Tunable Coffee Ring Formation on Polycarbonate Nanofiber Film for Sensitive SERS Detection of Phenylalanine in Urine.

A new method based on the coffee ring effect was developed for improving the sensitivity, simplicity, and robustness of surface-enhanced Raman scattering (SERS) in determining trace levels of analytes. In this method, a polyvinylpyrrolidone (PVP)-stabilized silver colloidal (AgC) solution was first prepared and mixed with a sample solution. Following deposition of the mixture solution on a solid substrate with a rough surface, a coffee ring was formed once the solvent had evaporated. The formation of a coffee ring not only concentrated the analyte but also reduced the space between silver nanoparticles (AgNPs) to strengthen the hotspot effect, thereby considerably improving SERS sensitivity. To strengthen the coffee ring effect further, the surface roughness of the solid support and PVP content of the AgC solution were investigated. The results indicated that an increase in surface roughness reduced the size of the coffee rings, whereas the addition of PVP not only stabilized the AgNPs but also improved the compactness of the coffee rings. When applying the proposed method to determine the phenylalanine (Phe) level in urine for rapid screening of the phenylketonuria disorder, strong chemical interference from uric acid (UA), which is a major component in urine, was observed. To minimize the interference from UA, ZnO powder was applied to the urine sample to adsorb UA prior to SERS detection. After cleaning by using ZnO, the SERS signals of Phe were revealed for quantitative purposes. Under the optimized conditions, both the sensitivity and reproducibility of SERS measurement considerably improved. Quantitative analyses revealed that the developed method is highly feasible for the rapid determination of Phe in real samples.

Preparation of silver nanoparticles coated ZnO/Fe3O4 composites using chemical reduction method for sensitive detection of uric acid via surface-enhanced Raman spectroscopy.

In this study, silver nanostructures decorated magnetic nanoparticles for surface-enhanced Raman scattering (SERS) measurements were prepared via heat induced catalytic activity of ZnO nanostructures. The ZnO/Fe3O4 composite was first prepared by dispersing pre-formed magnetic nanoparticles into alkaline zinc nitrate solutions. After annealing of the precipitates, the formed ZnO/Fe3O4 composites were successfully decorated with silver nanostructures by dispersing the composites into silver nitrate/ethylene glycol solution at 95 °C in water bath. To find the optimal condition when preparing Ag/ZnO/Fe3O4 composites for SERS measurements, factors such as reaction time and concentration of silver nitrate were studied. Results indicated that the formation of silver nanoparticles (AgNPs) on ZnO/Fe3O4 was significantly improved with the assistance of ZnO. The concentration of silver nitrate and reaction time affected the morphologies and sizes of the formed composites and optimal condition in preparation of the composites for SERS measurement was found using 100 mM of silver nitrate with a reaction time of 20 min. Under optimized conditions, the obtained SERS intensities were highly reproducible. The substrates were applied for quantitative analysis of uric acid in aqueous solution and a linear response for concentrations up to 10 µM was obtained. Successful application of these prepared composites to determine uric acid in urine sample without any pretreatment of the urine sample was done.

Single-Step Preparation of Silver-Doped Magnetic Hybrid Nanoparticles for the Catalytic Reduction of Nitroarenes.

This study adopts a simple but facile process for preparing silver-doped magnetic nanoparticles by the spontaneous oxidation-reduction/coprecipitation method. The preparation can be achieved in one pot with a single step, and the prepared silver-doped magnetic nanoparticles were utilized as nanocatalysts for the reduction of o-nitroaniline. Utilizing the magnetic characteristics of the prepared nanoparticles, the catalytic reactions can be carried out under quasi-homogeneous condition and the nanocatalysts can be easily collected after the conversion is achieved. It can be revealed from the results that the morphologies and the composition of the prepared silver-doped magnetic nanoparticles can be adjusted by changing the conditions during the production, which affects the efficacy of the catalysis. In addition, the catalysis efficiency is also controlled by the pH, temperature, and the amounts of nanocatalysts used during the catalytic reaction. Finally, the silver-doped magnetic nanocatalysts prepared in this study own the advantages of easy preparation, room-temperature catalysis, high conversion ability, and recyclability, which make them more applicable in real utilities.

Simultaneous Production and Surface Functionalization of Silver Nanoparticles for Label-free Colorimetric Detection of Copper Ion.

In this work, a simple method was developed to simultaneously fabricate silver nanoparticles (AgNPs) and modify their surfaces with recognition functional groups for colorimetric detection of Cu2+ ions. To prepare the AgNPs with proper functional group on their surface for detection of Cu2+ ions, photochemical reaction was employed and a photoactive species of tyrosine (Tyr) was used to trigger the photoreduction of AgNPs, while the oxidized Tyr (TyrOx) was used to functionalize the AgNPs surface at the same time. To understand the behaviors, the prepared color AgNPs colloidal solution was characterized by UV-visible spectrometer, FT-IR spectrometer, dynamic light scattering (DLS), X-ray photoelectron spectrometer (XPS) and density functional theory (DFT). Based on DFT calculation results, TyrOx was adsorbed on the surface of AgNPs by the quinone ring and its functional group of amino acid was freely exposed to the aqueous media for rapid interaction of Cu2+ ions. Based on detection of different metal ions, TyrOx@AgNPs were selective to interact with Cu2+ ions through formation of highly stable Cu2+-TyrOx@AgNPs complexes. The evidence in formation of Cu2+-TyrOx@AgNPs complex could be obtained through the red shift of the surface plasmonic resonance (SPR) band of TyrOx@AgNPs located at 557 nm, which gives a color change from light yellow to brown color allowing visual identification of Cu2+ ions for rapid screening purposes. For quantitative analysis, a band intensity ratio of A557/(A404-A557) was constructed to correlate with the concentration of Cu2+ ions. A linear range up to 10 µM with a detection limit close to 150 nM was found.

Three-Dimensional Surface-Enhanced Raman Scattering Substrate Fabricated Using Chemical Decoration of Silver Nanoparticles on Electrospun Polycarbonate Nanofibers.

In this work, a simple method via decoration of silver nanoparticles (AgNPs) on electrospun polycarbonate nanofibers (PCNFs) was proposed to prepare highly sensitive three-dimensional (3D) substrates for surface-enhanced Raman scattering (SERS) measurements. The method proposed in this work gave a high sensitive Ag@PCNFs substrate, which resulted from a successful production of high surface area of PCNFs with a high efficiency in the decoration of AgNPs. To produce PCNFs suitable for SERS application, parameters in fabrication of PCNFs were systematically examined and correlated with their corresponding scanning electron microscope (SEM) images. Examined parameters included the concentration of PC solution, the solvent to form PC solution, the applied voltage, and the rotating speed of a drum collector. Using the optimized condition, the bead-free PCNFs with a diameter in the range of 200-400 nm were successfully produced. To increase the efficiency in decoration of AgNPs, the surface properties of PNCFs were altered with an organic solvent, which was selected experimentally with guidance of Hildebrand solubility parameter. Results indicated that methanol was the most suitable solvent to effectively decorate AgNPs on PCNFs. By probing with para-hydroxythiophenol (pHTP), prepared SERS substrates of Ag@PCNFs provided an enhancement factor to the order of 7, which is at least an order of magnitude larger than the reported values in the literature for SERS substrates prepared with the electrospinning technique.

Rhenium-Based Molecular Trap as an Evanescent Wave Infrared Chemical Sensing Medium for the Selective Determination of Amines in Air.

An evanescent wave infrared chemical sensor was developed to selectively detect volatile amines with heterocyclic or phenyl ring. To achieve this goal, a rhenium-based metallacycle with a "molecular-trap" structure was designed and synthesized as host molecules to selectively trap amines with heterocyclic or phenyl ring through Re-amine and π-π interactions. To explore the trapping properties of the material, a synthesized Re-based molecular trap was treated on an IR sensing element, and wide varieties of volatile organic compounds (VOCs) were examined to establish the selectivity for detection of amines. Based on the observed IR intensities, the Re-based molecular trap favors interaction with amines as evidenced by the variation of absorption bands of the Re molecular trap. With extra π-π interaction force, molecules, such as pyridine and benzylamine, could be detected. After optimization of the parameters for IR sensing, a rapid response in the detection of pyridine was observed, and the linear ranges were generally up to 10 mg/L with a detection limit around 5.7 µg/L. In the presence of other VOCs, the recoveries in detection of pyridine were all close to 100%.

Silver Nanoparticle-Decorated Shape-Memory Polystyrene Sheets as Highly Sensitive Surface-Enhanced Raman Scattering Substrates with a Thermally Inducible Hot Spot Effect.

In this study, an active surface-enhanced Raman scattering (SERS) substrate with a thermally inducible hot spot effect for sensitive measurement of Raman-active molecules was successfully fabricated from silver nanoparticle (AgNP)-decorated shape-memory polystyrene (SMP) sheets. To prepare the SERS substrate, SMP sheets were first pretreated with n-octylamine for effective decoration with AgNPs. By varying the formulation and condition of the reduction reaction, AgNP-decorated SMP (Ag@SMP) substrates were successfully prepared with optimized particle gaps to produce inducible hot spot effects on thermal shrink. High-quality SERS spectra were easily obtained with enhancement factors higher than 108 by probing with aromatic thiols. Several Ag@SMP substrates produced under different reaction conditions were explored for the creation of inducible hot spot effects. The results indicated that AgNP spacing is crucial for strong hot spot effects. The suitability of Ag@SMP substrates for quantification was also evaluated according to the detection of adenine. Results confirmed that prepared Ag@SMP substrates were highly suitable for quantitative analysis because they yielded an estimated limit of detection as low as 120 pg/cm2, a linear range of up to 7 ng/cm2, and a regression coefficient (R2) of 0.9959. Ag@SMP substrates were highly reproducible; the average relative standard deviation for all measurements was less than 10%.

Analyte-induced photoreduction method for visual and colorimetric detection of tyrosine.

A new method based on photochemical formation of silver nanoparticles (AgNPs) was developed for detection of tyrosine (Tyr). To selectively detect Tyr and to simplify the detection procedure, the photoactivity of Tyr was utilized to trigger the photochemical reduction in production of AgNPs. The drastic change of solution color caused by the surface plasmon resonance (SPR) absorption band of the formed AgNPs was used to extract the quantitative information of Tyr. This developed method is simple in detection, while both the sensitivity and selectivity are significant improved. Meanwhile, the solution color was changed from colorless to dark yellow after the formation of AgNPs, which allows a much higher sensitivity in visual identification when compared with the SPR band shifting technique commonly, used in conventional colorimetric methods. To optimize the detection system and to understand the mechanism in this proposed method, parameters such as irradiation time, intensity of light source, and the concentration of Tyr were systematically examined. Results indicated that these factors mainly affected the reaction rate of photoreduction. The morphologies of the formed AgNPs were similar, but with small differences in particle sizes. In the examination of selectivity, sixteen other amino acids were examined. Results indicated that only amino acids of tryptophan, cysteine and histidine are photoactive and possess potential interferences in analysis of Tyr. Quantitative studies indicated that a linear response up to 10 µM with a detection limit of 100 nM could be obtained. For visually detection, color change could be observed with a concentration as low as 500 nM of Tyr.

Electroless reduction of silver chloride precipitates for the preparation of highly sensitive substrates for surface-enhanced infrared absorption (SEIRA) measurements.

To prepare silver nanoparticles (AgNPs) on infrared-transmitting crystal for surface-enhanced infrared absorption (SEIRA) measurements, a new strategy is proposed and demonstrated using electroless reduction of preformed silver chloride (AgCl) particles. Silver chloride precipitates were formed using an additive of polyvinyl pyrrolidone (PVP) to vary the size and shape of the precipitates. After settling on germanium substrates, the preformed particles of AgCl were reduced electrolessly and spontaneously coagulated to AgNPs. The resulting AgNPs showed a multilayer structure, but the AgNPs were isolated, as shown by the lack of absorption-band distortion in the SEIRA measurements. Hence, the sensitivity and analyte-loading capacity for SEIRA measurements are improved significantly. To optimize the chemical deposition and electroless reduction method, we examined several parameters, including the concentrations of reagents during AgCl precipitation and the reaction time required in the deposition-reduction steps. We used para-nitrobenzoic acid (pNBA) to probe the intensity of the SEIRA effect for the prepared substrates. To better correlate the SEIRA performances with each variable, we examined the prepared substrates using a scanning electron microscope and SEIRA. The results indicate that two major morphologies of AgNPs are observed: nanoparticles and nanorods. The distributions of nanorods we observed were related to the procedures used to prepare the substrates. Based on SEIRA signals, we observed enhancement factors approaching three orders of magnitude compared to conventional transmission measurement. Also, based on the morphologies, the large signals were mainly caused by the formation of multilayers of non-percolated AgNPs.

Sensitive and selective colorimetric detection of Cu(2+) in aqueous medium via aggregation of thiomalic acid functionalized Ag nanoparticles.

A simple and effective colorimetric method for determination of Cu(2+) in real samples was developed. In this method, thiomalic acid functionalized silver nanoparticles (TMA-AgNPs) were prepared and changes in solution color, induced by the aggregation of TMA-AgNPs in the presence of Cu(2+), were employed for quantitative analysis. The surface plasmon resonance (SPR) band of our synthesized TMA-AgNPs was located at 392 nm and shifted to a longer wavelength after aggregation due to the interactions between carboxylate and Cu(2+). A band intensity ratio of A455/(A392-A455) was constructed and used to correlate with the concentration of Cu(2+). A linear relationship was found with a linear response up to 50 nM of Cu(2+). Due to the formation of a stable carboxylate Cu(2+) complex, highly sensitive detection of Cu(2+) was achieved with the estimated detection limit approaching 1 nM. Moreover, the formation of the stable complex leads to high selectivity in the detection of Cu(2+), which was verified by examination of 12 other metal ions. In the detection of Cu(2+) in real samples, results indicated that our proposed method is simple, sensitive and selective for application in such measurements.

Photochemical decoration of magnetic composites with silver nanostructures for determination of creatinine in urine by surface-enhanced Raman spectroscopy.

In this study, silver nanostructures decorated magnetic nanoparticles for surface-enhanced Raman scattering (SERS) measurements were prepared via photoreduction utilizing the catalytic activity of ZnO nanostructure. The ZnO/Fe3O4 composite was first prepared by dispersing pre-formed magnetic nanoparticles into alkaline zinc nitrate solutions. After annealing of the precipitates, the formed ZnO/Fe3O4 composites were successfully decorated with silver nanostructures by soaking the composites into silver nitrate/ethylene glycol solution following UV irradiations. To find the optimal condition when preparing Ag@ZnO/Fe3O4 composites for SERS measurements, factors such as the reaction conditions, photoreduction time, concentration of zinc nitrate and silver nitrate were studied. Results indicated that the photoreduction efficiency was significantly improved with the assistance of ZnO but the amount of ZnO in the composite is not critical. The concentration of silver nitrate and UV irradiation time affected the morphologies of the formed composites and optimal condition in preparation of the composites for SERS measurement was found using 20mM of silver nitrate with an irradiation time of 90 min. Under the optimized condition, the obtained SERS intensities were highly reproducible with a SERS enhancement factor in the order of 7. Quantitative analyses showed that a linear range up to 1 µM with a detection limit lower than 0.1 µM in the detection of creatinine in aqueous solution could be obtained. Successful applying of these prepared composites to determine creatinine in urine sample was obtained.

Enhancement of Raman scattering for silver nanoparticles located on electrolessly roughened silicon.

To study the effect of roughness of a supporting substrate to Raman enhancement, silver nanoparticles (AgNPs) were prepared on Si with different degrees of roughness. To roughen the surface of silicon, electroless displacement was used first to grow AgNPs on smooth Si. By chemically removing the resulting AgNPs, an electrolessly roughened Si surface can be exposed. A second electroless displacement then was performed to grow new AgNPs on the roughened Si crystal to form surface-enhanced Raman scattering substrates. Another approach, called the protecting method, also was proposed and demonstrated to structure AgNPs on surface-roughened Si. In this second method, electroless displacement also was used to grow AgNPs on the Si crystal. The resulting AgNPs then were protected by thio compounds to control removal of the outer layer of AgNPs, thereby exposing the underlying AgNPs located directly on the electroless roughened Si surface. Results indicate that the structure of AgNPs on roughened Si surfaces provides approximately two orders of magnitude higher enhancement than AgNPs on non-roughened Si, and the substrates prepared in this work are highly sensitive, with enhancement factors reaching 10(8).

Photochemical decoration of silver nanoparticles on magnetic microspheres as substrates for the detection of adenine by surface-enhanced Raman scattering.

In this work, silver nanoparticles (AgNPs) decorated magnetic microspheres (MMs) are prepared as surface-enhanced Raman scattering (SERS) substrate for the analysis of adenine in aqueous solutions. To prepare these substrates, magnetic particles were first synthesized by coprecipitation of Fe(II) and Fe(III) with ammonium hydroxide. A thin layer of cross-linked polymer was formed on these magnetic particles by polymerization through suspension of magnetic particles into a solution of divinyl benzene/methyl methacrylate. The resulted polymer protected magnetic particles are round in shape with a size of 80 µm in diameter. To form AgNPs on these MMs, photochemical reduction method was employed and the factors in photochemical reduction method were studied and optimized for the preparation of highly sensitive and stable AgNPs on MMs substrates (abbreviated as AgMMs substrates). By dispersing the AgMMs in aqueous samples, cylindrical magnet was used to attract the AgMMs for SERS detections. The observed enhancement factor of AgMMs reached 7 orders in magnitude for detection of adenine with a detection limit approaching to few hundreds of nanomolar.

Sensitive cylindrical SERS substrate array for rapid microanalysis of nucleobases.

In this work, a cylindrical-substrate array for surface-enhanced Raman scattering (SERS) measurements was developed to enable analysis of nucleobases in a few microliters of liquid. To eliminate uncertainties associated with SERS detection of aqueous samples, a new type of cylindrical SERS substrate was designed to confine the aqueous sample at the tip of the SERS probe. Poly(methyl methacrylate) (PMMA) optical fibers in a series of different diameters were used as the basic substrate. A solution of poly(vinylidene fluoride)/dimethylformamide (PVDF/DMF) was used to coat the tip of each fiber to increase the surface roughness and facilitate adsorption of silver nanoparticles (AgNPs) for enhancing Raman signals. A chemical reduction method was used to form AgNPs in and on the PVDF coating layer. The reagents and reaction conditions were systematically examined with the aim of estimating the optimum parameters. Unlike the spreading of aqueous sample on most SERS substrates, particularly flat ones, the new SERS substrates showed enough hydrophobicity to restrict aqueous sample to the tip area, thus enabling quantitative analysis. The required volume of sample could be as low as 1 µL with no need for a drying step in the procedure. By aligning the cylindrical SERS substrates into a solid holder, an array of cylindrical substrates was produced for mass analysis of aqueous samples. This new substrate improves both reproducibility and sensitivity for detection in aqueous samples. The enhancement factor approaches 7 orders in magnitude with a relative standard error close to 8%. Using the optimized conditions, nucleobases of adenine, cytosine, thymine, and uracil could be detected with limits approaching a few hundreds nanomolar in only a few microliters of solution.

Silver nanoparticle-treated filter paper as a highly sensitive surface-enhanced Raman scattering (SERS) substrate for detection of tyrosine in aqueous solution.

Highly sensitive SERS substrates based on deposition of silver nanoparticles on commercially available filter paper were prepared in this work, and used to overcome problems found in analyses of aqueous samples. To prepare silver nanoparticle- (AgNP) doped filter substrates, a silver mirror reaction was used. The procedures for substrate preparation were systematically optimized. Pretreatment of filter paper, reaction time, temperature, and concentration of reagents for silver mirror reactions were studied. The morphologies of the resulting substrates were characterized by field-emission scanning electron microscopy (FE-SEM) and correlated with the SERS signals by probing with p-nitrothiophenol (pNTP). Filter papers with different pretreatments were found to have different sizes and distributions of AgNPs. The best performance was found when filter paper was pre-treated with ammonia solution before growth of AgNPs. Based on the SEM images, the resulting AgNPs had roughly spherical shape with a high degree of uniformity. The silver-coated filter paper substrates provide much higher SERS signals compared to glass substrates and the reproducibility was improved significantly. Based on statistical analyses, the relative standard deviations for substrate-to-substrate and spot-to-spot were both were less than 8% and the enhancement factors for the substrates were, in general, higher than 107. The SERS substrates were used to selectively detect tyrosine in aqueous solution. Results indicate that filter-based SERS substrates are highly suited to detection of tyrosine. Compared to glass-based SERS substrates, 50 times more SERS signal was observed in detection of tyrosine. The linear range can be up to 100 µM with a detection limit of 625 nM (SN(-1)=3).

Preparation of high-capacity substrates from polycrystalline silver chloride for the selective detection of tyrosine by surface-enhanced infrared absorption (SEIRA) measurements.

In this work, stacked but isolated silver nanoparticles (AgNPs) on silver chloride were prepared in order to create sensitive substrates that could be used to determine analytes in aqueous solution by performing surface-enhanced infrared absorption (SEIRA) measurements. These substrates have a high loading capacity, which improves sensitivity, thus allowing the detection of biospecies such as weak infrared absorbers (including amino acids) in aqueous solution. AgNPs were obtained by converting the surface layers of the silver chloride crystals into stacked but isolated AgNPs using reducing agents. To optimize the conditions used to prepare the SEIRA substrates, the roles of four common reducing agents-hydrazine, sodium borohydride, glucose, and formaldehyde-were explored by probing the finished substrates with para-nitrobenzoic acid (PNBA). Factors that influence the morphologies of the AgNPs were examined systemically. These factors include the pH of the reducing solution, the reaction time, and the concentration of the reducing agent. Results indicate that the concentration of the reducing agent and the pH of the solution strongly influence the AgNP morphology and hence the SEIRA signals. Under optimized conditions, the resulting substrates showed intense SEIRA spectra from PNBA, with enhancement factors of around two orders of magnitude compared to conventional transmission methods. The new substrates offer a high loading capacity and good heat tolerance, allowing the direct infrared detection of tyrosine in aqueous solution.

Gondola-shaped tetra-rhenium metallacycles modified evanescent wave infrared chemical sensors for selective determination of volatile organic compounds.

Water-stable and cavity-contained rhenium metallacycles were synthesized, and their ability to selectively interact with volatile organic compounds (VOCs) systematically studied using attenuated total reflection infrared (ATR-IR) spectroscopy. Integrating the unique properties of rhenium metallacycles into optical sensing technologies significantly improves selectivity in detecting aromatic compounds. To explore the interaction of rhenium metallacycles with VOCs, the surface of ATR sensing elements was modified with the synthesized rhenium metallacycles and used to detect VOCs. The results indicate that rhenium metallacycles have crown ether-like recognition sites, which can selectively interact with aromatic compounds, especially those bearing polar functional groups. The IR absorption bands of rhenium metallacycles shift significantly upon adsorption of aromatic VOCs, revealing a strong interaction between the tetra-rhenium metallacycles and guest aromatic compounds. Optimizing the thickness of the metallacycles coated on the surface of the sensing element led to rapid response in detection. The dynamic range of response was generally up to 30 mg/L with detection limits ca. 30 µg/L. Further studies of the effect of interferences indicate that recovery can be higher than 95% for most of the compounds tested. The results on the flow-cell device indicated that the performances were similar to a static detection system but the detection of VOCs can be largely simplified.

para-Mercaptobenzoic acid-modified silver nanoparticles as sensing media for the detection of ammonia in air based on infrared surface enhancement effect.

To utilize the large signals provided by surface-enhanced infrared absorption (SEIRA) measurements for chemical sensing, a new sensing scheme was proposed and demonstrated for detection of ammonia in air samples. To increase the SEIRA effect, a sensing phase composed of multi-layers of silver nanoparticles (AgNPs) was prepared using a chemically controlled electroless deposition method. para-Mercaptobenzoic acid (pMBA) served as the controlling agent in formation of AgNPs, a surface modification agent of AgNPs for sensing, and a stabilizer to protect the AgNPs from coagulation and oxidation. The sensing approach utilized the interaction between pMBA and ammonia, which involves the formation of carboxylate-ammonium complex. After interaction, the enhanced IR absorption bands of pMBA on AgNPs were significantly changed and able to provide quantitative information on the ammonia concentrations. To optimize the conditions for preparing sensing elements, parameters used to form multi-layers of AgNPs were systematically varied and their corresponding sensitivities in detection of ammonia were recorded. The results indicate that AgNPs with diameters in the range of 100 nm provided the best performance in terms of detecting ammonia via the SEIRA effect. Also, the analytical signal generally increased as the number of layers of AgNPs increased, but was limited to certain layers, depending on the reaction conditions used in preparation of AgNPs. The sensing elements were found to be highly selective to ammonia and the detection limit approached 150 ppb with a linear range up to 25 ppm.

Surface-enhanced infrared spectroscopic studies of the catalytic behavior of silver nanoparticles on a germanium substrate.

The catalytic activity of silver nanoparticles (AgNPs) on a germanium substrate is reported. Para-nitrothiophenol (pNTP) that had been adsorbed on this substrate is converted to p-aminothiophenol (pATP) under very mild reaction conditions, such as simply soaking in water. The AgNPs may be formed either by physical vapor deposition or by electroless deposition from a solution of silver nitrate. Analogous reactions were not observed on copper nanoparticles on germanium or AgNPs on silicon or zinc selenide even though very slow conversion of pNTP to pATP was observed with Au nanoparticles (AuNPs) on Ge under controlled reaction conditions. The effects of factors that could influence the catalytic reaction were examined; these included the particle size of the AgNPs, reaction temperature, concentration and chemical nature of other ions present in the solution, the pH of the water, and the nature of the substrate. The reaction rate was approximately independent of the particle size for AgNPs between 50 and 150 nm in diameter. Increasing the temperature accelerates the reaction significantly; at temperatures above 40 °C, the adsorbed pNTP is completely converted by water within five minutes. Not surprisingly, the reaction rate was increased as the pH of the solution was decreased, as the reduction of each nitro group to an amino group requires six protons. The presence of Br(-) and I(-) ions accelerated the reaction to the point that even at 4 °C, the conversion of the nitro group was still observable, while solutions containing chloride ions had to be heated to 40 °C before their effect became apparent. Apparently, Br(-) and I(-) ions remove the oxide layer from the surface of the germanium substrate, facilitating transfer of electrons from the germanium to the nitro group of the pNTP.

Chemical reduction method for preparation of silver nanoparticles on a silver chloride substrate for application in surface-enhanced infrared optical sensors.

A new method for the preparation of silver nanoparticles (AgNPs) on silver chloride discs was developed to integrate the unique properties of plasmonic nanoparticles into infrared optical sensing technologies. AgNP layers exhibiting strong infrared surface enhancement were prepared by reacting silver chloride discs in a solution containing hydrazine, which acts as a reducing agent. The silver ions in the outer layer of the disc could be reduced under proper conditions and the reduced silver coagulated to form suitable AgNPs for surface-enhanced infrared absorption (SEIRA) measurements. To examine the influences of the reaction solution composition and also to optimize preparation of SEIRA substrates, factors such as pH value, reaction time, and concentration of reducing agent were examined. Results indicated that both the concentrations of hydrazine and hydroxide strongly influenced the SEIRA signals. The strongest signals were observed when AgNPs on a AgCl substrate were prepared by using a reducing solution of 20 mM NaOH with 0.75 mM hydrazine. Using the optimized substrates, intense SEIRA spectra were observed with an enhancement factor around two orders of magnitude compared to measurements made using conventional sampling techniques.