Microbially Mediated Ore-Forming Processes and Cell Mineralization.

Sedimentary black shale-hosted manganese carbonate and oxide ores were studied by high-resolution in situ detailed optical and cathodoluminescence microscopy, Raman spectroscopy, and FTIR spectroscopy to determine microbial contribution in metallogenesis. This study of the Urucum Mn deposit in Brazil is included as a case study for microbially mediated ore-forming processes. The results were compared and interpreted in a comparative way, and the data were elaborated by a complex, structural hierarchical method. The first syngenetic products of microbial enzymatic oxidation were ferrihydrite and lepidocrocite on the Fe side, and vernadite, todorokite, birnessite, and manganite on the Mn side, formed under obligatory oxic (Mn) and suboxic (Fe) conditions and close to neutral pH. Fe- and Mn-oxidizing bacteria played a basic role in metallogenesis based on microtextural features, bioindicator minerals, and embedded variable organic matter. Trace element content is determined by source of elements and microbial activity. The present Urucum (Brazil), Datangpo (China), and Úrkút (Hungary) deposits are the result of complex diagenetic processes, which include the decomposition and mineralization of cell and extracellular polymeric substance (EPS) of Fe and Mn bacteria and cyanobacteria. Heterotrophic cell colonies activated randomly in the microbialite sediment after burial in suboxic neutral/alkaline conditions, forming Mn carbonates and variable cation-bearing oxides side by side with lithification and stabilization of minerals. Deposits of variable geological ages and geographical occurrences show strong similarities and indicate two-step microbial metallogenesis: a primary chemolithoautotrophic, and a diagenetic heterotrophic microbial cycle, influenced strongly by mineralization of cells and EPSs. These processes perform a basic role in controlling major and trace element distribution in sedimentary environments on a global level and place biogeochemical constraints on the element content of natural waters, precipitation of minerals, and water contaminants.

DFT Study on the Mechanism of Hydrogen Storage Based on the Formate-Bicarbonate Equilibrium Catalyzed by an Ir-NHC Complex: An Elusive Intramolecular C-H Activation.

A novel iridium based, water-soluble phosphine-NHC (N-heterocyclic carbene) complex, Na2[Ir( emim)(η4-COD)( mtppts)] was previously developed in our research group. It was shown that it is a very effective catalyst for the reversible storage of hydrogen based on the formate-bicarbonate equilibrium. In this paper, we present a DFT investigation on the noninnocent behavior of the NHC ligand toward C-H activation of the N-ethyl side chain and its possible role in the hydrogen storage mechanism. After preliminary investigations, using both computations and NMR measurements, we conclude that the COD ligand leaves the precatalyst irreversibly and the C-H activation takes place on a monophosphine complex. Two main pathways are considered in which the active Ir(III) complexes are generated differently: One is the cyclometalation path involving the ethyl side chain, the other is the oxidative addition step of a water molecule which has a higher barrier but provide a more stable starting state. We find that though the latter, a catalytic cycle where a hydride is abstracted from formate and gets protonated by solvent molecules gives the lowest calculated energy barrier, +25.8 kcal mol-1. That is, avoiding further redox processes is preferred. There are other pathways involving thermodynamically accessible C-H activated iridacycles but those involve slightly higher overall activation barriers due to the required Ir(I)/Ir(III) transitions. The cycle which involves only iridacycle intermediates offer the lowest energy span (energy difference calculated between only the highest and lowest energy points inside the cycle), however. Together with the experimental results, this implies that C-H activation of the N-ethyl side chain happens off-cycle or the starting solvent addition step of the dominant pathway is blocked kinetically. We also discuss the hydrogen uptake reaction catalyzed by cyclometalated species where the reduction of CO2 is preferred over reversing the first main cycle.

A novel carbohydrate labeling method utilizing transfer hydrogenation-mediated reductive amination.

One of the most frequently used high-resolution glycan analysis methods in the biopharmaceutical and biomedical fields is capillary electrophoresis with laser-induced fluorescence (CE-LIF) detection. Glycans are usually labeled by reductive amination with a charged fluorophore containing a primary amine, which reacts with the aldehyde group at the reducing end of the glycan structures. In this reaction, first a Schiff base is formed that is reduced to form a stable conjugate by a hydrogenation reagent, such as sodium cyanoborohydride. In large scale biopharmaceutical applications, such as clone selection for glycoprotein therapeutics, hundreds of reactions are accomplished simultaneously, so the HCN generated in the process poses a safety concern. To alleviate this issue, here we propose catalytic hydrogen transfer from formic acid catalyzed by water-soluble iridium(III)- and ruthenium(II)-phosphine complexes as a novel alternative to hydrogenation. The easily synthesized water-soluble iridium(III) and the ruthenium(II) hydrido complexes showed high catalytic activity in carbohydrate labeling. This procedure is environmentally friendly and reduces the health risks for the industry. Using carbohydrate standards, oligosaccharides released from glycoproteins with highly sialylated (fetuin), high mannose (ribonuclease B) and mixed sialo and neutral (human plasma) N-glycans, we demonstrated similar labeling efficiencies for iridium(III) dihydride to that of the conventionally used sodium cyanoborohydride based reaction. The derivatization reaction time was less than 20min with no bias towards the above mentioned specific glycan structures.

Water-Soluble Iridium-NHC-Phosphine Complexes as Catalysts for Chemical Hydrogen Batteries Based on Formate.

Molecular hydrogen, obtained by water electrolysis or photocatalytic water splitting, can be used to store energy obtained from intermittent sources such as wind and solar power. The storage and safe transportation of H2 , however, is an open and central question in such a hydrogen economy. Easy-to-synthesize, water-soluble iridium-N-heterocyclic carbene-phosphine (Ir(I) -NHC-phosphine) catalysts show unprecedented high catalytic activity in dehydrogenation of aqueous sodium formate. Fast reversible generation and storage of hydrogen can be achieved with these catalysts by a simple decrease or increase in the hydrogen pressure, respectively.

Classical and non-classical phosphine-Ru(II)-hydrides in aqueous solutions: many, various, and useful.

Hydrogenation of the water-soluble [{RuCl(2)(mtppms)(2)}(2)] (mtppms = monosulfonated triphenylphosphine) was studied in aqueous solutions in the presence of excess mtppms both with H(2) and with aqueous HCOONa. Depending on the reductant, the pH and H(2) pressure altogether nine hydride species were identified. In acidic solutions at 1 bar H(2) pressure the known [RuHCl(mtppms)(3)] (1) and [{RuHCl(mtppms)(2)}(2)] (3) were formed, however, elevated pressure led to the formation of trans-[RuH(2)(mtppms)(4)] (11). In basic solutions at atmospheric pressure cis-fac-[RuH(2)(H(2)O)(mtppms)(3)] (12) was observed which was readily replaced by [RuH(2)(η(2)-H(2))(mtppms)(3)] (13) at higher H(2) pressures. 13 is the first water-soluble and stable η(2)-H(2) Ru(II)-complex stabilized only by monodentate phosphine ligands. [RuHBr(mtppms)(3)] (9) and [RuHI(mtppms)(3)] (10) were obtained analogously to 1. In concentrated aqueous HCOONa solutions (often used in H-transfer hydrogenations) the major species was trans-[RuH(2)(HCOO)(mtppms)](-) (14) while in dilute solutions trans-[RuH(2)(H(2)O)(mtppms)(3)] (15) could be observed. Formation of these various hydride species offers an explanation for the earlier observed pH and pressure dependence of the rates and selectivities in hydrogenation of unsaturated aldehydes catalyzed by [{RuCl(2)(mtppms)(2)}(2)] + mtppms.