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1.
The molybdenum and tungsten dinitrogen-organonitrile complexes trans-[M(N2)(NCR)(dppe)2] (2, M=Mo; 4, M=W; R=Ph, C6H4Me-p, C6H4OMe-p, Me; dppe=Ph2PCH2CH2PPh2) underwent double protonation at the nitrile carbon atom with loss of N2 and a change in oxidation state to +4 on treatment with hydrochloric acid to afford the cationic imido complexes trans-[MCl(NCH2R)(dppe)2]+. The solid-state structure of trans-[WCl(NCH2CH3)(dppe)2][PF6]·CH2Cl2 was determined by single-crystal X-ray analysis. Protonation of complexes 2 by fluoroboric acid or hydrobromic acid also formed the similar imido complexes trans-[MoX(NCH2R)(dppe)2]+ (X=F, Br). In contrast, the dinitrogen complex trans-[Mo(N2)2(dppe)2] reacted with two equiv. of benzoylacetonitrile, a nitrile with acidic CH hydrogen atoms, to give the nitrido complex trans-[Mo(N)(NKCCHCOPh)(dppe)2] (12), which was accompanied by evolution of dinitrogen and the formation of 1-phenyl-2-propen-1-one in high yields. For complex 12, the zwitterionic structure, where the anionic enolate ligand PhC(O+)=CHCN coordinates to the cationic Mo(IV) center through its nitrogen atom, was confirmed by spectroscopic measurements and single-crystal X-ray analysis. A unique intermolecular aromatic C---HO hydrogen bonding was observed in that crystal structure. Complex 12 is considered to be formed via the cleavage of the CN triple bond of benzoylacetonitrile on the metal. A reaction mechanism is proposed, which includes the double protonation of the nitrile carbon atom of the ligating benzoylacetonitrile on a low-valent molybdenum center. 相似文献
2.
M. Y. Shukor M. F. Rahman Z. Suhaili N. A. Shamaan M. A. Syed 《World journal of microbiology & biotechnology》2009,25(7):1225-1234
A bacterium that was able to tolerate and reduce as high as 50 mM of sodium molybdate to molybdenum blue has been isolated
from a metal recycling ground. The isolate was tentatively identified as Serratia sp. strain Dr.Y8 based on the carbon utilization profiles using Biolog GN plates and partial 16S rDNA molecular phylogeny.
ANOVA analysis showed that isolate Dr.Y8 produced significantly higher (P < 0.05) amount of Mo-blue with 3, 5.1 and 11.3 times more molybdenum blue than previously isolated molybdenum reducers such
as Serratia
marcescens strain Dr.Y6, E. coli K12 and E. cloacae strain 48, respectively. Its molybdate reduction characteristics were studied in this work. Electron donor sources such as
sucrose, mannitol, fructose, glucose and starch supported molybdate reduction. The optimum phosphate, pH and temperature that
supported molybdate reduction were 5 mM, pH 6.0 and 37°C, respectively. The molybdenum blue produced from cellular reduction
exhibited a unique absorption spectrum with a maximum peak at 865 nm and a shoulder at 700 nm. Metal ions such as chromium,
silver, copper and mercury resulted in approximately 61, 57, 80, and 69% inhibition of the molybdenum-reducing activity at
1 mM, respectively. The reduction characteristics of strain Dr.Y8 suggest that it would be useful in future molybdenum bioremediation. 相似文献
3.
A. G. McEwan H. G. Wetzstein O. Meyer J. B. Jackson S. J. Ferguson 《Archives of microbiology》1987,147(4):340-345
The periplasmic dissimilatory nitrate reductase from Rhodobacter capsulatus N22DNAR+ has been purified. It comprises a single type of polypeptide chain with subunit molecular weight 90,000 and does not contain heme. Chlorate is not an alternative substrate. A molybdenum cofactor, of the pterin type found in both nitrate reductases and molybdoenzymes from various sources, is present in nitrate reductase from R. capsulatus at an approximate stoichiometry of 1 molecule per polypeptide chain. This is the first report of the occurrence of the cofactor in a periplasmic enzyme. Trimethylamine-N-oxide reductase activity was fractionated by ion exchange chromatography of periplasmic proteins. The fractionated material was active towards dimethylsulphoxide, chlorate and methionine sulphoxide, but not nitrate. A catalytic polypeptide of molecular weight 46,000 was identified by staining for trimethylamine-N-oxide reductase activity after polyacrylamide gel electrophoresis in the presence of sodium dodecyl sulphate. The same polypeptide also stained for dimethylsulphoxide reductase activity which indicates that trimethylamine-N-oxide and dimethylsulphoxide share a common reductase.Abbreviations DMSO
dimethylsulphoxide
- LDS
lithium dodecyl sulphate
- MVH
reduced methylviologen
- PAGE
polyacrylamide gel electrophoresis
- SDS
sodium dodecyl sulphate
- TMAO
trimethylamine-N-oxide 相似文献
4.
Sukhada Mohandas 《Plant and Soil》1985,86(2):283-285
Summary Bean (Phaseolus vulgaris L. Cv. Burpees Stringless) seeds were subjected to two cycles of presowing soaking and drying treatments with sodium molybdate and cobalt nitrite at 1 and 5 ppm concentrations used separately and also in combination. Sodium molybdate 2 ppm and cobalt nitrite 1 ppm used singly proved better than the remaining treatments with respect to nodulation, dry matter, nitrogen and yield. Combined treatment with sodium molybdate and cobalt nitrite did not produce additive effect on any parameter studied compared to their usage alone. 相似文献
5.
Anaerobic, Gram-positive cocci were obtained from chicken feces by direct isolation, which grew on the purines uric acid, xanthine, 6,8-dihydroxypurine, guanine, and hypoxanthine. Adenine and glycine were fermented, but not as readily. Acetate, formate, ammonia, and CO2 were products. The isolated strains were nutritionally non-fastidious, however, they required selenite, molybdate, and tungstate as micronutrients. The cells were spherical and 0.5–0.9 m in diameter. The addition of bile salts enhanced the growth rate in most cases. The organisms proved to be quite resistant to lysis. The guanosine-plus-cytosine (G+C) content of their deoxyribonucleic acid was 33.6 to 34.8 mol%. The peptidoglycan was of the same structure (Gly-Lys-d-Asp) as reported for the anaerobic cocci of Hare group IX. However, the latter strains could only utilize glycine, not purines. Therefore, it is proposed to form a new species, Peptostreptococcus barnesae sp. nov.This paper is dedicated to Prof. Dr. Norbert Pfennig on the occasion of his 60th birthday 相似文献
6.
V. Patinec J. J. Yaouanc H. Handel J. C. Clment H. des Abbayes 《Inorganica chimica acta》1994,220(1-2):347-348
After reaction with alkyl iodides and subsequent oxidative removal of the M(CO)3 triprotection, molybdenum and chromium fac-LM(CO)3 complexes of cyclen (L) unexpectedly lead to N1,N7-dialkylated cyclen derivatives. 相似文献
7.
Mutant plants defective in the assimilation of nitrate can be selected by their resistance to the herbicide chlorate. In Arabidopsis thaliana, mutations at any one of nine distinct loci confer chlorate resistance. Only one of the CHL genes, CHL3, has been shown genetically to be a nitrate reductase (NR) structural gene (NIA2) even though two NR genes (NIA1 and NIA2) have been cloned from the Arabidopsis genome. Plants in which the NIA2 gene has been deleted retain only 10% of the wildtype shoot NR activity and grow normally with nitrate as the sole nitrogen source. Using mutagenized seeds from the NIA2 deletion mutant and a modified chlorate selection protocol, we have identified the first mutation in the NIA1 NR structural gene. nia1, nia2 double mutants have only 0.5% of wild-type shoot NR activity and display very poor growth on media with nitrate as the only form of nitrogen. The nial-1 mutation is a single nucleotide substitution that converts an alanine to a threonine in a highly conserved region of the molybdenum cofactor-binding domain of the NR protein. These results show that the NIA1 gene encodes a functional NR protein that contributes to the assimilation of nitrate in Arabidopsis. 相似文献
8.
Plasma molybdenum concentrations were determined in children, ages two to 12 yr, with and without phenylketonuria (PKU). Mean
plasma molybdenum concentrations did not differ significantly between the children with PKU (1.33±0.5 μg/L) and without PKU
(1.75±0.8 μg/L). Plasma molybdenum concentrations in both groups of children ranged from <1 to 3 μg/L.
When data from all children were combined and then separated based on gender, mean plasma molybdenum levels did not differ
significantly between 9 females (1.56±0.68 μg/L) and 12 males (1.58±0.76 μg/L). Data were also combined and mean (±SD) plasma
molybdenum concentrations calculated for age groups. Two children aged 1 to <4 yr had plasma molybdenum concentrations of
1.0 μg/L, and six children aged 4 to <7 yr had mean (±SD) plasma molybdenum concentrations of 1.5±0.8 μg/L. Eleven children
aged 7 to <11 yr had a mean plasma molybdenum concentration of 1.7±0.7 μg/L, and two children 11 to <14 yr had plasma molybdenum
concentrations of 1 μg/L and 2 μg/L. Plasma molybdenum concentrations did not differ significantly among children in the age
groups. 相似文献
9.
D. Sellmann Hans-Jörg Kremitzl Falk Knoch Matthias Moll 《Journal of biological inorganic chemistry》1996,1(2):127-135
In the quest for complexes modelling functional characteristics of metal sulfur oxidoreductases, a series of molybdenum nitrosyl complexes with sulfur-dominated coordination sphere was synthesized. Treatment of the 16, 17 and 18 valence electron (VE) complexes [Mo(L)(NO)('S4')] (1–3) [L?=?SPh (1), PMe3 (2), NO (3), 'S4'2–?=?1,2-bis-(2-mercaptophenylthio) ethane(2-)] with the Brönsted acid HBF4 resulted in formation of different types of products. 1 and 3 were reversibly protonated at one thiolate atom of the 'S4'2– ligand;2, however, yielded the phosphonium salt [HPMe3]BF4 and the dinuclear [Mo(NO)('S4')]2. Alkylation of 1, 2 and 3 by Me3OBF4 or Et3OBF4 uniformly resulted in high yields of [Mo(L)(NO)(R-'S4')]BF4 complexes [L?=?SPh: R?=?Me (5), Et (6); L?=?PMe3: R?=?Me (7); L?=?NO: R?=?Me (8), Et (9)] in which one thiolate atom of the 'S4'2– ligand had become alkylated; the NMR spectra of 5, 6, 8 and 9 indicated that only one out of four theoretically possible diastereoisomers had formed. 5 and 6 were characterized also by single-crystal X-ray structure analyses. A comparison of ν(NO) bands and redox potentials (cyclic voltammetry) of parent complexes and alkylated derivatives showed that alkylation leads to a decrease in electron density at the molybdenum center and to a positive shift in redox potentials. The 16 VE complex 1 could be reduced, also chemically, to give the corresponding 17 VE anion [1]–, and inserted elemental sulfur into the Mo-SPh bond, forming the 18 VE phenylperthio complex [Mo(η2–SSPh)(NO)('S4')] (11) which, upon reaction with PPh3, gave SPPh3 and regenerated the parent complex 1. These results are discussed with regard to the sequence of proton and electron transfer steps occurring in substrate conversions catalyzed by metal sulfur oxidoreductases. 相似文献
10.
Marie Kselíková Tomáš Mařík Bedřich Bíbr Jaroslav Lener 《Biological trace element research》1980,2(1):57-64
This study describes the interaction of molybdenum with blood components. Molybdenum-99 was added to blood, and after four
washings, 3% of the total radioactivity was found in red cells. More specifically, the radioactivity was determined to be
associated with the cell membrane.
Molybdenum-99 in the +VI form did not interact with the human erythrocyte membrane; however, Mo(V) forms did interact. Of
five different compounds, the highes uptake was observed with a brown Mo(V)-ascorbate complex generated from Mo(VI) and ascorbic
acid in the molar ratio 1∶20. A membrane suspension of Mo-ascorbate-treated human erythrocytes was prepared and the solubilized
proteins were separated on a polyacrylamide gel in the presence of sodium dodecyl sulfate (SDS). Molybdenum-99 binding to
spectrin was demonstrated, as well as some minor interactions with membrane hemoglobin and bands 6 and 8. 相似文献