Contribution of charge-transfer mechanisms to surface-enhanced Raman scattering with near-IR excitation.

Surface-enhanced Raman scattering under near-IR excitation is investigated for p-aminothiophenol (PATP) molecules that are either adsorbed on an electrochemically roughened silver electrode or embedded in an Au/PATP/Ag molecular junction assembled on an indium-doped tin oxide electrode. The contribution from chemical enhancement can be amplified relative to the contribution from electromagnetic enhancement, because the energy of the near-IR excitation is far from the surface plasmon resonance of the nanosized metal particles. The energy required for the charge-transfer process for the Au/PATP/Ag molecular junction is much lower than that of the PATP molecules adsorbed on the electrochemically roughened silver electrode. Coadsorption of chloride ions on the metal nanoparticles may result in an alteration of the local Fermi level of the metal nanoparticles, thus leading to better energy matching between the energy level of the interconnecting PATP molecules and the Fermi level of the metal nanoparticles.     

Electron Transfer in Peptides: On the Formation of Silver Nanoparticles

Some microorganisms perform anaerobic mineral respiration by reducing metal ions to metal nanoparticles, using peptide aggregates as medium for electron transfer (ET). Such a reaction type is investigated here with model peptides and silver as the metal. Surprisingly, Ag⁺ ions bound by peptides with histidine as the Ag⁺‐binding amino acid and tyrosine as photoinducible electron donor cannot be reduced to Ag nanoparticles (AgNPs) under ET conditions because the peptide prevents the aggregation of Ag atoms to form AgNPs. Only in the presence of chloride ions, which generate AgCl microcrystals in the peptide matrix, does the synthesis of AgNPs occur. The reaction starts with the formation of 100 nm Ag@AgCl/peptide nanocomposites which are cleaved into 15 nm AgNPs. This defined transformation from large nanoparticles into small ones is in contrast to the usually observed Ostwald ripening processes and can be followed in detail by studying time‐resolved UV/Vis spectra which exhibit an isosbestic point.     

Efficient immobilization of silver nanoparticles on metal substrates through various thiol molecules to utilize a gap mode in surface enhanced Raman scattering

To utilize a gap mode in surface enhanced Raman scattering, we elucidated the interaction between adsorbed species and Ag nanoparticles (AgNPs). Various thiol molecules such as normal alkanethiols, thiols with a phenyl, cyclohexane or naphthalene ring on Ag films immobilized AgNPs through van der Waals force, and electrostatic interaction. Immobilized AgNPs provided enormous Raman enhancement by a factor of 10⁷–10¹⁰ for thiol molecules at a nanogap, in consistent with that anticipated by finite difference time domain calculations. Only alkanethiols with a tert-methyl group and those with a carboxylic group did not immobilize any AgNPs probably owing to steric hindrance. A gap mode is relevant for a variety of metals even with large damping like Pt and Fe, indicating a crucial role of electric multipoles in AgNPs generated by a localized surface plasmon and induced mirror images in metal substrates for markedly enhanced electric field at a nanogap.     

Colorimetric and bare-eye detection of alkaline earth metal ions based on the aggregation of silver nanoparticles functionalized with thioglycolic acid

We describe a simple and rapid method for colorimetric and bare-eye detection of the alkaline earth metal ions Mg(II), Ca(II), Sr(II) and Ba(II) based on the use of silver nanoparticles (AgNPs) functionalized with thioglycolic acid (TGA). The TGA ligand was self-assembled onto the AgNPs to form a probe that undergoes a color change from yellow to orange or red on exposure to the alkaline earth ions. It is presumed that the color change is a result of the aggregation of the AgNPs caused by the interaction of the bivalent ions with the carboxy groups on the AgNPs. The color change can be used for bare-eye and colorimetric determination of the alkaline earth metal ions, for example to rapidly determine water hardness.

Effect of substrate on surface-enhanced Raman scattering of molecules adsorbed on immobilized silver nanoparticles

Silver nanoparticles were assembled on polyvinylpyridine (PVP) derivatized glass slides. Charge transfer between the adsorbed 4-aminothiophenol (PATP) and the immobilized silver nanoparticles was studied by surface-enhanced Raman spectroscopy with 1064 nm excitation, and compared with that of the silver nanoparticles in the colloid. It was demonstrated that the positive charges of the PVP layer could alter the charge distribution in the immobilized nanoparticles and induce the formation of the dipole in the nanoparticles, leading to less charge transfer from the metal to the adsorbed molecules. The coadsorption of chloride ions on the surface of the immobilized silver nanoparticles resulted in the redistribution of the charges in the nanoparticles and, in turn, altered the charge transfer between the adsorbed PATP molecules and the silver nanoparticles.     

CuAg nanoparticles formed in situ on electrochemically pre‐anodized screen‐printed carbon electrodes for the detection of nitrate and nitrite anions

CuAg nanoparticles (CuAgNPs) were electrochemically formed in situ on pre‐anodized, screen‐printed carbon electrodes (SPCEs) that possessed many oxygen‐containing functional groups capable of adsorbing metal ions, namely Cu²⁺ and Ag⁺. Pre‐anodization was achieved using continuous cyclic voltammetry in the range of potential 0.3–2.0 V under a scan rate of 50 mV/s. Cu²⁺ and Ag⁺ ions were adsorbed on the pre‐anodized SPCE by immersing the electrode in solutions containing both metal ions, and then CuAgNPs were formed in situ via electrochemical reduction in a deaerated, neat NaClO₄ solution after the electrode was ultrasonicated to remove physically adsorbed metal ions. Although CuNPs showed higher activity than AgNPs toward both nitrate (NO₃⁻) and nitrite (NO₂⁻) ions, the instability of CuNPs hindered the application, so CuAgNPs were employed to achieve a compromise between sensitivity and stability. The SPCE/anodized/CuAgNP electrodes showed activity toward the electrochemical reduction of NO₃⁻ and NO₂⁻, respectively, with the limit of detection (LOD) of 15.6 μM (0.97 ppm) and 11.1 μM (0.51 ppm), which is sufficient to fit the allowed values (50 and 3 ppm, respectively) in drinking water as suggested by the World Health Organization (WHO).     

Highly sensitive Raman spectroscopy using a gap mode plasmon under an attenuated total reflection geometry

We investigated a gap mode plasmon under an attenuated total reflection (ATR) configuration toward realization of near-field Raman spectroscopy with a single molecule sensitivity and spatial resolution. Additional enhancement in Raman scattering at a nanogap was obtained by a coupling of a propagating surface plasmon (PSP) of Ag films on a prism, and a gap mode between Ag films and Ag nanoparticles (AgNPs). Immobilization of AgNPs on Ag films through thiol-SAM slightly up-shifted the resonance angle of a PSP, which broadened the reflectivity dip owing to an increased out-coupling of a PSP. Raman enhancement factor at a nanogap increased with decreasing surface coverage of AgNPs, albeit the enhancement factor averaged over illuminated area in Ag films decreased, ensuring the largest enhancement factor in tip-enhanced Raman scattering. This is due to increased efficiency for a PSP excitation at lower coverage of AgNPs in consistent with that in theoretical evaluation using finite difference time domain calculations. A gap mode under an ATR configuration was applied to elucidate a plausible photochemical reaction of p-amino thiophenol (PATP) adsorbed on Ag films on a prism. Spectral changes in Raman scattering under laser illumination were observed for PATP with a deuterated amino group, but suppressed by a dimethyl amino group owing to steric hindrance, supporting the photochemical dimerization.     

Biosynthesis and Characterization of Extracellular Silver Nanoparticles from Streptomyces aizuneusis: Antimicrobial,Anti Larval,and Anticancer Activities

The ability of microorganisms to reduce inorganic metals has launched an exciting eco-friendly approach towards developing green nanotechnology. Thus, the synthesis of metal nanoparticles through a biological approach is an important aspect of current nanotechnology. In this study, Streptomyces aizuneusis ATCC 14921 gave the small particle of silver nanoparticles (AgNPs) a size of 38.45 nm, with 1.342 optical density. AgNPs produced by Streptomyces aizuneusis were characterized by means of UV-VIS spectroscopy and transmission electron microscopy (TEM). The UV-Vis spectrum of the aqueous solution containing silver ion showed a peak between 410 to 430. Moreover, the majority of nanoparticles were found to be a spherical shape with variables between 11 to 42 nm, as seen under TEM. The purity of extracted AgNPs was investigated by energy dispersive X-ray analysis (EDXA), and the identification of the possible biomolecules responsible for the reduction of Ag⁺ ions by the cell filtrate was carried out by Fourier Transform Infrared spectrum (FTIR). High antimicrobial activities were observed by AgNPs at a low concentration of 0.01 ppm, however, no deleterious effect of AgNPs was observed on the development and occurrence of Drosophila melanogaster phenotype. The highest reduction in the viability of the human lung carcinoma and normal cells was attained at 0.2 AgNPs ppm.     

Preparation of Silver Nanoparticles Reduced by Formamidinesulfinic Acid and Its Application in Colorimetric Sensor

A rapid one-step preparation approach of silver nanoparticles (AgNPs) was reported by employing formamidinesulfinic acid as reducing agent and soluble starch as stabilizing agent. The formation of AgNPs was further confirmed by using UV–Vis absorption spectroscopy, X-ray diffraction spectroscopy and transmission electron microscopy techniques. The resultant AgNPs could be directly used for the colorimetric reaction with metal ions. The results showed that Al³⁺, Cr³⁺, Fe³⁺ and Hg²⁺ ions could induce the color change of AgNPs from yellow to pink (Al³⁺), orange (Cr³⁺) and colorless (Fe³⁺ and Hg²⁺), respectively, which can be observed by the naked eye. Based on these, a sensitive colorimetric sensor for Al³⁺, Fe³⁺, Cr³⁺ and Hg²⁺ ions detection was developed.     

Inhibition and enhancement of glucose oxidase activity in a chitosan-based electrode filled with silver nanoparticles

A chitosan-based electrode filled with silver nanoparticles (AgNPs) and glucose oxidase (GOD) was used as an enzyme electrode to investigate the effect of aging process of AgNPs on the GOD activity. Freshly prepared AgNPs inhibit the GOD activity, however, the inhibitory effect decreased with the increase of aging time. After aged for a period of time, AgNPs showed enhancement effect on the GOD activity. The effect of aging was studied by the measurements of Ag⁺ ions concentration, zeta (ζ) potential and X-ray photoelectron spectroscopy (XPS). And the results indicated that the concentration of Ag⁺ ions in the silver sol decreased during the aging period (i.e. Ag⁺ ions converted to more inert silver metal Ag⁰). The effect of AgNPs on the GOD activity can be changed by controlling the aging time of AgNPs. This research provides a new and simple approach to mediate AgNPs property, which is of great value in potential application of AgNPs in biosensors and nanoscale devices.     

Characterization of 11-mercaptoundecanoic and 3-mercaptopropionic acids adsorbed on silver by surface-enhanced Raman scattering

Functionalized n-alkanethiols such as 11-mercaptoundecanoic (MUA) and 3-mercaptopropionic (MPA) acids are likely to adsorb in silver nanoparticles (AgNPs) solely through the thiol group (-SH) or also involving the carboxylate group (−COO⁻) in their structures. The relative tendency is closely related to pH conditions, solvent or the surface potential of the metallic nanoparticles. The SERS effect (Surface Enhancement Raman Scattering) was used for improving the understanding of MUA and MPA group interaction as well as the orientation of these organic compounds adsorbed on AgNPs and the influence of Cu(II) in solution. When analyzing the MPA SERS spectrum, it was verified that the thiol moiety was preferred to adsorb on the AgNPs surface in the thiolate form, presenting both anti and gauche conformations in both acidic and basic media. MUA SERS spectrum however, indicated that solely an anti conformation for the thiol moiety adsorbed on the AgNPs surface in both acidic and basic media. Adding Cu²⁺ ion resulted in coordination to the carboxyl or carboxylate moieties was confirmed by the downshift of the band assigned to OCO stretching. The presence of Cu(II) increased the tendency of gauche conformation for MPA; the coordination of MUA to Cu(II) resulted in a more upright conformation of the carboxylic/carboxylate moieties in both acidic and basic media, respectively.     

Green Synthesis of Silver Nanoparticles Using Acacia farnesiana (Sweet Acacia) Seed Extract Under Microwave Irradiation and Their Biological Assessment

In the present study, Acacia farnesiana (Sweet acacia) seed extract is used to reduce Ag⁺ → Ag⁰ under microwave irradiation. The formation of silver nanoparticles (AgNPs) is monitored by recording the UV–Vis absorption spectra for surface plasmon resonance (SPR) peak at ~450 nm. The absorbance of SPR increases linearly with increasing temperature of the reaction mixture. Rapid reduction of silver ions occurred to form AgNPs, 80–90 % yield in about 150 s. A marginal decrease in pH and increase in solution potential (E) of the reaction mixture during the formation of AgNPs are in agreement with the proposed mechanism. XRD pattern of the AgNPs agree with the fcc structure of Ag metal, and the calculated crystallite size is ~17 nm. FT-IR and solid-state ¹³C NMR spectra indicate the functional groups of flavonones and terpenoids (biomolecules from plant extract) which are adsorbed on AgNPs, thereby the present method led to in situ biofunctionalization/bio-capping of AgNPs. TG analysis shows the thermal decomposition of these plant residues present on AgNPs at about 250 °C. The spherical shape of the particles with a diameter (?) in the range of ~15–20 nm is evident from FE-SEM image. Elemental analysis by EDX analysis confirms the presence of Ag as the only major element. The in vitro antibacterial screening of AgNPs shows that these bio-capped AgNPs have higher inhibitory action for E. coli and S. aureus followed by B. subtilis and P. aeruginosa. In addition, AgNPs show very good antioxidant property.     

Three-dimensional printed knotted reactors enabling highly sensitive differentiation of silver nanoparticles and ions in aqueous environmental samples

Whether silver nanoparticles (AgNPs) persist or release silver ions (Ag⁺) when discharged into a natural environment has remained an unresolved issue. In this study, we employed a low-cost stereolithographic three-dimensional printing (3DP) technology to fabricate the angle-defined knotted reactors (KRs) to construct a simple differentiation scheme for quantitative assessment of Ag⁺ ions and AgNPs in municipal wastewater samples. We chose xanthan/phosphate-buffered saline as a dispersion medium for in situ stabilization of the two silver species, while also facilitating their extraction from complicated wastewater matrices. After method optimization, we measured extraction efficiencies of 54.5 and 32.3% for retaining Ag⁺ ions and AgNPs, respectively, in the printed KR (768-turn), with detection limits (DLs) of 0.86 and 0.52 ng L⁻¹ when determining Ag⁺ ions and AgNPs, respectively (sample run at pH 11 without a rinse solution), and 0.86 ng L⁻¹ when determining Ag⁺ ions alone (sample run at pH 12 with a 1.5-mL rinse solution). The proposed scheme is tolerant of the wastewater matrix and provides more reliable differentiation between Ag⁺/AgNPs than does a conventional filtration method. The concept and applicability of adopting 3DP technology to renew traditional KR devices were evidently proven by means of these significantly improved analytical performance. Our analytical data suggested that the concentrations of Ag⁺ ions and AgNPs in the tested industrial wastewater sample were both higher than those in domestic wastewater, implying that industrial activity might be a main source of environmental silver species, rather than domestic discharge from AgNP-containing products.     

Use of unmodified silver nanoparticles (AgNPs) as colorimetric Hg(II) sensor: A new approach to sensitive and high sample throughput determination of Hg(II) under high influence of ionic suppression

Facile unmodified silver nanoparticles (AgNPs) as colorimetric sensor for determination of Hg(II) ions in aqueous samples were developed using UV-Vis spectrophotometry. Abrupt change in absorbance of the AgNPs was observed, which progressively decreased and slightly shifted to the blue wavelength as the concentration of Hg(II) increased. It appears that the AgNPs were oxidized by Hg(II), resulting in disintegration of the AgNPs and Hg(0). Deposition of Hg(0) on the surface of AgNPs also occurred, resulting in amalgam particles of mercury (Hg-Ag). Interestingly, the developed approach showed a significant enhancement in the Hg(II) analytical sensitivity when formic acid was doped onto the AgNPs, with the linearity range of 0.01–10 mg L^?1 (r² = 0.999) providing the quantitative detection limit of 0.007 mg L^?1 (3SD blank/slope of the calibration curve). Greater selectivity toward Hg(II) over other ions and colour dyes was also observed, likely a result of stabilization by polyvinylpyrrolidone (PVP), which kept the AgNPs well-stabilized and dispersed in the bulk aqueous environment making them resistant to ionic suppression. Under using a 96-well microplate and a smartphone equipped with homemade application as a colorimetric analyzer under controlled lighting, high sample throughput (128 sample h^?1, n = 4) was achieved, establishing its potential for practical analysis. The percentage recoveries of spiked aqueous samples obtained from the microplate-based system were in acceptable range, in agreement with the values obtained from the UV-Vis spectrophotometry-based system. The proposed colorimetric sensor has been shown to provide a rapid, simple, sensitive and selective detection of Hg(II) ions in various aqueous samples.     

Eco‐friendly Sensors Developed by Herbal Based Silver Nanoparticles for Electrochemical Detection of Mercury (II) Ion

In our study, the single‐use & eco‐friendly electrochemical sensor platform based on herbal silver nanoparticles (AgNPs) was developed for detection of mercury (II) ion (Hg²⁺). For this purpose, the surface of pencil graphite electrode (PGE) was modified with AgNPs and folic acid (FA), respectively. The concentrations of AgNPs and FA were firstly optimized by differential pulse voltammetry (DPV) to obtain an effective surface modification of PGE. Each step at the surface modification process was characterized by using cyclic voltammetry (CV) and electrochemical impedence spectroscopy (EIS). The limit of detection (LOD) for Hg²⁺ was estimated and found to be 8.43 μM by CV technique. The sensor presented an excellent selectivity for Hg²⁺ against to other heavy metal ions such as Ca²⁺, Cd²⁺, Cr³⁺, Cu²⁺, Mg²⁺, Ni²⁺, Pb²⁺, Zn²⁺, Co²⁺ and Mn²⁺. Moreover, a rapid, selective and sensitive detection of Hg²⁺ was successfully performed in the samples of tap water within 1 min.     

The adsorption of methamphetamine on Ag nanoparticles dispersed in agarose gel – Detection of methamphetamine in fingerprints by SERS

Surface-enhanced Raman scattering (SERS) has been used to investigate the adsorption of methamphetamine hydrochloride (MA) on AgNPs surfaces characterized by the dispersion of AgNPs on agarose gel (AgNPs/Agar). The AgNPs/Agar was characterized by transmission electron microscopy (TEM) as being formed by AgNPs with a mean diameter of 13.5 nm. The AgNPs/Agar films presented a surface plasmon resonance absorption band centered at 421 nm. SERS spectra, excited at 632.8 nm, of MA adsorbed onto AgNPs/Agar films were recorded for MA concentrations down to 1.0 × 10⁻⁵ mol L^-1. The results have also shown that MA adsorbs on the Ag surface forming ionic pairs with adsorbed chloride following a Frumkin adsorption isotherm with a ΔG_ads of −24 kJ mol^-1 and a g parameter characteristic of attractive lateral interaction. The AgNPs/Agar SERS substrate was further evaluated for MA detection on latent fingerprints (LFP). The AgNPs/Agar films prove to be a suitable substrate for recording fingerprints contaminated with MA making possible the detection of ca. 190 μg of MA, before and after LFP development. The SERS signal of MA adsorbed onto AgNPs/Agar films remained stable for at least 180 days.     

Probing the Catalytic Activity of Reduced Graphene Oxide Decorated with Au Nanoparticles Triggered by Visible Light

Hybrid materials in which reduced graphene oxide (rGO) is decorated with Au nanoparticles (rGO–Au NPs) were obtained by the in situ reduction of GO and AuCl₄^?_(aq) by ascorbic acid. On laser excitation, rGO could be oxidized as a result of the surface plasmon resonance (SPR) excitation in the Au NPs, which generates activated O₂ through the transfer of SPR‐excited hot electrons to O₂ molecules adsorbed from air. The SPR‐mediated catalytic oxidation of p‐aminothiophenol (PATP) to p,p′‐dimercaptoazobenzene (DMAB) was then employed as a model reaction to probe the effect of rGO as a support for Au NPs on their SPR‐mediated catalytic activities. The increased conversion of PATP to DMAB relative to individual Au NPs indicated that charge‐transfer processes from rGO to Au took place and contributed to improved SPR‐mediated activity. Since the transfer of electrons from Au to adsorbed O₂ molecules is the crucial step for PATP oxidation, in addition to the SPR‐excited hot electrons of Au NPs, the transfer of electrons from rGO to Au contributed to increasing the electron density of Au above the Fermi level and thus the Au‐to‐O₂ charge‐transfer process.     

Sol–gel synthesis of nanosilver embedded hybrid materials using combined organosilica precursors

A facile sol–gel route to the fabrication of size-controllable nanosilver embedded hybrid materials at room-temperature is presented. The preparation process involves using three kind of organosilica precursors, i.e. tetraethoxysilane, 3-mercaptopropyltrimethoxysilane and polymethylhydrosiloxane, which behaved as framework constructor, complexing agent toward metal ions and in situ reducing agent for Ag⁺ ions, respectively, under alcohol-rich synthesis conditions. The prepared hybrid materials were characterized by Ultraviolet–visible diffuse reflectance spectra, Fourier transform infrared, transmission electron microscopy, X-ray diffraction, nitrogen adsorption–desorption measurements. It was shown that well-dispersed silver nanoparticles (AgNPs) with small particle size were successfully embedded in the hybrid skeleton, and the mean particle size of AgNPs could be controlled at ca. 2–5 nm.     

Effect of Graphene Characteristics on Morphology and Performance of Composite Noble Metal-Reduced Graphene Oxide SERS Substrate

Graphene/noble metal substrates for surface enhanced RAMAN scattering (SERS) possess synergistically improved performance, due to the strong chemical enhancement mechanism accounted to graphene and the electromagnetic mechanism raised from the metal nanoparticles. However, only the effect of noble metal nanoparticles characteristics on the SERS performance was studied so far. In attempts to bring a light to the effect of quality of graphene, in this work, two different graphene oxides were selected, slightly oxidized GOS (20%) with low aspect ratio (1000) and highly oxidized (50%) GOG with high aspect ratio (14,000). GO and precursors for noble metal nanoparticles (NP) simultaneous were reduced, resulting in rGO decorated with AgNPs and AuNPs. The graphene characteristics affected the size, shape, and packing of nanoparticles. The oxygen functionalities actuated as nucleation sites for AgNPs, thus GOG was decorated with higher number and smaller size AgNPs than GOS. Oppositely, AuNPs preferred bare graphene surface, thus GOS was covered with smaller size, densely packed nanoparticles, resulting in the best SERS performance. Fluorescein in concentration of 10⁻⁷ M was detected with enhancement factor of 82 × 10⁴. This work demonstrates that selection of graphene is additional tool toward powerful SERS substrates.     

Concentration-Dependent Influence of Silver Nanoparticles on Amyloid Fibrillation Kinetics of Hen Egg-White Lysozyme

Understanding the influence of nanoparticles on the formation of protein amyloid fibrillation is crucial to extend their application in related biological diagnosis and nanomedicines. In this work, Raman spectroscopy was used to probe the amyloid fibrillation of hen egg-white lysozyme in the presence of silver nanoparticles (AgNPs) at different concentrations, combined with atomic force microscopy and thioflavin T (ThT) fluorescence assays. Four representative Raman indicators were utilized to monitor transformation of the protein tertiary and secondary structures at the molecular level: the Trp doublet bands at 1340 and 1360 cm^-1, the disulfide stretching vibrational peak at 507 cm^-1, the N-C$\alpha$-C stretching vibration at 933 cm^-1, and the amide Ⅰ band. All experimental results confirmed the concentration-dependent influence of AgNPs on the hen egg-white lysozyme amyloid fibrillation kinetics. In the presence of AgNPs at low concentration (17 μg/mL), electrostatic interaction of the nanoparticles stabilizes disulfide bonds, and protects the Trp residues from exposure to hydrophilic environment, thus leading to formation of amorphous aggregates rather than fibrils. However, with the action of AgNPs at high concentration (1700 μg/mL), the native disulfide bonds of hen egg-white lysozyme are broken to form Ag-S bonds owing to the competition of electrostatic interaction from a great deal of nanoparticles. As for providing functional surfaces for protein to interact with, AgNPs play a bridge role in direct transformation from $\alpha$-helices to organized $\beta$-sheets. The present investigation sheds light on the controversial effects of AgNPs on the kinetics of hen egg-white lysozyme amyloid fibrillation.