The vast unexplored virus biodiversity makes the application of virus templates to nanomaterial synthesis especially promising. Here, a new biotemplate, Barley stripe mosaic virus (BSMV) was successfully used to synthesize organic-metal nanorods of similarly high quality to those produced with Tobacco mosaic virus (TMV). The mineralization behavior was characterized in terms of the reduction and adsorption of precursor and nanocrystal formation processes. The BSMV surface-mediated reduction of Pd proceeded via first-order kinetics in both Pd and BSMV. The adsorption equilibrium relationship of PdClHO on the BSMV surface was described by a multistep Langmuir isotherm suggesting alternative adsorbate-adsorbent interactions when compared to those on TMV. It was deduced that the first local isotherm is governed by electrostatically driven adsorption, which is then followed by sorption driven by covalent affinity of metal precursor molecules for amino acid residues. Furthermore, the total adsorption capacity of palladium species on BSMV is more than double of that on TMV. Finally, study of the BSMV-Pd particles by combining USAXS and SAXS enabled the characterization of all length scales in the synthesized nanomaterials. Results confirm the presence of core-shell cylindrical particles with 1-2 nm grains. The nanorods were uniform and monodisperse, with controllable diameters and therefore, of similar quality to those synthesized with TMV. Overall, BSMV has been confirmed as a viable alternate biotemplate with unique biomineralization behavior. With these results, the biotemplate toolbox has been expanded for the synthesis of new materials and comparative study of biomineralization processes.
An environmentally friendly technique has been developed to produce metal nanoparticles using green synthesis methods. In this study, silver nanostructures were synthesized using different sugar substitutes and artificial sweeteners as green reducing agents in an aqueous solution at low temperature. The main ingredients (such as maltodextrin, sucrose, saccharin, and sucralose) of the artificial sweeteners acting as reducing agents were used to reduce Ag+ ions to Ag0. The pH of the solution was controlled during synthesis through the addition of sodium hydroxide (NaOH) to increase the strength of the reducing agents by converting nonreducing sugars to reducing ones and consequently increasing the rate of silver nanoparticle formation. The size and morphology of the synthesized nanostructures were characterized by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDX). The formation of nanostructures during the course of the reactions was investigated by UV-visible (UV-vis) spectroscopy characterization of an aliquot of sample at specific intervals. The function of each artificial sweetener and corresponding ingredients as a reducing agent and capping agent was investigated by Fourier-transform infrared spectroscopy (FTIR) and mass spectrometry (MS).
There is a lack of fundamental information about the molecular processes governing biomineralization of inorganic materials to produce nanostructures on biological templates. This information is essential for the directed synthesis of high quality nanomaterials via biotemplating. We characterized palladium (Pd) mineralization via the individual adsorption, reduction, and nanocrystal growth processes, which simultaneously occur during the hydrothermal synthesis on the Tobacco mosaic virus (TMV). The adsorption of precursor and reduction of palladium were decoupled through UV-vis Spectroscopy and in situ X-ray absorption spectroscopy studies. The role of additional cysteine (Cys) residues, ionic strength, and coating density on the fundamental parameters describing these processes were quantitatively evaluated. Primary nanocrystal growth and structural orientation of Pd nanoparticles was characterized using in situ small angle X-ray scattering. The adsorption, reduction of Pd species, and nanocrystal sizes were significantly changed on addition of Cys residues to the amino terminus of the TMV coat protein. Reduction of Pd on an already coated virion was dependent on the Pd surface area, and was hindered by the presence of residual salt. Furthermore, trends in Pd adsorption intensity and capacity suggested that chloride ions affected the adsorption equilibrium. Application of this fundamental approach with further optimization of parameters dictating biomineralization would facilitate directed synthesis and scale up of bioinorganic systems.
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