5.1. Nanoalloys of Group 11 (Cu, Ag, Au) 865 5.1.1. Cu−Ag 866 5.1.2. Cu−Au 867 5.1.3. Ag−Au 870 5.1.4. Cu−Ag−Au 872 5.2. Nanoalloys of Group 10 (Ni, Pd, Pt) 872 5.2.1. Ni−Pd 872 * To whom correspondence should be addressed. Phone: +39010 3536214. Fax:+39010 311066. E-mail: ferrando@fisica.unige.it. † Universita di Genova. ‡ Argonne National Laboratory. § University of Birmingham. | As of October 1, 2007, Chemical Sciences and Engineering Division. Volume 108, Number 3

Nanoalloys: From Theory to Applications of Alloy Clusters and Nanoparticles

We are just beginning to understand the metabolism of heavy metals and to use their metabolic functions in biotechnology, although heavy metals comprise the major part of the elements in the periodic table. Because they can form complex compounds, some heavy metal ions are essential trace elements, but, essential or not, most heavy metals are toxic at higher concentrations. This review describes the workings of known metal-resistance systems in microorganisms. After an account of the basic principles of homoeostasis for all heavy-metal ions, the transport of the 17 most important (heavy metal) elements is compared.

Microbial heavy-metal resistance

Rapid synthesis of Au, Ag, and bimetallic Au core-Ag shell nanoparticles using Neem (Azadirachta indica) leaf broth.

The synthesis of nanocrystals is in the limelight in modern nanotechnology. Biosynthesis of nanoparticles by plant extracts is currently under exploitation. Not only could silver nanoparticles ranging from 55 to 80 nm in size be fabricated, but also triangular or spherical shaped gold nanoparticles could be easily modulated by reacting the novel sundried biomass of Cinnamomum camphora leaf with aqueous silver or gold precursors at ambient temperature. The marked difference of shape control between gold and silver nanoparticles was attributed to the comparative advantage of protective biomolecules and reductive biomolecules. The polyol components and the water-soluble heterocyclic components were mainly responsible for the reduction of silver ions or chloroaurate ions and the stabilization of the nanoparticles, respectively. The sundried leaf in this work was very suitable for simple synthesis of nanoparticles.

https://iopscience.iop.org/article/10.1088/0957-4484/18/10/105104/pdf

Biosynthesis of silver and gold nanoparticles by novel sundried Cinnamomum camphora leaf

Nanotechnology involves the production, manipulation and use of materials ranging in size from less than a micron to that of individual atoms. Although nanomaterials may be synthesized using chemical approaches, it is now possible to include the use of biological materials. In this review, we critically assess the role of microorganisms and plants in the synthesis of nanoparticles.

Biosynthesis of nanoparticles: technological concepts and future applications

Worldwide usage of platinum group metals is increasing, prompting new recovery technologies. Resting cells of Desulfovibrio desulfuricans reduced soluble Pd2+ to elemental, cell-bound Pd0 supported by pyruvate, formate, or H2 as the electron donor without biochemical cofactors. Pd reduction was O2 insensitive, opening the way for recycling and recovery of Pd under oxic conditions.

Enzymatic Recovery of Elemental Palladium by Using Sulfate-Reducing Bacteria

The reduction of Pd(II) to Pd(0) was accelerated by using the sulfate-reducing bacterium Desulfovibrio desulfuricans NCIMB 8307 at the expense of formate or H(2) as electron donors at pH 2-7. With formate no reduction occurred at pH 2, but with H(2) 50% of the activity was retained at pH 2, with the maximum rate (1.3-1.4 micromol min(-1) mg dry cells(-1)) seen at pH 3-7, which was similar to the rate with formate at neutral pH. Excess nitrate was inhibitory to Pd(II) reduction using formate, but not H(2). Chloride ion was inhibitory as low as 100 mM using formate but with H(2) only ca. 25% inhibition was observed at 500 mM Cl(-) and H(2) was concluded to be the electron donor of choice for the potential remediation of industrial wastes. Deposited Pd was visible on the cells using transmission and scanning electron microscopy and analysis by energy dispersive X-ray microanalysis (EDAX) identified the deposit as Pd, confirmed as Pd(0) by X-ray powder diffraction analysis (XRD). The crystal size of the biodeposited Pd(0) was determined to be only 50% of the size of Pd(0) crystals manufactured chemically from Pd(II) at the expense of H(2) and, unlike the chemically manufactured material, the biocrystal size was independent of the pH. The "biological" Pd(0) functioned as a superior chemical catalyst in a test reaction which liberated hydrogen from hypophosphite. Pd, and also Pt and Rh, could be recovered by resting cell suspensions under H(2) from an industrial processing wastewater, suggesting a possible future application of bioprocessing technology for precious metals.

Bioreduction and biocrystallization of palladium by Desulfovibrio desulfuricans NCIMB 8307

A Citrobacter sp. accumulated uranyl ion (UO2(2+)) via precipitation with phosphate ligand liberated by phosphatase activity. The onset and rate of uranyl phosphate deposition were promoted by NH4(+), forming NH(4)UO(2)PO(4), which has a lower solubility product than NaUO(2)PO(4). This acceleration decoupled the rate-limiting chemical crystallization process from the biochemical phosphate ligand generation. This provided a novel approach to monitor the cell-surface-associated changes using atomic-force microscopy in conjunction with transmission electron microscopy and electron-probe X-ray microanalysis, to visualize deposition of uranyl phosphate at the cell surface. Analysis of extracted surface materials by (31)P NMR spectroscopy showed phosphorus resonances at chemical shifts of 0.3 and 2.0 p.p.m., consistent with monophosphate groups of the lipid A backbone of the lipopolysaccharide (LPS). Addition of fUO2(2+) to the extract gave a yellow precipitate which contained uranyl phosphate, while addition of Cd(2+) gave a chemical shift of both resonances to a single new resonance at 3 p.p.m. Acid-phosphatase-mediated crystal growth exocellularly was suggested by the presence of acid phosphatase, localized by immunogold labelling, on the outer membrane and on material exuded from the cells. Metal deposition is proposed to occur via an initial nucleation with phosphate groups localized within the LPS, shown by other workers to be produced exocellularly in association with phosphatase. The crystals are further consolidated with additional, enzymically generated phosphate in close juxtaposition, giving high loads of LPS-bound uranyl phosphate without loss of activity and distinguishing this from simple biosorption, or periplasmic or cellular metal accumulation mechanisms. Accumulation of 'tethered' metal phosphate within the LPS is suggested to prevent fouling of the cell surface by the accumulated precipitate and localization of phosphatase exocellularly is consistent with its possible functions in homeostatis and metal resistance.

Enzymically mediated bioprecipitation of uranium by a Citrobacter sp. : a concerted role for exocellular lipopolysaccharide and associated phosphatase in biomineral formation.

Palladium uptake by resting cell suspensions of Desulfovibrio desulfuricans NCIMB 8307 was studied without or with electron donor (formate), which gave metal uptake attributable to biosorption of Pd(II) and bioreduction of Pd(II) to Pd(0), respectively. The maximum biosorption capacity of palladium (at pH 2) was up to 196 mg Pd g−1 dry cells (1.85 mmol g−1; approx 20% of the dry weight). Biosorption was to 85% of the maximum in less than 10 min and the biomass was saturated within 30 min. Biosorption of Pd(II) was greater from the chloro- than the ammine complex and was inhibited in the presence of excess chloride ion. Bioreductive accumulation of Pd(II) from Pd(NH3)42+ was achieved in the presence of electron donor (formate) but was also inhibited by excess Cl−. Up to 100% of Pd(II) reduction to Pd(0) was achieved within 5 min anaerobically at pH 7 and 30 min at pH 3. Pd(0) was localized on the biomass surface using electron microscopy and was characterized using energy dispersive X-ray microanalysis (EDAX) and X-ray diffraction analysis (XRD). Biosorption was Pd-specific with respect to Pt and Rh using test solutions and acid (aqua regia) leachates from spent automotive catalysts. The total Pd removed from the latter was only 15%, attributable to the inhibitory effect of residual chloride ion from the acidic extractant. Pd biorecovery is limited by the need for an improved extraction technology to minimize the formation of PdCl42− in solution rather than by constraints of the Pd-accumulating biomass.



© 2002 Society of Chemical Industry

Bioaccumulation of palladium by Desulfovibrio desulfuricans

The complete and continuous reduction of 1 mM Cr(VI) to Cr(III) was achieved in a flow-through reactor using a novel bioinorganic catalyst (“MM-bio-Pd(0)”), which was produced by single-step reduction of platinum group metals (PGM) from industrial waste solution onto biomass of Desulfovibrio desulfuricans ATCC 29577. Two flow-through reactor systems were compared using both “MM-bio-Pd(0)” and chemically reduced Pd(0). Reactors containing the latter removed Cr(VI) for 1 week only at the expense of formate as the electron donor, whereas the former gave complete Cr(VI) removal for 3 months of continuous operation. Mass balance analysis showed 100% reduction of Cr(VI) to soluble Cr(III) in the bioreactor exit solution. With the use of electron paramagnetic resonance (EPR) no intermediate Cr(V) species could be detected. Pd(0) was biodeposited similarly using Escherichia coli MC4100 and “bio-Pd(0)”. The latter was used to recover Pd(II) from two acidic industrial waste leachates to generate two types of “MM-bi...

Biorecovered precious metals from industrial wastes: single-step conversion of a mixed metal liquid waste to a bioinorganic catalyst with environmental application.

Ping Yong

Papers

Enzymatic Recovery of Elemental Palladium by Using Sulfate-Reducing Bacteria

Bioreduction and biocrystallization of palladium by Desulfovibrio desulfuricans NCIMB 8307

Enzymically mediated bioprecipitation of uranium by a Citrobacter sp. : a concerted role for exocellular lipopolysaccharide and associated phosphatase in biomineral formation.

Bioaccumulation of palladium by Desulfovibrio desulfuricans

Biorecovered precious metals from industrial wastes: single-step conversion of a mixed metal liquid waste to a bioinorganic catalyst with environmental application.