc transporter SLC30A8/ZnT8 may increase susceptibility to type 2 diabetes provided novel insights into the role of zinc in diabetes. Our group and others showed that altered ZnT8 function may be involved in the pathogenesis of type 2 diabetes, indicating that the precise control of zinc homeostasis is crucial for maintaining health and preventing various diseases, including lifestyle-assocd. diseases. Recently, the role of the zinc transporter ZIP13 in the regulation of beige adipocyte biogenesis was clarified, which indicated zinc homeostasis regulation as a possible therapeutic target for obesity and metabolic syndrome. Here we review advances in the role of zinc homeostasis in the pathophysiol. of diabetes, and propose that inadequate zinc distribution may affect the onset of diabetes and metabolic diseases by regulating various crit. biol. events.
- 8Dhawan, D. K.; Chadha, V. D. Zinc: A promising agent in dietary chemoprevention of cancer. Indian J. Med. Res. 2010, 132 (6), 676– 682There is no corresponding record for this reference.
- 9Wenzlau, J. M.; Juhl, K.; Yu, L.; Moua, O.; Sarkar, S. A.; Gottlieb, P.; Rewers, M.; Eisenbarth, G. S.; Jensen, J.; Davidson, H. W. The cation efflux transporter ZnT8 (Slc30A8) is a major autoantigen in human type 1 diabetes. Proc. Natl. Acad. Sci. U.S.A. 2007, 104 (43), 17040– 17045, DOI: 10.1073/pnas.0705894104There is no corresponding record for this reference.
- 10Goldberg, J. M.; Lippard, S. J. Mobile zinc as a modulator of sensory perception. FEBS Lett. 2023, 597 (1), 151– 165, DOI: 10.1002/1873-3468.1454410https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XjtFOltLnJ&md5=24044fa68553e11f6a6eed6a357032cdMobile zinc as a modulator of sensory perceptionGoldberg, Jacob M.; Lippard, Stephen J.FEBS Letters (2023), 597 (1), 151-165CODEN: FEBLAL; ISSN:0014-5793. (Wiley-Blackwell)A review. Mobile zinc is an abundant transition metal ion in the central nervous system, with pools of divalent zinc accumulating in regions of the brain engaged in sensory perception and memory formation. Here, we present essential tools that we developed to interrogate the role(s) of mobile zinc in these processes. Most important are (a) fluorescent sensors that report the presence of mobile zinc and (b) fast, Zn-selective chelating agents for measuring zinc flux in animal tissue and live animals. The results of our studies, conducted in collaboration with neuroscientist experts, are presented for sensory organs involved in hearing, smell, vision, and learning and memory. A general principle emerging from these studies is that the function of mobile zinc in all cases appears to be downregulation of the amplitude of the response following overstimulation of the resp. sensory organs. Possible consequences affecting human behavior are presented for future investigations in collaboration with interested behavioral scientists.
- 11Zhou, T.; Lu, D.; She, Q.; Chen, C.; Chen, J.; Huang, Z.; Feng, S.; You, R.; Lu, Y. Hypersensitive detection of IL-6 on SERS substrate calibrated by dual model. Sens. Actuators, B 2021, 336, 129597, DOI: 10.1016/j.snb.2021.129597There is no corresponding record for this reference.
- 12Zhou, T.; Fan, M.; You, R.; Lu, Y.; Huang, L.; Xu, Y.; Feng, S.; Wu, Y.; Shen, H.; Zhu, L. Fabrication of Fe(3)O(4)/Au@ATP@Ag Nanorod sandwich structure for sensitive SERS quantitative detection of histamine. Anal. Chim. Acta 2020, 1104, 199– 206, DOI: 10.1016/j.aca.2020.01.017There is no corresponding record for this reference.
- 13Xiao, C.; Izquierdo-Roca, V.; Rivera-Gil, P. Real Time and Spatiotemporal Quantification of pH and H(2)O(2) Imbalances with a Multiplex Surface-Enhanced Raman Spectroscopy Nanosensor. ACS Mater. Au 2023, 3 (2), 164– 175, DOI: 10.1021/acsmaterialsau.2c00069There is no corresponding record for this reference.
- 14Lu, Y.; Zhou, T.; You, R.; Wu, Y.; Shen, H.; Feng, S.; Su, J. Fabrication and Characterization of a Highly-Sensitive Surface-Enhanced Raman Scattering Nanosensor for Detecting Glucose in Urine. Nanomaterials (Basel) 2018, 8 (8), 629, DOI: 10.3390/nano8080629There is no corresponding record for this reference.
- 15Rivera_Gil, P.; Vazquez-Vazquez, C.; Giannini, V.; Callao, M. P.; Parak, W. J.; Correa-Duarte, M. A.; Alvarez-Puebla, R. A. Plasmonic nanoprobes for real-time optical monitoring of nitric oxide inside living cells. Angew. Chem., Int. Ed. Engl. 2013, 52 (51), 13694– 13698, DOI: 10.1002/anie.201306390There is no corresponding record for this reference.
- 16García-Algar, M.; Tsoutsi, D.; Sanles-Sobrido, M.; Cabot, A.; Izquierdo-Roca, V.; Gil, H. P. R. Subcellular Optical pH Nanoscale Sensor. ChemistrySelect 2017, 2 (26), 8115– 8121, DOI: 10.1002/slct.20170108716https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhsFWntbzK&md5=e9a6742e193d08f42ee2a31fcf8248ebSubcellular Optical pH Nanoscale SensorGarcia-Algar, Manuel; Tsoutsi, Dionysia; Sanles-Sobrido, Marcos; Cabot, Andreu; Izquierdo-Roca, Victor; Gil, Pilar RiveraChemistrySelect (2017), 2 (26), 8115-8121CODEN: CHEMUD; ISSN:2365-6549. (Wiley-VCH Verlag GmbH & Co. KGaA)Coated gold nanoparticles bearing a pH-sensitive mol. serve as nanoscale optical sensors for non-invasive pH quantification of their endocytosis through surface-enhanced Raman scattering. Our sensor consists in colloidal gold spheres coated either with (polyethylene glycol) PEG mols. or a silica shell. They carry a sensor mol. that specifically recognize protons. The read out for monitoring changes in the pH is the Raman shift of the sensor mol. that is enhanced on the surface of the plasmonic spheres. Sensing was performed along the way of internalization from the extracellular site through different endo/lysosomal compartments where they are closely packed. The creation of hot spots favored by particle agglomeration inside cells was responsible for the enhancement of changes in signal intensity and was dependent on the surface chem. We establish a correlation between the physicochem. properties of the nanoscale sensor (shape, surface chem.) and its ability to monitor the different pH along its cellular internalization. The PEGylated spheres can sensitively track the pH along their cellular internalization whereas the silica coated ones fail.
- 17Sanles-Sobrido, M.; Exner, W.; Rodríguez-Lorenzo, L.; Rodríguez-González, B.; Liz-Marzán, L. M.; Correa-Duarte, M. A.; Álvarez-Puebla, R. A. Design of SERS-Encoded, Submicron, Hollow Particles Through Confined Growth of Encapsulated Metal Nanoparticles. J. Am. Chem. Soc. 2009, 131 (7), 2699– 2705, DOI: 10.1021/ja808844417https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhtlegsbw%253D&md5=fc67a96f5cc7db89468bab7fec7811beDesign of SERS-Encoded, Submicron, Hollow Particles Through Confined Growth of Encapsulated Metal NanoparticlesSanles-Sobrido, Marcos; Exner, Wibke; Rodriguez-Lorenzo, Laura; Rodriguez-Gonzalez, Benito; Correa-Duarte, Miguel A.; Alvarez-Puebla, Ramon A.; Liz-Marzan, Luis M.Journal of the American Chemical Society (2009), 131 (7), 2699-2705CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)The synthetic architectures of complex inorg. nanostructures, including multifunctional hollow capsules, are expected to play key roles in many different applications, such as drug delivery, photonic crystals, nanoreactors, and sensing. Implementation of novel strategies for the fabrication of such materials is needed because of the infancy of this knowledge, which still limits progress in certain areas. Herein the authors report a straightforward synthetic approach for the development of multifunctional submicron reactors comprising catalytic gold nanoparticles (2-3 nm) confined inside hollow silica capsules. Addnl., the confined growth of encapsulated metal nanoparticles was carried out to evidence the usefulness and functionality of these reactors in catalytic applications and as an approach for the development of novel complex nanostructures. Their potential and multifunctionality were pointed out by fabrication of SERS-encoded submicrometer particles with shape and size uniformity for use in antigen biosensing; this was accomplished via codification of gold nanoparticle islands grown onto their inner surfaces.
- 18Šloufová, I.; Vlčková, B.; Mojzeš, P.; Matulková, I.; Císařová, I.; Procházka, M.; Vohlídal, J. Probing the Formation, Structure, and Reactivity of Zn(II), Ag(I), and Fe(II) Complexes with 2,2′:6′,2″-Terpyridine on Ag Nanoparticles Surfaces by Time Evolution of SERS Spectra, Factor Analysis, and DFT Calculations. J. Phys. Chem. C 2018, 122 (11), 6066– 6077, DOI: 10.1021/acs.jpcc.7b12157There is no corresponding record for this reference.
- 19Constable, E. C.; Hermann, B. A.; Housecroft, C. E.; Neuburger, M.; Schaffner, S.; Scherer, L. J. 2,2′:6′,2″-Terpyridine-4′(1′H)-thione: a missing link in metallosupramolecular chemistry. New J. Chem. 2005, 29 (11), 1475, DOI: 10.1039/b510792jThere is no corresponding record for this reference.
- 20Eilers, P.; Boelens, H. Baseline Correction with Asymmetric Least Squares Smoothing. Life Sci. 2005, 1, 1– 26There is no corresponding record for this reference.
- 21Tsoutsi, D.; Sanles-Sobrido, M.; Cabot, A.; Gil, P. R. Common Aspects Influencing the Translocation of SERS to Biomedicine. Curr. Med. Chem. 2018, 25 (35), 4638– 4652, DOI: 10.2174/092986732566618010510184121https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXisF2gsrrE&md5=c6b667f540f1bfca9dd47f32d9c35f1dCommon Aspects Influencing the Translocation of SERS to BiomedicineTsoutsi, Dionysia; Sanles-Sobrido, Marcos; Cabot, Andreu; Gil, Pilar-RiveraCurrent Medicinal Chemistry (2018), 25 (35), 4638-4652CODEN: CMCHE7; ISSN:0929-8673. (Bentham Science Publishers Ltd.)This review overviews the impact in biomedicine of surface enhanced. Raman scattering motivated by the great potential we believe this technique has. We present the advantages and limitations of this technique relevant to bioanal. in vitro and in vivo and how this technique goes beyond the state of the art of traditional anal., labeling and healthcare diagnostic technologies.
- 22Nyamekye, C. K. A.; Weibel, S. C.; Smith, E. A. Directional Raman scattering spectra of metal-sulfur bonds at smooth gold and silver substrates. J. Raman Spectrosc. 2021, 52 (7), 1246– 1255, DOI: 10.1002/jrs.6124There is no corresponding record for this reference.
- 23Osterloh, F.; Hiramatsu, H.; Porter, R.; Guo, T. Alkanethiol-Induced Structural Rearrangements in Silica–Gold Core–Shell-type Nanoparticle Clusters: An Opportunity for Chemical Sensor Engineering. Langmuir 2004, 20, 5553– 5558, DOI: 10.1021/la034871923https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXktlWgsrs%253D&md5=f0884f31b60aeb4e70b7b8b5d090392dAlkanethiol-Induced Structural Rearrangements in Silica-Gold Core-Shell-type Nanoparticle Clusters: An Opportunity for Chemical Sensor EngineeringOsterloh, Frank; Hiramatsu, Hiroki; Porter, Rhiannon; Guo, TingLangmuir (2004), 20 (13), 5553-5558CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)Electrostatically bonded SiO2·Au nanoparticle clusters form by reaction of 3-aminopropylsilane-modified SiO2 spheres (470 nm) with citrate-coated gold nanoparticles (9.7 nm) in water. Reaction of the clusters with 0.01M KBr or HCl soln. induces desorption of the gold nanoparticles within minutes. Reaction of the clusters with alkanethiols CnH2n+1SH (n = 2-18) at 80° causes the gold nanoparticles to form stringlike gold nanoparticle structures for thiols with short alkane groups (n = 2, 3, 4) and hexagonally packed arrays of gold nanoparticles for thiols with long alkane groups (n = 5-18) on the silica surfaces. The structural changes indicate that the bonding between Au and SiO2 nanoparticles has changed from electrostatic to van der Waals. Elemental analyses show that the reaction with hexanethiol does not affect the Au/Si/O compn. of the SiO2·Au cluster, and Raman spectra on the hexanethiol-reacted cluster indicate the formation of a thiol SAM on the gold nanoparticles. The thiol-reacted SiO2·Au clusters display characteristic shifts of the absorption maxima in the visible spectra, and there is an inverse relation between these shifts and the lengths of the alkyl groups in the thiols. This relation can be understood in terms of the free electron model for metals. The use of SiO2·Au nanoparticle clusters as coulometric sensors for the qual. detection of thiols is discussed.
- 24Zhao, Y.; Newton, J. N.; Liu, J.; Wei, A. Dithiocarbamate-coated SERS substrates: sensitivity gain by partial surface passivation. Langmuir 2009, 25 (24), 13833– 13839, DOI: 10.1021/la902087e24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhtVSgt7nE&md5=86e589d11c53db79c8b94f04768c4614Dithiocarbamate-coated SERS substrates: sensitivity gain by partial surface passivationZhao, Yan; Newton, James N.; Liu, Jie; Wei, AlexanderLangmuir (2009), 25 (24), 13833-13839CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)The surface-enhanced Raman scattering (SERS) activity of nanoporous gold (NPG) can be boosted by controlled surface passivation. The SERS activities of unfunctionalized NPG were 1st optimized by etching substrates with NaI/I2 (triiodide) and using 2-mercaptopyridine (2-MP) as the probing analyte. Gains in analyte sensitivity were then achieved by passivating the superficial regions of the NPG substrates with dimethyldithiocarbamate (Me2DTC) while leaving the more recessed hot spots available for SERS detection. Partial surface passivation with DTCs increased the substrate sensitivity to chemisorptive analytes such as 2-MP by an order of magnitude, whereas surface satn. lowered the sensitivity by an order of magnitude. The partially passivated NPG films can also be functionalized with supramol. receptors for chemoselective SERS. Installation of a DTC-anchored terpyridine enabled the detection of divalent metal ions at trace levels, as detd. by the complexation-induced shift of a characteristic Raman peak of the metal ion receptor.
- 25Wright, D.; Lin, Q.; Berta, D.; Földes, T.; Wagner, A.; Griffiths, J.; Readman, C.; Rosta, E.; Reisner, E.; Baumberg, J. J. Mechanistic study of an immobilized molecular electrocatalyst by in situ gap-plasmon-assisted spectro-electrochemistry. Nature Catalysis 2021, 4 (2), 157– 163, DOI: 10.1038/s41929-020-00566-x25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXht1eqtbbP&md5=248c90dc521668f3b6106f7630a6c360Mechanistic study of an immobilized molecular electrocatalyst by in situ gap-plasmon-assisted spectro-electrochemistryWright, Demelza; Lin, Qianqi; Berta, Denes; Foldes, Tamas; Wagner, Andreas; Griffiths, Jack; Readman, Charlie; Rosta, Edina; Reisner, Erwin; Baumberg, Jeremy J.Nature Catalysis (2021), 4 (2), 157-163CODEN: NCAACP; ISSN:2520-1158. (Nature Research)Immobilized first-row transition metal complexes are potential low-cost electrocatalysts for selective CO2 conversion in the prodn. of renewable fuels. Mechanistic understanding of their function is vital for the development of next-generation catalysts, although the poor surface sensitivity of many techniques makes this challenging. Here, a nickel bis(terpyridine) complex is introduced as a CO2 redn. electrocatalyst in a unique electrode geometry, sandwiched by thiol-anchoring moieties between two gold surfaces. Gap-plasmon-assisted surface-enhanced Raman scattering spectroscopy coupled with d. functional theory calcns. reveals that the nature of the anchoring group plays a pivotal role in the catalytic mechanism. Our in situ spectro-electrochem. measurement enables the detection of as few as eight mols. undergoing redox transformations in individual plasmonic hotspots, together with the calibration of elec. fields via vibrational Stark effects. This advance allows rapid exploration of non-resonant redox reactions at the few-mol. level and provides scope for future mechanistic studies of single mols. [graphic not available: see fulltext].
- 26Hühn, D.; Kantner, K.; Geidel, C.; Brandholt, S.; De Cock, I.; Soenen, S. J. H.; Rivera_Gil, P.; Montenegro, J. M.; Braeckmans, K.; Müllen, K.; Nienhaus, G. U.; Klapper, M. Polymer-Coated NanoparticlesInteracting with Proteins and Cells:Focusing on the Sign of the Net Charge. ACS Nano 2013, 7 (4), 3253– 3263, DOI: 10.1021/nn305929526https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC3srjt12juw%253D%253D&md5=632e347ce062315a6488277e97a9a2c6Polymer-coated nanoparticles interacting with proteins and cells: focusing on the sign of the net chargeHuhn Dominik; Kantner Karsten; Geidel Christian; Brandholt Stefan; De Cock Ine; Soenen Stefaan J H; Rivera Gil Pilar; Montenegro Jose-Maria; Braeckmans Kevin; Mullen Klaus; Nienhaus G Ulrich; Klapper Markus; Parak Wolfgang JACS nano (2013), 7 (4), 3253-63 ISSN:.To study charge-dependent interactions of nanoparticles (NPs) with biological media and NP uptake by cells, colloidal gold nanoparticles were modified with amphiphilic polymers to obtain NPs with identical physical properties except for the sign of the charge (negative/positive). This strategy enabled us to solely assess the influence of charge on the interactions of the NPs with proteins and cells, without interference by other effects such as different size and colloidal stability. Our study shows that the number of adsorbed human serum albumin molecules per NP was not influenced by their surface charge. Positively charged NPs were incorporated by cells to a larger extent than negatively charged ones, both in serum-free and serum-containing media. Consequently, with and without protein corona (i.e., in serum-free medium) present, NP internalization depends on the sign of charge. The uptake rate of NPs by cells was higher for positively than for negatively charged NPs. Furthermore, cytotoxicity assays revealed a higher cytotoxicity for positively charged NPs, associated with their enhanced uptake.
- 27Jiang, X.; Valdeperez, D.; Nazarenus, M.; Wang, Z.; Stellacci, F.; Parak, W. J.; del Pino, P. Future Perspectives Towards the Use of Nanomaterials for Smart Food Packaging and Quality Control. Particle & Particle Systems Characterization 2015, 32 (4), 408– 416, DOI: 10.1002/ppsc.201400192There is no corresponding record for this reference.
- 28Abhijnakrishna, R.; Magesh, K.; Ayushi, A.; Velmathi, S. Advances in the Biological Studies of Metal-Terpyridine Complexes: An Overview From 2012 to 2022. Coord. Chem. Rev. 2023, 496, 215380, DOI: 10.1016/j.ccr.2023.215380There is no corresponding record for this reference.
- 29Sant’Ana, A. C.; Alves, W. A.; Santos, R. H. A.; Ferreira, A. M. D.; Temperini, M. L. A. The adsorption of 2,2′:6′,2″-terpyridine, 4′-(5-mercaptopentyl)-2,2′:6′,2″-terpyridinyl, and perchlorate on silver and copper surfaces monitored by SERS. Polyhedron 2003, 22 (13), 1673– 1682, DOI: 10.1016/S0277-5387(03)00325-5There is no corresponding record for this reference.
- 30Carregal-Romero, S.; Montenegro, J. M.; Parak, W. J.; Rivera_Gil, P. Subcellular carrier-based optical ion-selective nanosensors. Front. Pharmacol 2012, 3, 70, DOI: 10.3389/fphar.2012.0007030https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC38ngsVWksw%253D%253D&md5=cd1118809fb9f476d8eb7ac7b33779b6Subcellular carrier-based optical ion-selective nanosensorsCarregal-Romero Susana; Montenegro Jose-Maria; Parak Wolfgang J; Rivera Gil PilarFrontiers in pharmacology (2012), 3 (), 70 ISSN:.In this review, two carrier systems based on nanotechnology for real-time sensing of biologically relevant analytes (ions or other biological molecules) inside cells in a non-invasive way are discussed. One system is based on inorganic nanoparticles with an organic coating, whereas the second system is based on organic microcapsules. The sensor molecules presented within this work use an optical read-out. Due to the different physicochemical properties, both sensors show distinctive geometries that directly affect their internalization patterns. The nanoparticles carry the sensor molecule attached to their surfaces whereas the microcapsules encapsulate the sensor within their cavities. Their different size (nano and micro) enable each sensors to locate in different cellular regions. For example, the nanoparticles are mostly found in endolysosomal compartments but the microcapsules are rather found in phagolysosomal vesicles. Thus, allowing creating a tool of sensors that sense differently. Both sensor systems enable to measure ratiometrically however, only the microcapsules have the unique ability of multiplexing. At the end, an outlook on how more sophisticated sensors can be created by confining the nano-scaled sensors within the microcapsules will be given.
- 31Peana, M.; Pelucelli, A.; Chasapis, C. T.; Perlepes, S. P.; Bekiari, V.; Medici, S.; Zoroddu, M. A. Biological Effects of Human Exposure to Environmental Cadmium. Biomolecules 2022, 13 (1), 36, DOI: 10.3390/biom13010036There is no corresponding record for this reference.
- 32Jin, L.; She, G.; Mu, L.; Shi, W. Highly uniform indicator-mediated SERS sensor platform for the detection of Zn2+. RSC Adv. 2016, 6 (20), 16555– 16560, DOI: 10.1039/C5RA28041AThere is no corresponding record for this reference.
- 33Lee, N.; Ly, N. H.; Kim, J. S.; Jung, H. S.; Joo, S.-W. A selective triarylmethine-based spectroscopic probe for Zn2+ ion monitoring. Dyes Pigm. 2019, 171, 107721, DOI: 10.1016/j.dyepig.2019.107721There is no corresponding record for this reference.
- 34Li, D.; Ma, Y.; Duan, H.; Jiang, F.; Deng, W.; Ren, X. Fluorescent/SERS dual-sensing and imaging of intracellular Zn2+. Anal. Chim. Acta 2018, 1038, 148– 156, DOI: 10.1016/j.aca.2018.07.02034https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtlOisb7F&md5=a06c154304f3b6fc2281fc08647d69cdFluorescent/SERS dual-sensing and imaging of intracellular Zn2+Li, Dan; Ma, Yadan; Duan, Huazhen; Jiang, Fei; Deng, Wei; Ren, XingangAnalytica Chimica Acta (2018), 1038 (), 148-156CODEN: ACACAM; ISSN:0003-2670. (Elsevier B.V.)A fluorescent and surface-enhanced Raman spectroscopy (SERS) dual-mode probe is developed for imaging of intracellular Zn2+ based on N-(2-(bis(pyridine-2-ylmethyl)amino)ethyl)-2-mercaptoacetamide (MDPA) modified gold nanoparticles (MDPA-GNPs). Benefiting from the chelation-enhanced fluorescence (CHEF) between MDPA-GNPs and Zn2+, the fluorescent intensities of MDPA-GNPs are substantially enhanced with the increment of Zn2+ concns., which can be clearly obsd. by the naked eye. Under physiol. conditions, the probe exhibits a stable response for Zn2+ from 1 μM to 120 μM, with a detection limit of 0.32 μM in aq. solns. The resultant MDPA-GNPs can be used for ultrasensitive SERS detection of Zn2+ because of the strong interparticle plasmonic coupling generated in the process of Zn2+-triggered MDPA-GNPs self-aggregation, with a low detection limit of 0.28 pM, which is eight order of magnitude lower than the United States Environmental Protection Agency (US EPA)-defined limit (76 μM) in drinkable water. More importantly, the proposed probe can be applied for efficient detection of intracellular Zn2+ with excellent biocompatibility and cellular imaging capability. Therefore, a highly sensitive and selective nanosensor has been demonstrated for both reliable quant. detection of Zn2+ in aq. soln. and real-time imaging of intracellular Zn2+, suggesting its significant potential utility in bioanal. and biomedical detection in the future.
- 35Zhu, L.; Yuan, Z.; Simmons, J. T.; Sreenath, K. Zn(II)-coordination modulated ligand photophysical processes - the development of fluorescent indicators for imaging biological Zn(II) ions. RSC Adv. 2014, 4 (39), 20398– 20440, DOI: 10.1039/C4RA00354CThere is no corresponding record for this reference.
- 36Hancock, R. D.; Martell, A. E. Ligand design for selective complexation of metal ions in aqueous solution. Chem. Rev. 1989, 89 (8), 1875– 1914, DOI: 10.1021/cr00098a01136https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL1MXmsVWiurY%253D&md5=22b2ce07e68c61d4db06b2c2f0bd164fLigand design for selective complexation of metal ions in aqueous solutionHancock, Robert D.; Martell, Arthur E.Chemical Reviews (Washington, DC, United States) (1989), 89 (8), 1875-914CODEN: CHREAY; ISSN:0009-2665.A review on the role of steric strain in ligand design for size-match selectivity of macrocycles toward metal ions. About 155 res.
- 37Hancock, R. D. Molecular mechanics calculations and metal ion recognition. Acc. Chem. Res. 1990, 23 (8), 253– 257, DOI: 10.1021/ar00176a00337https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3cXkvVCqtbg%253D&md5=f767ffc78196895ff33f9e285601b7a8Molecular mechanics calculations and metal ion recognitionHancock, Robert D.Accounts of Chemical Research (1990), 23 (8), 253-7CODEN: ACHRE4; ISSN:0001-4842.A review with 39 refs. The results of authors studies on the relation between the cations size and the stability of a complex with a tetraaza microcycle were examd. and compared with results of mol. mechanics calcns.
- 38Ejarque, D.; Calvet, T.; Font-Bardia, M.; Pons, J. Steric crowding of a series of pyridine based ligands influencing the photophysical properties of Zn(II) complexes. CrystEngComm 2021, 23 (35), 6199– 6213, DOI: 10.1039/d1ce00833aThere is no corresponding record for this reference.
- 39Pearson, R. G. Hard and Soft Acids and Bases. J. Chem. Educ. 1968, 45 (9), 581, DOI: 10.1021/ed045p58139https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaF1cXltVShs74%253D&md5=d8780153780b30b62dae6309891fb283Hard and soft acids and bases (HSAB). I. Fundamental principlesPearson, Ralph G.Journal of Chemical Education (1968), 45 (9), 581-7CODEN: JCEDA8; ISSN:0021-9584."The principle of hard and soft acids and bases," which classified acids and bases as hard, soft, or borderline, is discussed. The rule states that hard acids prefer to bind to hard bases and soft acids prefer to bind to soft bases. The use of the rule for predicting chem. behavior, and in correlating the vast amt. of chem. information at hand is discussed.
- 40Pearson, R. G. Hard and soft acids and bases, HSAB, part 1: Fundamental principles. J. Chem. Educ. 1968, 45 (9), 581, DOI: 10.1021/ed045p58140https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaF1cXltVShs74%253D&md5=d8780153780b30b62dae6309891fb283Hard and soft acids and bases (HSAB). I. Fundamental principlesPearson, Ralph G.Journal of Chemical Education (1968), 45 (9), 581-7CODEN: JCEDA8; ISSN:0021-9584."The principle of hard and soft acids and bases," which classified acids and bases as hard, soft, or borderline, is discussed. The rule states that hard acids prefer to bind to hard bases and soft acids prefer to bind to soft bases. The use of the rule for predicting chem. behavior, and in correlating the vast amt. of chem. information at hand is discussed.
- 41Wang, S.; Cao, J.; Jia, W.; Guo, W.; Yan, S.; Wang, Y.; Zhang, P.; Chen, H. Y.; Huang, S. Single molecule observation of hard-soft-acid-base (HSAB) interaction in engineered Mycobacterium smegmatis porin A (MspA) nanopores. Chem. Sci. 2020, 11 (3), 879– 887, DOI: 10.1039/C9SC05260G41https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitlGgsrjE&md5=d26bcf0b5af36e0b047ca98d385684fdSingle molecule observation of hard-soft-acid-base (HSAB) interaction in engineered Mycobacterium smegmatis porin A (MspA) nanoporesWang, Sha; Cao, Jiao; Jia, Wendong; Guo, Weiming; Yan, Shuanghong; Wang, Yuqin; Zhang, Panke; Chen, Hong-Yuan; Huang, ShuoChemical Science (2020), 11 (3), 879-887CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)In the formation of coordination interactions between metal ions and amino acids in natural metalloproteins, the bound metal ion is crit. either for the stabilization of the protein structure or as an enzyme co-factor. Though extremely small in size, metal ions, when bound to the restricted environment of an engineered biol. nanopore, result in detectable perturbations during single channel recordings. All reported work of this kind was performed with engineered α-hemolysin nanopores and the obsd. events appear to be extremely small in amplitude (∼1-3 pA). We speculate that the cylindrical pore restriction of a-hemolysin may not be optimal for probing extremely small analytes. Mycobacterium smegmatis porin A (MspA), a conical shaped nanopore, was engineered to interact with Ca2+, Mn2+, Co2+, Ni2+, Zn2+, Pb2+ and Cd2+ and a systematically larger event amplitude (up to 10 pA) was obsd. The measured rate const. suggests that the coordination of a single ion with an amino acid follows hard-soft-acid-base theory, which has never been systematically validated in the case of a single mol. By adjusting the measurement pH from 6.8 to 8.0, the duration of a single ion binding event could be modified with a ∼46-fold time extension. The phenomena reported suggest MspA to be a superior engineering template for probing a variety of extremely small analytes, such as monat. and polyat. ions, small mols. or chem. intermediates, and the principle of hard-soft-acid-base interaction may be instructive in the pore design.
- 42Vogel-Gonzalez, M.; Musa-Afaneh, D.; Rivera Gil, P.; Vicente, R. Zinc Favors Triple-Negative Breast Cancer’s Microenvironment Modulation and Cell Plasticity. Int. J. Mol. Sci. 2021, 22 (17), 9188, DOI: 10.3390/ijms22179188There is no corresponding record for this reference.
- 43Nowakowski, A. B.; Petering, D. H. Reactions of the fluorescent sensor, Zinquin, with the zinc-proteome: adduct formation and ligand substitution. Inorg. Chem. 2011, 50 (20), 10124– 10133, DOI: 10.1021/ic201076wThere is no corresponding record for this reference.
- 44Zalewski, P. D.; Forbes, I. J.; Betts, W. H. Correlation of apoptosis with change in intracellular labile Zn(II) using Zinquin [(2-methyl-8-p-toluenesulphonamido-6-quinolyloxy)acetic acid], a new specific fluorescent probe for Zn(II). Biochem. J. 1993, 296, 403– 408, DOI: 10.1042/bj296040344https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2cXjvVer&md5=8ccb1d326f48b1cefce05f36611b2990Correlation of apoptosis with change in intracellular labile zinc(II) using zinquin [(2-methyl-8-p-toluenesulfonamido-6-quinolyloxy)acetic acid], a new specific fluorescent probe for zinc(II)Zalewski, Peter D.; Forbes, Ian J.; Betts, W. HenryBiochemical Journal (1993), 296 (2), 403-8CODEN: BIJOAK; ISSN:0264-6021.Zinquin, a membrane-permeant fluorophore specific for Zn(II), was used with spectrofluorometry and video image anal. to reveal and quantify labile intracellular Zn. Zinquin labeled human chronic-lymphocytic-leukemia lymphocytes, rat splenocytes and thymocytes with a weak diffuse fluorescence that was quenched when intracellular Zn was chelated with N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN) and was greatly intensified by pretreatment of cells with the Zn ionophore pyrithione and exogenous Zn. There was substantial heterogeneity of labile Zn among ionophore-treated cells, and fluorescence was largely extranuclear. The av. contents of labile Zn in human leukemic lymphocytes, rat splenocytes and rat thymocytes were approx. 20, 31 and 14 pmol/106 cells resp. Morphol. changes and internucleosomal DNA fragmentation indicated substantial apoptosis in these cells when the level of intracellular labile Zn was decreased by treatment with TPEN. Conversely, increasing labile Zn by pretreatment with Zn plus pyrithione suppressed both spontaneous DNA fragmentation and that induced by the potent apoptosis-induced agents colchicine and dexamethasone. These results suggest that prevention of apoptosis is a function of labile Zn, and that a redn. below a threshold concn. in this Zn pool induces apoptosis.
- 45Chen, Q. G.; Zhang, Z.; Yang, Q.; Shan, G. Y.; Yu, X. Y.; Kong, C. Z. The role of zinc transporter ZIP4 in prostate carcinoma. Urol Oncol 2012, 30 (6), 906– 911, DOI: 10.1016/j.urolonc.2010.11.010There is no corresponding record for this reference.
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