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在C5系列的综合利用中近年来倍受关注的环烯烃共聚物是最具有发展潜力的高端产品之一。本文评述了用于乙烯和降冰片烯类共聚合体系新型加成催化剂的最新进展,包括茂金属催化剂、非茂金属催化剂和后过渡金属催化剂三大类。开发新型半夹心型催化剂是茂金属研究领域的热点,目前主要有两类:1.限定几何构型催化剂(CGC);2. Cp’MX3和Cp’M(R)X2 (Cp’=茂基或取代茂基;M=Ti, Zr, Hf;X=卤素或烷基;R=OAr, NR2, NPR3)。非茂金属催化剂则具有亲电能力更强的活性中心及更开放的配位空间,通常具有更高的NB插入率,甚至在一定条件下具有类活性聚合的特征。而后过渡金属催化剂由于对氧(或Lewis酸)更不敏感,导致对极性基团有更好的耐受性。此外,重点围绕配体结构对催化特性的影响,如何提高分子量和环烯烃的有效插入率及其序列结构的调控等进行了对比和剖析,并展望其今后发展趋势。 相似文献
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Exploring Coordination Modes: Late Transition Metal Complexes with a Methylene‐bridged Macrocyclic Tetra‐NHC Ligand 下载免费PDF全文
Philipp J. Altmann Dr. Daniel T. Weiss Christian Jandl Prof. Dr. Fritz E. Kühn 《化学:亚洲杂志》2016,11(10):1597-1605
A tetranuclear silver(I) N‐heterocyclic carbene (NHC) complex bearing a macrocyclic, exclusively methylene‐bridged, tetracarbene ligand was synthesized and employed as transmetalation agent for the synthesis of nickel(II), palladium(II), platinum(II), and gold(I) derivatives. The transition metal complexes exhibit different coordination geometries, the coinage metals being bound in a linear fashion forming molecular box‐type complexes, whereas the group 10 metals adapt an almost ideal square planar coordination geometry within the ligand's cavity, resulting in saddle‐shaped complexes. Both the AgI and the AuI complexes show ligand‐induced metal–metal contacts, causing photoluminescence in the blue region for the gold complex. Distinct metal‐dependent differences of the coordination behavior between the group 10 transition metals were elucidated by low‐temperature NMR spectroscopy and DFT calculations. 相似文献
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Satoru Tomita Seishi Ikeda Shogo Tsuda Nobutaka Someya Kenji Asano Jun Kikuchi Eisuke Chikayama Hiroshi Ono Yasuyo Sekiyama 《Magnetic resonance in chemistry : MRC》2017,55(2):120-127
Non‐targeted nuclear magnetic resonance (NMR)‐based metabolic profiling was applied to potato leaves to survey metabolic changes associated with late blight resistance under field conditions. Potato plants were grown in an experimental field, and the compound leaves with no visible symptoms were collected from 20 cultivars/lines at two sampling time points: (i) the time of initial presentation of symptoms in susceptible cultivars and (ii) 12 days before this initiation. 1H NMR spectra of the foliar metabolites soluble in deuterium oxide‐ or methanol‐d4‐based buffers were measured and used for multivariate analysis. Principal component analysis for six cultivars at symptom initiation showed a class separation corresponding to their levels of late blight resistance. This separation was primarily explained by higher levels of malic acid, methanol, and rutin and a lower level of sucrose in the resistant cultivars than in the susceptible ones. Partial least squares regression revealed that the levels of these metabolites were strongly associated with the disease severity measured in this study under field conditions. These associations were observed only for the leaves harvested at the symptom initiation stage, but not for those collected 12 days beforehand. Subsequently, a simple, alternative enzymatic assay for l ‐malic acid was used to estimate late blight resistance, as a model for applying the potential metabolic marker obtained. This study demonstrated the potential of metabolomics for field‐grown plants in combination with targeted methods for quantifying marker levels, moving towards marker‐assisted screening of new cultivars with durable late blight resistance. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
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One hundred and forty-seven species of spores and pollen referred to 77 genera found in the crudeoil samples taken from four petroliferous provinces of the Tarim Basin of Xinjiang Provincehave been studied in this paper. By means of these spore and pollen fossils, the geological ages anddistribution of the petroleum source rocks of the basin are judged. Also, the principles and methodsto judge the petroleum source of a petroleum province by spore/pollen and other microfossils in crudeoils are explained. 相似文献
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Xiaoqiang Hu Dr. Yixin Zhang Baixiang Li Prof. Dr. Zhongbao Jian 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(46):11935-11942
Fluorine substituents in transition metal catalysts are of great importance in olefin polymerization catalysis; however, the comprehensive effect of fluorine substituents is elusive in seminal late transition metal α-diimine catalytic system. In this contribution, fluorine substituents at various positions (ortho-, meta-, and para-F) and with different numbers (Fn; n=0, 1, 2, 3, 5) were installed into the well-defined N-terphenyl amine and thus were studied for the first time in the nickel α-diimine promoted ethylene polymerization and copolymerization with polar monomers. The position of the fluorine substituent was particularly crucial in these polymerization reactions in terms of catalytic activity, polymer molecular weight, branching density, and incorporation of polar monomer, and thus a picture on the fluorine effect was given. As a notable result, the ortho-F substituted α-diimine nickel catalyst produced highly linear polyethylenes with an extremely high molecular weight (Mw=8703 kDa) and a significantly low degree of branching of 1.4/1000 C; however, the meta-F and/or para-F substituted α-diimine nickel catalysts generated highly branched (up to 80.2/1000 C) polyethylenes with significantly low molecular weights (Mw=20-50 kDa). 相似文献
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宛小平 《贵州师范大学学报(社会科学版)》2007,(2):94-101
方东美的美学方法和他所回答的种种问题在逻辑上是一致的.他是从人文途径建构了一个"既超越又内在"形上学方法,并以此反对西方二元对峙的方法.他的美学和哲学是浑为一体的,是步了"天人合一"的理路.他把人、自然、宇宙的统一看作是生命情调以美学化方式的一种渲泄.方东美美学的方法还可以称作是"全体的直透"法.由于把宇宙、人皆看作是有生命的"情理集团",他对美的解释是庄子所谓的"大美",是"原天地之美而达万物之理".同时,他主张这个天地之美寄于生命,形于创造.总之,方东美的美学思想既承续了中国传统体用不二的路数,又借鉴了西方柏格森、怀特海许多有益的因子,构成了一个独具特色的当代中国美学的思想体系. 相似文献
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通过对山东肥城矿区晚石炭世苔藓虫的进一步研究,又发现了以往在山东乃至华北未曾报道过的苔藓虫化,属隐口目中的两个科,计有两属六种,其中新种四个,近似种两个,进一步丰富了山东乃至华北石炭纪的苔藓虫化石资料。 相似文献