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排序方式: 共有3411条查询结果,搜索用时 15 毫秒
1.
Science China Mathematics - Linear factor models are familiar tools used in many fields. Several pioneering literatures established foundational theoretical results of the quasi-maximum likelihood... 相似文献
2.
Xinyu Zhang Linxuan Li Prof. Giuseppe Zanoni Xinyue Han Prof. Xihe Bi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(22):e202200280
The direct gem-difluoroalkenylation of X−H bonds represents the most straightforward approach to access heteroatomic gem-difluoroalkenes that, as the isostere of the carbonyl group, have great potency in drug discovery. However, the construction of tetrasubstituted heteroatomic gem-difluoroalkenes by this strategy is still an unsolved problem. Here, we report the first direct X−H bond gem-difluoroalkenylation of amines and alcohols with trifluoromethyl ketone N-triftosylhydrazones under silver (for (hetero)aryl hydrazones) or rhodium (for alkyl hydrazones), thereby providing a most powerful method for the synthesis of tetrasubstituted heteroatomic gem-difluoroalkenes. This method features a broad substrate scope, high product yield, excellent functional group tolerance, and operational simplicity (open air conditions). Moreover, the site-specific replacement of the carbonyl group with a gem-difluorovinyl ether bioisostere in drug Trimebutine and the post-modification of bioactive molecules demonstrates potential use in medicinal research. Finally, the reaction mechanism was investigated by combining experiments and DFT calculations, and disclosed that the key step of HF elimination occurred via five-membered ring transition state, and the difference in the electrophilicity of Ag- and Rh-carbenes as well as the multiple intermolecular interactions rendered the effectiveness of Rh catalyst selectively for alkyl hydrazones. 相似文献
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以1978年改革开放以来人民教育出版社出版的5套高中化学教科书作为研究对象,梳理其物质结构内容的演变,发现近40年来高中化学教科书中物质结构内容选择呈钟摆现象,同时其内容组织的结构化理念日益清晰。此外,为新时期我国高中化学教科书的编写提供了一些建议。 相似文献
5.
Dr. Rong-Lin Zhong Dr. Feng-Wei Gao Dr. Hong-Liang Xu Prof. Zhong-Min Su 《Chemphyschem》2019,20(14):1879-1884
The nature of the 2e/12c bond and its conversion to a carbon-carbon single bond in phenalenyl dimers have prompted a great deal of interests recently. In this work, we theoretically investigated a series of π-stacking phenalenyl derivatives with 2e/12c bonding character by density functional theory (DFT) calculations to elucidate origin of this unusual bond conversion. Results show that bond-conversion of the phenalenyl dimer easily occurs at room-temperature both dynamically and thermodynamically. However, bond-conversion of hetero π-stacking adducts, in which the two center carbon atoms were substituted by boron and nitrogen atoms, respectively, is much more difficult, because the 2e/12c bond is stabilized by its charge transfer character. Consequently, the bond-conversion is an endothermic process, albeit with a low conversion barrier. Interestingly, Lewis acid-base interactions would be induced by substitution of the center nitrogen atom to phosphorus atom. The 2e/12c bond is further stabilized by 5.9 kcal mol−1 and its conversion is also thermodynamically unfavorable. 相似文献
6.
《中国化学快报》2020,31(6):1593-1597
As one of the most environmentally friendly photovoltaic(PV) conversion equipments,aqueousprocessed CdTe nanocrystal solar cells(NC SCs) have attracted great interest in recent years because of their excellent properties such as high charge-carrier mobility and broad absorption.However,two issues including interfacial recombination and leakage current seriously restrict their performance.In this paper,insulating polymer poly(vinyl pyrrolidone)(PVP) is introduced into CdTe NC SCs to solve the problems.The experimental results of transmission electron microscopy(TEM),atomic force micro scopy(AFM) and dark current measurements,etc.,demonstrate the leakage current is effectively suppressed by introducing PVP.Through further designing device structure,the reduction of interfacial recombination after introducing PVP is confirmed.By strategically taking the advantages of PVP properties(e.g.,water solubility and thermostability),the power conversion efficiency of the devices with PVP is enhanced by almost 37% compared to pure CdTe devices.This work demonstrates an effective and low-cost method to fabricate NC SCs via aqueous route.Moreover,it also proves that appropriate content of insulating polymer is of beneficial in promoting the PV performance. 相似文献
7.
《Stochastic Processes and their Applications》2020,130(7):3943-3966
In this article we define the discrete Gaussian free field (DGFF) on a compact manifold. Since there is no canonical grid approximation of a manifold, we construct a random graph that suitably replaces the square lattice in Euclidean space, and prove that the scaling limit of the DGFF is given by the manifold continuum Gaussian free field (GFF). Furthermore using Voronoi tessellations we can interpret the DGFF as element of a Sobolev space and show convergence to the GFF in law with respect to the strong Sobolev topology. 相似文献
8.
Dr. Yaru Gong Chao Qin Yuteng Zhang Prof. Chunyi Sun Prof. Qinhe Pan Xinlong Wang Zhongmin Su 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(49):22218-22222
Systematic design and self-assembly of metal–organic polyhedra with predictable configurations has been a long-standing challenge in crystal engineering. Herein a concave polyoxovanadate cluster, [V6O6(OCH3)9(SO4)4]5−, which can be generated in situ under specific reaction conditions, is reported. Based on this cluster, a potential trivalent molecular building block, [V6O6(OCH3)9(SO4)(CO2)3]2−, can be obtained by the bridging-ligand-substitution strategy and it possesses appropriate angle information for the design of molecular cubes. Utilizing the face-directed assembly of the trivalent molecular building block and a diverse set of tetratopic carboxylate linkers, a series of metal–organic cubes ( VMOC-1 – VMOC-5 ) with the same topology but different functionalities and dimensions were designed and constructed. An inclusion study using VMOC-3 shows that they are potential molecular receptors for selective capture of size-matching polycyclic aromatic hydrocarbon guest molecules. 相似文献
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Gold nanostars(Au NSs) are asymmetric anisotropic nanomaterials with sharp edge structure. As a promising branched nanomaterial, Au NS has excellent plasmonic absorption and scattering properties. In order to tune the plasmonic photothermal and surface-enhanced Raman scattering(SERS) activity of Au NSs to obtain the desired characteristics, the effects of reagents on the local surface plasmon resonance(LSPR) bands of Au NSs were studied and the morphology and size were regulated. Nanoparticles with different sharp edges were synthesized to make their local plasmon resonance mode tunable in the visible and near-infrared region. The effects of the number and sharpness of different tips under the control of AgNO3 on the photothermal response of Au NSs and the SERS activity and their mechanism were discussed in detail. The results show that as the length of the branch tip becomes longer and the sharpness increases, the plasmonic photothermal effect of Au NSs is strengthened, and the photothermal conversion efficiency is the highest up to 40% when the length of Au NSs is the longest. Au NSs with high SERS activity are used for the Raman detection substrate. Based on this property, the quantitative detection of the pesticide thiram is achieved. 相似文献