155 research outputs found
Fe(ii) and Fe(iii) dithiocarbamate complexes as single source precursors to nanoscale iron sulfides: a combined synthetic and in situ XAS approach
Nanoparticulate iron sulfides have many potential applications and are also proposed to be prebiotic catalysts for the reduction of CO2 to biologically important molecules, thus the development of reliable routes to specific phases with controlled sizes and morphologies is important. Here we focus on the use of iron dithiocarbamate complexes as single source precursors (SSPs) to generate greigite and pyrrhotite nanoparticles. Since these minerals contain both iron(III) and iron(II) centres, SSPs in both oxidation states, [Fe(S2CNR2)3] and cis-[Fe(CO)2(S2CNR2)2] respectively, have been utilised. Use of this Fe(II) precursor is novel and it readily loses both carbonyls in a single step (as shown by TGA measurements) providing an in situ source of the extremely air-sensitive Fe(II) dithiocarbamate complexes [Fe(S2CNR2)2]. Decomposition of [Fe(S2CNR2)3] alone in oleylamine affords primarily pyrrhotite, although by careful control of reaction conditions (ca. 230 °C, 40–50 nM SSP) a window exists in which pure greigite nanoparticles can be isolated. With cis-[Fe(CO)2(S2CNR2)2] we were unable to produce pure greigite, with pyrrhotite formation dominating, a similar situation being found with mixtures of Fe(II) and Fe(III) precursors. In situ X-ray absorption spectroscopy (XAS) studies showed that heating [Fe(S2CNiBu2)3] in oleylamine resulted in amine coordination and, at ca. 60 °C, reduction of Fe(III) to Fe(II) with (proposed) elimination of thiuram disulfide (S2CNR2)2. We thus carried out a series of decomposition studies with added thiuram disulfide (R = iBu) and found that addition of 1–2 equivalents led to the formation of pure greigite nanoparticles between 230 and 280 °C with low SSP concentrations. Average particle size does not vary significantly with increasing concentration, thus providing a convenient route to ca. 40 nm greigite nanoparticles. In situ XAS studies have been carried out and allow a decomposition pathway for [Fe(S2CNiBu2)3] in oleylamine to be established; reduction of Fe(III) to Fe(II) reduction triggers substitution of the secondary amide backbone by oleylamine (RNH2) resulting in the in situ formation of a primary dithiocarbamate derivative [Fe(RNH2)2(S2CNHR)2]. This in turn extrudes RNCS to afford molecular precursors of the observed FeS nanomaterials. The precise role of thiuram disulfide in the decomposition process is unknown, but it likely plays a part in controlling the Fe(III)–Fe(II) equilibrium and may also act as a source of sulfur allowing control over the Fe : S ratio in the mineral products
A manually annotated Actinidia chinensis var. chinensis (kiwifruit) genome highlights the challenges associated with draft genomes and gene prediction in plants
Most published genome sequences are drafts, and most are dominated by computational gene prediction. Draft genomes typically incorporate considerable sequence data that are not assigned to chromosomes, and predicted genes without quality confidence measures. The current Actinidia chinensis (kiwifruit) 'Hongyang' draft genome has 164\ua0Mb of sequences unassigned to pseudo-chromosomes, and omissions have been identified in the gene models
ChemInform Abstract: A NOVEL INTRAMOLECULAR EXCHANGE REACTION BETWEEN COORDINATED NITROSYL AND NITRO GROUPS IN CIS-NITROSYLNITROBIS(DITHIOCARBAMATO)IRON
ChemInform Abstract: IRON-SULFUR COMPLEXES OF NITRIC OXIDE. 2. SYNTHESIS AND EXCHANGE STUDIES OF FE(NO)X(S2CN(CH3)2)2. CRYSTAL AND MOLECULAR STRUCTURE OF CIS-BIS(DIETHYLDITHIOCARBAMATO)(NITRO)NITROSYLIRON
ChemInform Abstract: CRYSTAL AND MOLECULAR STRUCTURE OF IRON(II) BIS(DIETHYLDITHIOCARBAMATE)
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