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

Sensitive Cylindrical SERS Substrate Array for Rapid Microanalysis of Nucleobases

In this work, a cylindrical-substrate array for surfaceenhanced 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

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

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

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

An oxidation layer for regulating galvanically grown silver nanoparticles on silicon crystal for highly sensitive surface-enhanced Raman scattering measurements

In this study, a new method was developed in which an oxidation layer is used to regulate the morphology of silver nanoparticles (AgNPs) formed on Si crystals during galvanic displacement (GD). Using an oxidation layer yielded reproducible and stable AgNPs@Si substrates for sensitive surface-enhanced Raman scattering (SERS) measurements. The estimated SERS enhancement was at least an order of magnitude greater than for substrates prepared using a conventional GD method. The formation of Si–O− on the Si surface increased the adsorption of the AgNPs. Highly reproducible results were obtained, with a relative standard deviation of approximately 5%. To investigate the role of the oxidation layer and to optimize the reaction conditions, the oxidation layer thickness and chemical composition of the reaction solution were adjusted. The degree of aggregation in AgNP formation was mainly controlled by the thickness of the oxidation layer, whereas the size of the AgNPs was affected by both the concentration of AgNO3 and hydrofluoric acid in the reaction solution and the GD reaction time. When the optimized reaction conditions were used, the AgNPs@Si substrate had an enhancement factor of >107