Precise electro-reduction of alkyl halides for radical defluorinative alkylation

Reported here is a precise electro-reduction strategy for radical defluorinative alkylation towards the synthesis of gem-difluoroalkenes from α-trifluoromethylstyrenes. According to the redox-potential difference of the radical precursors, direct or indirect electrolysis is respectively adopted to realize the precise reduction. An easy-to-handle, catalyst-and metal-free condition is developed for the reduction of alkyl radical precursors that are generally easier to be reduced than α-trifluorome...     

First Organic–Inorganic Hybrid Compounds Formed by Ge-V-O Clusters and Transition Metal Complexes of Aromatic Organic Ligands

Three compounds based on Ge-V-O clusters were hydrothermally synthesized and characterized by IR, UV-Vis, XRD, ESR, elemental analysis and X-ray crystal structural analysis. Both [Cd(phen)(en)]₂[Cd₂(phen)₂V₁₂O₄₀Ge₈(OH)₈(H₂O)]∙12.5H₂O (1) and [Cd(DETA)]₂[Cd(DETA)₂]_0.5[Cd₂(phen)₂V₁₂O₄₁Ge₈(OH)₇(0.5H₂O)]∙7.5H₂O (2) (1,10-phen = 1,10-phenanthroline, en = ethylenediamine, DETA = diethylenetriamine) are the first Ge-V-O cluster compounds containing aromatic organic ligands. Compound 1 is the first dimer of Ge-V-O clusters, which is linked by a double bridge of two [Cd(phen)(en)]²⁺. Compound 2 exhibits an unprecedented 1-D chain structure formed by Ge-V-O clusters and [Cd₂(DETA)₂]⁴⁺ transition metal complexes (TMCs). [Cd(en)₃]{[Cd(η₂-en)₂]₃[Cd(η₂-en)(η₂-μ₂-en)(η₂-en)Cd][Ge₆V₁₅O₄₈(H₂O)]}∙5.5H₂O (3) is a novel 3-D structure which is constructed from [Ge₆V₁₅O₄₈(H₂O)]¹²⁻ and four different types of TMCs. We also synthesized [Zn₂(enMe)₃][Zn(enMe)]₂[Zn(enMe)₂(H₂O)]₂[Ge₆V₁₅O₄₈(H₂O)]∙3H₂O (4) and [Cd(en)₂]₂{H₈[Cd(en)]₂Ge₈V₁₂O₄₈(H₂O)}∙6H₂O (5) (enMe = 1,2-propanediamine), which have been reported previously. In addition, the catalytic properties of these five compounds for styrene epoxidation have been assessed.     

Joint Detection of Community and Structural Hole Spanner of Networks in Hyperbolic Space

Community detection and structural hole spanner (the node bridging different communities) identification, revealing the mesoscopic and microscopic structural properties of complex networks, have drawn much attention in recent years. As the determinant of mesoscopic structure, communities and structural hole spanners discover the clustering and hierarchy of networks, which has a key impact on transmission phenomena such as epidemic transmission, information diffusion, etc. However, most existing studies address the two tasks independently, which ignores the structural correlation between mesoscale and microscale and suffers from high computational costs. In this article, we propose an algorithm for simultaneously detecting communities and structural hole spanners via hyperbolic embedding (SDHE). Specifically, we first embed networks into a hyperbolic plane, in which, the angular distribution of the nodes reveals community structures of the embedded network. Then, we analyze the critical gap to detect communities and the angular region where structural hole spanners may exist. Finally, we identify structural hole spanners via two-step connectivity. Experimental results on synthetic networks and real networks demonstrate the effectiveness of our proposed algorithm compared with several state-of-the-art methods.     

Faraday-Michelson system for quantum cryptography

Quantum key distribution provides unconditional security for communication. Unfortunately, current experimental schemes are not suitable for long-distance fiber transmission because of phase drift or Rayleigh backscattering. In this Letter we present a unidirectional intrinsically stable scheme that is based on Michelson-Faraday interferometers, in which ordinary mirrors are replaced with 90 degree Faraday mirrors. With the scheme, a demonstration setup was built and excellent stability of interference fringe visibility was achieved over a fiber length of 175 km. Through a 125 km long commercial communication fiber cable between Beijing and Tianjin, the key exchange was performed with a quantum bit-error rate of less than 6%, which is to our knowledge the longest reported quantum key distribution experiment under field conditions.     

Computational Insight into Biotransformation Profiles of Organophosphorus Flame Retardants to Their Diester Metabolites by Cytochrome P450

Biotransformation of organophosphorus flame retardants (OPFRs) mediated by cytochrome P450 enzymes (CYPs) has a potential correlation with their toxicological effects on humans. In this work, we employed five typical OPFRs including tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), tris(1-chloro-2-propyl) phosphate (TCIPP), tri(2-chloroethyl) phosphate (TCEP), triethyl phosphate (TEP), and 2-ethylhexyl diphenyl phosphate (EHDPHP), and performed density functional theory (DFT) calculations to clarify the CYP-catalyzed biotransformation of five OPFRs to their diester metabolites. The DFT results show that the reaction mechanism consists of Cα-hydroxylation and O-dealkylation steps, and the biotransformation activities of five OPFRs may follow the order of TCEP ≈ TEP ≈ EHDPHP > TCIPP > TDCIPP. We further performed molecular dynamics (MD) simulations to unravel the binding interactions of five OPFRs in the CYP3A4 isoform. Binding mode analyses demonstrate that CYP3A4-mediated metabolism of TDCIPP, TCIPP, TCEP, and TEP can produce the diester metabolites, while EHDPHP metabolism may generate para-hydroxyEHDPHP as the primary metabolite. Moreover, the EHDPHP and TDCIPP have higher binding potential to CYP3A4 than TCIPP, TCEP, and TEP. This work reports the biotransformation profiles and binding features of five OPFRs in CYP, which can provide meaningful clues for the further studies of the metabolic fates of OPFRs and toxicological effects associated with the relevant metabolites.     

“社会学本土化”的德国经验：“角色之争”及其去美国化效应

在西方先进国家中,德国社会学的发展相对晚进且历程坎坷。德国社会学在20世纪初萌芽之时,就因纳粹的“夺权”而停滞发展。第二次世界大战结束之后,在学科重建阶段又因美国的挟持而陷入了美国化危机。在此危难之时,达伦多夫1958年出版的著作《社会人》,意外引发德国社会学界关于“社会角色”概念的学术争辩,史称“角色之争”。这场大规模的学术论战,让德国社会学出现了“通过超美国化以去美国化”与“通过国际化以抵消美国化”的学科发展方向,对德国社会学发展历程中的去美国化与国际化产生了不小的推动效应。当今中国在建立具有国际影响力的中国特色社会学学术话语体系之时,德国社会学极富戏剧性的“复兴”之路,值得参考借鉴。     

创新导向减税与就业结构升级—基于研发费用加计扣除的检验

创新在中国经济社会发展中的作用愈发突出,如何促进高技能劳动力向创新主体部门集聚,值得深入探索。基于2018年企业所得税研发费用加计扣除比例提升冲击,利用A股上市公司2016−2019年数据,本文研究了创新导向减税对就业结构的影响。研究发现,加计扣除比例提升显著提高了企业雇佣劳动力中研究生所占比例,促进了企业创新人力资本积累。异质性分析显示,政策在非公有制企业、主板上市企业中效果更明显。对企业各层次雇佣规模的评估表明,雇佣总量及研究生、本科生雇佣数均有所提高,同时本科以下学历人员并未明显减少,这意味着政策未产生明显的挤出效应,高技能劳动力雇佣的增加并不以低技能劳动力的减少为代价。综合来看,政策不但能促进企业加大研发投入,还有助于提高全要素生产率和盈利水平。本文结论为通过实施结构性减税,推动创新驱动发展提供了经验支撑。     

单层2H-MoTe2光电效应的理论研究

材料的禁带宽度是影响光电探测器探测范围的重要因素.单层2H-MoTe2因具有合适的禁带宽度引起了科研人员广泛的研究兴趣.本文基于非平衡态格林函数-密度泛函理论,采用第一性原理方法,研究了单层2H-MoTe2的光电效应.结果表明:在线性偏振光照射下,MoTe2产生的光电流函数与唯象理论相吻合;在光子能量范围1.6～1.8...     

新型聚苯胺共聚物季铵盐的合成与性能研究

以邻硝基苯甲酸和苯胺为原料,经6步反应合成了一种新型的聚[苯胺-N-(2-氯乙基)-2-氨基苯甲酰胺]共聚物季铵盐(6),其结构和性能经UV-Vis,IR,X-射线衍射和离子交换容量表征。结果表明,季铵化成盐后,6的IR和UV吸收带发生了明显蓝移;6具有较好的共轭性,可能呈导电性;6呈非晶态结构,能溶于甲醇和DMF等极性溶剂,具有一定的离子交换能力。