蚯蚓对土壤中8:2与10:2氟调醇的生物富集与转化

以蚯蚓(Eisenia fetida)为受试生物,研究了8:2和10:2氟调醇(FTOH)在蚯蚓体内的生物富集特性、清除速率和生物转化等.结果表明,全氟辛酸(PFOA)是8:2 FTOH主要的末端降解产物,全氟癸酸(PFDA)是10:2 FTOH主要的末端降解产物.暴露30 d后,蚯蚓体内的全氟化合物浓度达到最高,分别为PFDA(565 ng/g)8:2 FTOH(505 ng/g)PFOA(179 ng/g)10:2 FTOH(148 ng/g).清除阶段8:2 FTOH,10:2 FTOH,PFOA和PFDA半衰期(t1/2)分别为23.1 d,16.5 d,5.8 d和11.4 d,其对应的清除速率常数(ke)分别为0.03/d,0.042/d,0.12/d,0.061/d,说明长碳链的PFCAs更难从生物体内清除,母体化合物FTOHs在蚯蚓体内的持久性更强.     

An Easy Synthesis of Monofluorinated Derivatives of Pyrroles from β-Fluoro-β-Nitrostyrenes

The catalyst-free conjugate addition of pyrroles to β-Fluoro-β-nitrostyrenes was investigated. The reaction was found to proceed under solvent-free conditions to form 2-(2-Fluoro-2-nitro-1-arylethyl)-1H-pyrroles. The effectiveness of this approach was demonstrated through the preparation of a series of the target products in a quantitative yield. The kinetics of a conjugate addition of pyrrole was studied in detail to reveal the substituent effect and activation parameters of the reaction. The subsequent base-induced elimination of nitrous acid afforded a series of novel 2-(2-Fluoro-1-arylvinyl)-1H-pyrroles prepared in up to an 85% isolated yield. The two-step sequence herein proposed is an indispensable alternative to a direct reaction with elusive and unstable 1-Fluoroacetylenes.     

A Close-to-Aromatize Approach for the Late-Stage Functionalization through Ring Closing Metathesis

An efficient approach for the synthesis of monosubstituted aromatic compounds relying on a ring-closing metathesis followed by spontaneous 1,2-elimination is presented. The efficiency for late-stage functionalization is highlighted in various solvents (up to 920 TON). This approach is compatible with strained cycles and other multiple bonds in the substrate.     

一种高准确率的交通监控视频车辆检测算法

针对高速视频监控的车辆识别易受几何变换影响且准确度不高的问题,提出了高效的阴影去除和车辆分类两种视频处理算法来提高车辆识别性能。利用阴影区域前景和背景的对比度参数进行有效的阴影去除;利用Hu不变矩表征车辆,从而克服了几何变换的影响。对比试验结果证明,本算法具有较高的阴影检测性能和极佳的车辆分类性能,明显优于其他同类型算法。     

Gas‐phase elimination kinetics of selected aliphatic α,β‐unsaturated aldehydes catalyzed by hydrogen chloride

The gas‐phase elimination of 2‐methyl‐2‐propenal catalyzed by HCl yields propene and CO gas, while E‐2‐pentenal with the same catalyst gives butene and CO gas. The kinetics determinations were carried out in a static system with the reaction vessels deactivated with allyl bromide and the presence of the free radical inhibitor toluene. Temperature and pressure ranges were 350.0–410.0 °C and 34–76 Torr. The elimination reactions are homogeneous and unimolecular, and follow a first‐order rate law. The rate coefficients for the reactions are expressible by the following Arrhenius equations: Data from the kinetic and thermodynamic parameters of these catalyzed elimination reactions implies a mechanism of a concerted five‐membered cyclic transition state structure for the formation of the corresponding olefin and carbon monoxide. Copyright © 2015 John Wiley & Sons, Ltd.     

Rollover‐Assisted C(sp2)C(sp3) Bond Formation

Rollover cyclometalation involves bidentate heterocyclic donors, unusually acting as cyclometalated ligands. The resulting products, possessing a free donor atom, react differently from the classical cyclometalated complexes. Taking advantage of a “rollover”/“retro‐rollover” reaction sequence, a succession of oxidative addition and reductive elimination in a series of platinum(II) complexes [Pt(N,C)(Me)(PR₃)] resulted in a rare C(sp²)?C(sp³) bond formation to give the bidentate nitrogen ligands 3‐methyl‐2,2′‐bipyridine, 3,6‐dimethyl‐2,2′‐bipyridine, and 3‐methyl‐2‐(2′‐pyridyl)‐quinoline, which were isolated and characterized. The nature of the phosphane PR₃ is essential to the outcome of the reaction. This route constitutes a new method for the activation and functionalization of C?H bond in the C(3) position of bidentate heterocyclic compounds, a position usually difficult to functionalize.     

Facile CH Bond Formation by Reductive Elimination at a Dinuclear Metal Site

The electronically unsaturated dirhenium complex [Re₂(CO)₈(µ‐AuPPh₃)(µ‐Ph)] ( 1 ) was obtained from the reaction of [Re₂(CO)₈{µ‐η²‐C(H)?C(H)nBu}(µ‐H)] with [Au(PPh₃)Ph]. The bridging {AuPPh₃} group was replaced by a bridging hydrido ligand to yield the unsaturated dirhenium complex [Re₂(CO)₈(µ‐H)(µ‐Ph)] ( 2 ) by reaction of 1 with HSnPh₃. Compound 2 reductively eliminates benzene upon addition of NCMe at 25 °C. The electronic structure of 2 and the mechanism of the reductive elimination of the benzene molecule in its reaction with NCMe were investigated by DFT computational analyses.     

Transfer of Aryl Halide to Alkyl Halide: Reductive Elimination of Alkylhalide from Alkylpalladium Halides Containing syn‐β‐Hydrogen Atoms

β‐Hydride abstraction is a well‐accepted elementary step for catalytic cycles in organometallic chemistry. It is usually anticipated that alkylpalladium halides containing syn‐β‐hydrogen atoms will undergo β‐hydride abstraction to afford the Heck‐type products. However, this study discloses that the above general knowledge is only conditionally correct. Our experimental results demonstrate that the reductive elimination of alkylhalides from alkylpalladium halides containing syn‐β‐hydrogen atoms may surpass the β‐hydride abstraction or even become exclusive in certain cases.     

新型1,1-双二茂铁基丁烷衍生物的合成

1,1-双二茂铁基丁烷和乙酸酐经Friedel-Crafts酰基化反应得6-乙酰基-1,1-双二茂铁基丁烷(2);2经LiAlH4还原得6-α-羟乙基-1,1-双二茂铁基丁烷(3);3经消除反应合成了6-乙烯基-1,1-双二茂铁基丁烷(4)。2~4为新化合物,其结构经1H NMR,IR,MS和元素分析表征。     

亚乙基桥联多取代茚-芴锆、铪配合物的合成、结构及催化丙烯选择性齐聚研究

合成并表征了一系列新型亚乙基桥联多取代茚-芴锆、铪配合物ansa-C₂H₄-{2-Me-3-Bn-5,6-[1,3-（CH₂）₃]Ind}-（Flu） ZrCl₂（C1）,ansa-C₂H₄-{2-Me-3-Bn-5,6-[1,3-（CH₂）₃]Ind}（2,7-^tBu₂-Flu） ZrCl₂（C2）,ansa-C₂H₄-{2-Me-3-Bn-5,6-[1,3-（CH₂）₃]Ind}（3,6-^tBu₂-Flu） ZrCl₂（C3）,ansa-C₂H₄-{2-Me-3-Bn-5,6-[1,3-（CH₂）₃]Ind}（Flu） HfCl₂（C4）,并对典型配合物进行了X射线单晶衍射分析,确定了其空间结构.研究了该系列配合物在助催化剂作用下催化丙烯齐聚的行为,考察了催化剂结构及反应条件对齐聚反应的影响.配合物C1～C4与改性甲基铝氧烷（MMAO）或三异丁基铝/三苯甲基四（五氟苯基）硼酸盐（TIBA/TrB）组成的催化体系对丙烯齐聚表现出中等到高的催化活性.锆配合物C2和C3在40～100℃条件下普遍具有较高的β-甲基消除（β-Me消除）选择性（最高可达86%）,实现了分子量M_n在400到4500 g·mol^－1范围内的烯丙基封端丙烯齐聚物的高效合成.铪催化剂体系C4/TIBA/TrB的β-Me消除选择性明显高于相应的锆催化剂体系,同时所得齐聚物的分子量更低.