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111.
Oliver Wuerfel Frank Thomas Marcel Sven Schulte Reinhard Hensel Roland Arturo Diaz‐Bone 《应用有机金属化学》2012,26(2):94-101
Metal(loid)s are subject to many transformation processes in the environment, such as oxidation, reduction, methylation and hydride generation, predominantly accomplished by prokaryotes. Since these widespread processes affect the bioavailability and toxicity of metal(loid)s to a large extent, the investigation of their formation is of high relevance. Methanogenic Archaea are capable of methylating and hydrogenating Group 15 and 16 metal(loid)s arsenic, selenium, antimony, tellurium, and bismuth due to side reactions between central methanogenic cofactors, methylcobalamin (CH3Cob(III)) and cob(I)alamin (Cob(I)). Here, we present systematic mechanistic studies on methylation and hydride generation of Group 15 and 16 metal(loid)s by CH3Cob(III) and Cob(I). Pentavalent arsenical species showed neither methylation nor reduction as determined by using a newly developed oxidation state specific hydride generation technique, which allows direct determination of tri‐ and pentavalent arsenic species in a single batch. In contrast, efficient methylation of trivalent species without a change in oxidation state indicated that the methyl transfer does not proceed via a Challenger‐like oxidative methylation, but via a non‐oxidative methylation. Our findings also point towards a similar mechanism for antimony, bismuth, selenium, and tellurium. Overall, we suggest that the transfer of a methyl group does not involve a free reactive species, such as a radical, but instead is transferred either in a concerted nucleophilic substitution or in a caged radical mechanism. For hydride generation, we propose the intermediate formation of hydridocobalamin, transferring a hydride ion to the metal(loid)s. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
112.
Atsushi Sudo Masato Sato Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2001,39(21):3789-3796
A polymer with a 2‐azetidinone moiety in its main chain was efficiently synthesized by [2 + 2] cycloaddition of bisimine with bisketene. The bisketene was easily prepared by dehydrochlorination of the corresponding dicarboxylic acid chloride and was used without purification. The treatment of the obtained polymer with lithium aluminum hydride resulted in a reductive ring‐opening reaction of the 2‐azetidinone moiety in the main chain that gave the corresponding linear polyamine with hydroxymethyl side chains. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3789–3796, 2001 相似文献
113.
Benan K?lba?Author VitaeMetin BalciAuthor Vitae 《Tetrahedron》2011,67(13):2355-2389
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本文用ESR方法考察了Cp2ZrH) Cl与RNCSR=C6H5,c-C6H11,n-C4H9)的反应的过程,结果表明,在这类反应过程中,Zr-H键发生均裂,中心金属锆经过+4-→+3-→+4的价态变化,反应通过自由基机理进行. 相似文献
117.
The efficiency of the extraction of butyltin compounds from sediments and biological matter by acid leaching procedures has been evaluated on real samples using the hydride generation gas chromatography quartz furnace atomic absorption (GC AA) speciation method. The most efficient method uses cold pure acetic acid over a period of four hours. Hydride generation using sodium tetrahydroborate (NaBH4) is dependent on matrix composition and care must be taken to adapt the amount of reactant to the organic content of the sample. 相似文献
118.
Bin HU Kun XIAO Jing Kang SHEN State Key Laboratory of Drug Research Shanghai Institute of Materia Medica Shanghai Institutes for Biological Sciences Chinese Academy of Sciences Shanghai 《中国化学快报》2006,(9)
N-Boc-α-aminoaldehydes, represented by Boc-L-leucinal and its congener Boc-L- phenylalaninal, have received considerable attention in the past four decades1. This interest mainly stems from their wide application as important synthons in the preparation … 相似文献
119.
Analysis of ethyl glucuronide and ethyl sulfate using aqueous normal‐phase chromatography with mass spectrometry 下载免费PDF全文
The use of aqueous normal‐phase chromatography is explored as a possible format for the analysis of the forensically significant compounds ethyl glucuronide and ethyl sulfate. Standard solutions of the two compounds are used to verify the retention capabilities of two stationary phases (diamond hydride and undecanoic acid). These results are then compared to data obtained on hair extracts to determine if any matrix effects exist with respect to both retention and peak shape. The undecanoic stationary phase is used for the establishment of calibration curves for quantitative analysis. These curves are utilized to determine the concentration of ethyl glucuronide in several hair samples tested. 相似文献
120.
建立氢化物发生–原子吸收光谱法联用测定铅粉中痕量砷、锑的方法。试样用稀硝酸溶解,用5%抗坏血酸溶液作为砷(Ⅴ)、锑(Ⅴ)的预还原剂,5%的硫脲溶液作为其它元素的掩蔽剂,选用1%硼氢化钠溶液作为还原剂,氢化物反应在10%盐酸介质中进行。在优化的试验条件下,砷、锑的质量浓度在0~20 ng/m L范围内与吸光度线性相关,相关系数r2分别为砷0.999 6,锑0.993 8,方法的检出限分别为砷0.40 ng/m L,锑0.75 ng/m L。砷、锑测定结果的相对标准偏差分别为4.96%,6.27%(n=6),铅粉样品加标回收率分别为砷87.6%,锑79.3%。该方法准确可靠,可用于测定铅粉中痕量砷、锑。 相似文献