Ex situ formation of metal selenide quantum dots using bacterially derived selenide precursors.

Luminescent quantum dots were synthesized using bacterially derived selenide (Se(II-)) as the precursor. Biogenic Se(II-) was produced by the reduction of Se(IV) by Veillonella atypica and compared directly against borohydride-reduced Se(IV) for the production of glutathione-stabilized CdSe and ß-mercaptoethanol-stabilized ZnSe nanoparticles by aqueous synthesis. Biological Se(II-) formed smaller, narrower size distributed QDs under the same conditions. The growth kinetics of biologically sourced CdSe phases were slower. The proteins isolated from filter sterilized biogenic Se(II-) included a methylmalonyl-CoA decarboxylase previously characterized in the closely related Veillonella parvula. XAS analysis of the glutathione-capped CdSe at the S K-edge suggested that sulfur from the glutathione was structurally incorporated within the CdSe. A novel synchrotron based XAS technique was also developed to follow the nucleation of biological and inorganic selenide phases, and showed that biogenic Se(II-) is more stable and more resistant to beam-induced oxidative damage than its inorganic counterpart. The bacterial production of quantum dot precursors offers an alternative, 'green' synthesis technique that negates the requirement of expensive, toxic chemicals and suggests a possible link to the exploitation of selenium contaminated waste streams.

Synthesis and properties of titanomagnetite (Fe(3-x)Ti(x)O4) nanoparticles: a tunable solid-state Fe(II/III) redox system.

Titanomagnetite (Fe(3-x)Ti(x)O(4)) nanoparticles were synthesized by room temperature aqueous precipitation, in which Ti(IV) replaces Fe(III) and is charge compensated by conversion of Fe(III) to Fe(II) in the unit cell. A comprehensive suite of tools was used to probe composition, structure, and magnetic properties down to site-occupancy level, emphasizing distribution and accessibility of Fe(II) as a function of x. Synthesis of nanoparticles in the range 0≤x≤0.6 was attempted; Ti, total Fe and Fe(II) content were verified by chemical analysis. TEM indicated homogeneous spherical 9-12 nm particles. µ-XRD and Mössbauer spectroscopy on anoxic aqueous suspensions verified the inverse spinel structure and Ti(IV) incorporation in the unit cell up to x≤0.38, based on Fe(II)/Fe(III) ratio deduced from the unit cell edge and Mössbauer spectra. Nanoparticles with a higher value of x possessed a minor amorphous secondary Fe(II)/Ti(IV) phase. XANES/EXAFS indicated Ti(IV) incorporation in the octahedral sublattice (B-site) and proportional increases in Fe(II)/Fe(III) ratio. XA/XMCD indicated that increases arise from increasing B-site Fe(II), and that these charge-balancing equivalents segregate to those B-sites near particle surfaces. Dissolution studies showed that this segregation persists after release of Fe(II) into solution, in amounts systematically proportional to x and thus the Fe(II)/Fe(III) ratio. A mechanistic reaction model was developed entailing mobile B-site Fe(II) supplying a highly interactive surface phase that undergoes interfacial electron transfer with oxidants in solution, sustained by outward Fe(II) migration from particle interiors and concurrent inward migration of charge-balancing cationic vacancies in a ratio of 3:1.

Use of biogenic and abiotic elemental selenium nanospheres to sequester elemental mercury released from mercury contaminated museum specimens.

Mercuric chloride solutions have historically been used as pesticides to prevent bacterial, fungal and insect degradation of herbarium specimens. The University of Manchester museum herbarium contains over a million specimens from numerous collections, many preserved using HgCl(2) and its transformation to Hg(v)(0) represents a health risk to herbarium staff. Elevated mercury concentrations in work areas (∼ 1.7 µg m(-3)) are below advised safe levels (<25 µg m(-3)) but up to 90 µg m(-3) mercury vapour was measured in specimen boxes, representing a risk when accessing the samples. Mercury vapour release correlated strongly with temperature. Mercury salts were observed on botanical specimens at concentrations up to 2.85 wt% (bulk); XPS, SEM-EDS and XANES suggest the presence of residual HgCl(2) as well as cubic HgS and HgO. Bacterially derived, amorphous nanospheres of elemental selenium effectively sequestered the mercury vapour in the specimen boxes (up to 19 wt%), and analysis demonstrated that the Hg(v)(0) was oxidised by the selenium to form stable HgSe on the surface of the nanospheres. Biogenic Se(0) can be used to reduce Hg(v)(0) in long term, slow release environments.

Biomineralization: linking the fossil record to the production of high value functional materials.

The microbial cell offers a highly efficient template for the formation of nanoparticles with interesting properties including high catalytic, magnetic and light-emitting activities. Thus biomineralization products are not only important in global biogeochemical cycles, but they also have considerable commercial potential, offering new methods for material synthesis that eliminate toxic organic solvents and minimize expensive high-temperature and pressure processing steps. In this review we describe a range of bacterial processes that can be harnessed to make precious metal catalysts from waste streams, ferrite spinels for biomedicine and catalysis, metal phosphates for environmental remediation and biomedical applications, and biogenic selenides for a range of optical devices. Recent molecular-scale studies have shown that the structure and properties of bionanominerals can be fine-tuned by subtle manipulations to the starting materials and to the genetic makeup of the cell. This review is dedicated to the late Terry Beveridge who contributed much to the field of biomineralization, and provided early models to rationalize the mechanisms of biomineral synthesis, including those of geological and commercial potential.

XAS and XMCD evidence for species-dependent partitioning of arsenic during microbial reduction of ferrihydrite to magnetite.

Poorly crystalline Fe(III) oxyhydroxides, ubiquitously distributed as mineral coatings and discrete particles in aquifer sediments, are well-known hosts of sedimentary As. Microbial reduction of these phases is widely thought to be responsible for the genesis of As-rich reducing groundwaters found in many parts of the world, most notably in Bangladesh and West Bengal, India. As such, it is important to understand the behavior of As associated with ferric oxyhydroxides during the early stages of Fe(lll) reduction. We have used X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) to elucidate the changes in the bonding mechanism of As(III) and As(V) as their host Fe(III) oxyhydroxide undergoes bacterially induced reductive transformation to magnetite. Two-line ferrihydrite, with adsorbed As(III) or As(V), was incubated under anaerobic conditions in the presence of acetate as an electron donor, and Geobacter sulfurreducens, a subsurface bacterium capable of respiring on Fe(lll), but not As(V). In both experiments, no increase in dissolved As was observed during reduction to magnetite (complete upon 5 days incubation), consistent with our earlier observation of As sequestration by the formation of biogenic Fe(III)-bearing minerals. XAS data suggested that the As bonding environment of the As(III)-magnetite product is indistinguishable from that obtained from simple adsorption of As(lll) on the surface of biogenic magnetite. In contrast, reduction of As(V)-sorbed ferrihydrite to magnetite caused incorporation of As5+ within the magnetite structure. XMCD analysis provided further evidence of structural partitioning of As5+ as the small size of the As5+ cation caused a distortion of the spinel structure compared to standard biogenic magnetite. These results may have implications regarding the species-dependent mobility of As undergoing anoxic biogeochemical transformations, e.g., during early sedimentary diagenesis.