title: Decoupling and elucidation of surface-driven processes during inorganic mineralization on virus templates.
abstract: 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.
authors.affiliation: 480 Stadium Mall Drive, School of Chemical Engineering, Purdue University, West Lafayette, IN 47907, United States.
authors.forename: Oluwamayowa O
authors.initials: OO
authors.lastname: Adigun
authors.affiliation: 480 Stadium Mall Drive, School of Chemical Engineering, Purdue University, West Lafayette, IN 47907, United States.
authors.forename: Gloria
authors.initials: G
authors.lastname: Novikova
authors.affiliation: 480 Stadium Mall Drive, School of Chemical Engineering, Purdue University, West Lafayette, IN 47907, United States.
authors.forename: Erin Lynn
authors.initials: EL
authors.lastname: Retzlaff-Roberts
authors.affiliation: 915 West State Street, Department of Botany and Plant Pathology, Purdue University, West Lafayette, IN 47907, United States.
authors.forename: BongSuk
authors.initials: B
authors.lastname: Kim
authors.affiliation: 480 Stadium Mall Drive, School of Chemical Engineering, Purdue University, West Lafayette, IN 47907, United States.
authors.forename: Jeffrey T
authors.initials: JT
authors.lastname: Miller
authors.affiliation: 915 West State Street, Department of Botany and Plant Pathology, Purdue University, West Lafayette, IN 47907, United States.
authors.forename: L Sue
authors.initials: LS
authors.lastname: Loesch-Fries
authors.affiliation: 480 Stadium Mall Drive, School of Chemical Engineering, Purdue University, West Lafayette, IN 47907, United States. Electronic address: mtharris@purdue.edu.
authors.forename: Michael T
authors.initials: MT
authors.lastname: Harris
mesh_terms: D000327:Adsorption; D036022:Capsid Proteins / Q000737:chemistry* / Q000235:genetics / Q000378:metabolism; D003545:Cysteine / Q000737:chemistry*; D015870:Gene Expression; D006358:Hot Temperature; D007700:Kinetics; D053768:Metal Nanoparticles / Q000737:chemistry* / Q000648:ultrastructure; D009154:Mutation; D009994:Osmolar Concentration; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry*; D013329:Structure-Activity Relationship; D013499:Surface Properties; D014027:Tobacco Mosaic Virus / Q000737:chemistry* / Q000235:genetics / Q000378:metabolism
chemical_list: D036022:Capsid Proteins; D010165:Palladium; D003545:Cysteine
keywords: Adsorption; Biomineralization; Cysteine; Nanocrystal growth; Reduction; Small angle X-ray scattering; Tobacco mosaic virus; X-ray absorption spectroscopy