[(Ph3PCu(I))6{(CH2)4Sn(IV)S2}6Cu(I)4Sn(II)], a walnut-type, heterometallic, heterovalent cluster, as confirmed by density functional theory calculations, was obtained under reductive solvothermal conditions and features an unprecedented metalloid core within a metal sulfide shell and an organic surface. 相似文献
The iromycins A-D are members of a new family of rare alpha-pyridone metabolites. The isolation and structure elucidation of these microbial secondary metabolites from Streptomyces sp. Dra 17 revealed a N-heterocyclic core structure with two unusual side chains. Iromycins act as inhibitors of nitric oxide synthases (NOS), a protein family, which produces the crucial second messenger nitric oxide (NO). Importantly, these compounds inhibit selectively endothelial NOS rather than neuronal NOS and thus set prospects for both medical therapy and basic research. Feeding experiments with 13C- and 15N -labeled precursors indicated an uncommon type of polyketide biosynthesis and clearly ruled out an isoprenoid origin. A detoxification pathway of a particular secondary metabolite in the host strain is a rare observation and here we demonstrate it with the iromycin family. 相似文献
The new cobalt(II) phosphine oxide complexes Co(Cy3PO)2Cl2 (1), Co(Cy3PO)2Br2 (2), Co(Cy3PO)2I2 (3), Co(Ph2CyPO)2Cl2 (4), Co(Ph2CyPO)2Br2 (5), Co(Ph2CyPO)2I2 (6), Co(Ph2EtPO)2Br2 (7), Co(Cy3PO)2(NCS)2 (8) and Co(Cy3PO)2(NO3)2 (9) have been prepared mainly by the reaction of anhydrous CoX2 (X = Cl, Br, I, NCS, NO3) with the appropriate phosphine oxide. The complexes were characterised by single-crystal X-ray crystallography supported by IR and UV-Vis absorption spectroscopy. The structural analyses show that the cobalt(II) centre adopts a distorted tetrahedral coordination geometry except for 9 which displays an octahedral geometry. Systematic structural features of these complexes are explained within this paper. 相似文献
A novel dihydroazepine-bridged BIPHEP phosphoramidite ligand with an amino acid moiety in the backbone was synthesized and evaluated in the Rh-catalyzed asymmetric hydrogenation. The scorpion tail-like amino acid backbone is capable of hydrogen bond formation and able to shift the rotamer composition of the biphenyl axis with the two scissor-like arms. Pivaloyl-l -valine was studied as chiral selector unit and compared with pivaloylglycine as the achiral reference substance. The enantiomerization barrier of the pivaloylglycine-modified biphenylamide was determined to be ΔG≠=110 kJ/mol. In the case of pivaloyl-l -valine, the (Sax) isomer is thermodynamically favored. Due to the relatively high barrier, the ligand is atropisomeric at room temperature and allows the preparative separation of the stereoisomers. The obtained phosphoramidite ligands were separated by chiral HPLC. For the first eluting rotamer, Rh complex ([Rh(cod)(L)2]BF4) was generated in situ and examined in the enantioselective hydrogenation of 2-acetamidoacrylate and methyl 2-acetamido-3-phenylacrylate, achieving enantiomeric excesses of up to 94 %. 相似文献
Synthesis of Phosphido Chalcogenido Bridged Dirhenium Complexes of the Type Re2(μ‐PCy2)(μ‐ER)(CO)8 (E = S, Se, Te; R = org. Residue) The reaction of Re2(μ‐Br)(μ‐PCy2)(CO)8 with nucleophiles MER (M = Na, Li; E = S, Se, Te; R = org. residue) gives via substitution of the bromido bridge phosphido chalcogenido bridged dirhenium complexes of the general formula Re2(μ‐PCy2)(μ‐ER)(CO)8. The new compounds were characterized by IR, 1H and 13C NMR spectroscopic data and by elemental analyses. In addition the molecular structures for E = S, Se, Te and R = Ph as well as for E = S and R = H, n‐Bu, 2‐pyridyl have been established by single crystal X‐ray analysis. 13C NMR spectra of Re2(μ‐PCy2)(μ‐EPh)(CO)8 (E = S, Se, Te) prove that the sulfur and selenium compounds are at room temperature dynamic molecules due to inversion of the pyramidal chalcogenido bridge. The tellurium compound, however, is rigid on the time scale of 13C NMR spectroscopy. Eventually the reactivity of the SH function of the novel complex Re2(μ‐PCy2)(μ‐SH)(CO)8 was investigated by reaction with Re2(CO)8(MeCN)2. In toluene at 90 °C the novel spirocyclic complex Re2(μ‐PCy2)(CO)8(μ4‐S)Re2(μ‐H)(CO)8 was formed by SH oxidative addition. 相似文献
Red blood cell (RBC) folate levels are established at the time of erythropoiesis and therefore provide a surrogate biomarker for the average folate status of an individual over the preceding four months. Folates are present as folylpolyglutamates, highly polar molecules that cannot be secreted from the RBCs, and must be converted into their monoglutamate forms prior to analysis. This was accomplished using an individual's plasma pteroylpolyglutamate hydrolase by lysing the RBCs in whole blood at pH 5 in the presence of ascorbic acid. Quantitative conversion of formylated tetrahydrofolate derivatives into the stable 5,10-methenyltetrahydrofolate (5,10-MTHF) form was conducted at pH 1.5 in the presence of [(13)C(5)]-5-formyltetrahydrofolate. The resulting [(13)C(5)]-5,10-MTHF was then used as an internal standard for the formylated forms of tetrahydrofolate that had been converted into 5,10-MTHF as well any 5,10-MTHF that had been present in the original sample. A stable isotope dilution liquid chromatography-multiple reaction monitoring/mass spectrometry method was validated and then used for the accurate and precise quantification of RBC folic acid, 5-methyltetrahydrofolate (5-MTHF), tetrahydrofolate (THF), and 5,10-MTHF. The method was sensitive and robust and was used to assess the relationship between different methylenetetrahydrofolate reductase (MTHFR) 677C>T genotypes and RBC folate phenotypes. Four distinct RBC folate phenotypes could be identified. These were classified according to the relative amounts of individual RBC folates as type I (5-MTHF >95%; THF <5%; 5,10-MTHF <5%), type II (5-MTHF <95%; THF 5% to 20%; 5,10-MTHF <5%), type III (5-MTHF >55%; THF >20%; 5,10-MTHF >5%), and type IV (5-MTHF <55%; THF >20%; 5,10-MTHF >5%). 相似文献
We present the results from a reactivity study of the binary anion (TlBi3)2? towards Group 12 metal compounds MPh2 (M=Zn, Cd, Hg) to gain access to coordination compounds of polycyclic polypnictide molecules such as Bi73? or Bi113?. The coordination chemistry of these polybismuthide cages has been unprecedented to date, while it has been known for a long time for the lighter Group 15 anions Pn73? (Pn=P, As, Sb). The use of (TlBi3)2?, previously shown to release Tl under certain conditions in situ, resulted in the formation of the first heterometallic polyanion in which a nortricyclane‐type polybismuthide coordinates a transition‐metal atom, [(Bi7)Cd(Bi7)]4?. Reactions with the lighter Group 12 metal precursor yielded the uncommon ternary cluster [(Bi6)Zn3(TlBi5)]4?, most likely representing a reaction intermediate, and at the same time hinting at the formation of the nortricyclane‐shaped cage. Quantum‐chemical studies provide deeper insight into the stability trends of the [(E7)M(E7)]4? anion family and reveal a complex bonding situation in [(Bi6)Zn3(TlBi5)]4?, which features both localized and multi‐center bonding. 相似文献
As part of a multi-centre European project, FOOD-PCR, the feasibility of a novel approach for production of dried bacterial DNA that could be used as certified reference materials (CRM) was assessed. Selected strains of Salmonella typhimurium, Listeria monocytogenes, Escherichia coli O157, Campylobacter jejuni and Yersinia enterocolitica were used to produce genomic DNA (gDNA). These preparations gave support to method development for qualitative polymerase chain reaction (PCR) detection methods for food-borne pathogens. Purified gDNA was transformed into stable and dry gDNA by using polypropylene vials as carrier and applying a vacuum-drying technique. The gDNA preparations were shown to be sufficiently stable under ambient transport conditions without cooling and proved to have long-term stability at 5°C of at least 22 months. The dried DNA was easily reconstituted by addition of distilled water then gentle shaking. These studies have shown that production of stable and dry bacterial gDNA material is feasible and could help satisfy the increasing need for certified reference DNA positive control samples in the field of PCR testing for detection and verification of food-borne microbial pathogens.