Alkenylation of C(sp3)−H Bonds by Zincation/Copper‐Catalyzed Cross‐Coupling with Iodonium Salts

α‐Vinylation of phosphonates, phosphine oxides, sulfones, sulfonamides, and sulfoxides has been achieved by selective C?H zincation and copper‐catalyzed C(sp³)?C(sp²) cross‐coupling reaction using vinylphenyliodonium salts. The vinylation transformation proceeds in high efficiency and stereospecificity under mild reaction conditions. This zincative cross‐coupling reaction represents a general alkenylation strategy, which is also applicable for α‐alkenylation of esters, amides, and nitriles in the synthesis of β,γ‐unsaturated carbonyl compounds.     

REVERSE ATOM TRANSFER RADICAL POLYMERIZATION OF STYRENE WITH COPPER-BASED CATALYST

 "Living"/controlled radical polymerization of styrene was carried out with diethyl 2,3-dicyano-2,3-diphenylsuccinate (DCDPS)/CuCl₂/bipyridine (bipy) initiation system at 120℃. The molecular weights of resultant PSt increased with the monomer conversion and the polydispersities were in the range of 1.37 ～ 1.52. A linear ln([M]o/[M])versus time plot was also obtained indicating the constant concentration of growing radicals during the polymerization with this initiation system. End group analysis by ¹H-NMR spectroscopic studies showed that the end groups of the polymer obtained is cω-functionalized by a chlorine group from the catalyst and a-functionalized by a (carbethoxy-cyano-phenyl)methyl group from the fragments of the initiator. Having C1 atom at the chain end, the PSt obtained can be used as a macroinitiator to promote a chain-extension reaction with fresh St and block copolymerization reaction with a second monomer, such as methyl methacrylate, in the presence of CuC1/bipy catalyst via a conventional ATRP process.     

多核NMR在相图研究中的应用——Na2SO4-Al2(SO4)3-H2O体系的23Na、27Al NMR研究

In the present paper, Na_2SO_4-Al_2(SO_4)_3-H_2O system has been studied by ~(23)Na and ~(27)Al NMR quantitative method. It has been shown that the existence of double salt can be easily identified by this method.     

Asymmetric synthesis of cis- and trans-2,5-disubstituted pyrrolidines from 3-oxo pyrrolidine 2-phosphonates: synthesis of (+)-preussin and analogs

Pyrrolidine enones, derived from 3-oxo pyrrolidine 2-phosphonates and a HWE reaction with aldehydes, on Luche reduction give pyrrolidine allylic alcohols. The alcohols on hydrogenation (Pd/H2) give cis-2,5-disubstituted pyrrolidines and on treatment with TFA-NaBH3CN undergo a hydroxy directed reduction to trans-2,5-disubstituted pyrrolidines.     

5-溴水杨基荧光酮-溴化十六烷基三甲基铵吸光光度法测定微量锗

研究了在表面活性剂CTMAB存在下锗与5-溴水杨基荧光酮形成配合物的显色反应,在2mol·L~(-1)H_2SO_4介质中测得配合物的表观摩尔吸光系数为1.62×10~5.锗量在0～8μg/25ml范围内符合比耳定律.该体系反应酸度高,选择性好.方法稳定、决速.已用于水相直接测定人参、当归、灵芝、枸杞子和竹沥汁等中药材中微量锗,结果满意     

Electrochemiluminescence Behavior of Ru(bpy)32+/Carbofuran System on an Electrically Heated Microelectrode Chip

An electrically heated microelectrode chip (HMEC) was designed and the Ru(bpy)₃²⁺/carbofuran electrochemiluminescence (ECL) systems were applied to characterize the performance of the HMEC. The ECL intensities increase at elevated electrode temperature, and the detection limit at 60°C (electrode surface temperature) was about 10 times lower than that at 30°C. The results indicate that new heated electrode can be handled easily and can be mass produced, the difference between the electrodes was little. The stability of the HMEC was good since the electrode surface can hardly be destroyed during detection and storage.     

闽西晚中生代基性脉岩稀土元素地球化学特征

利用稀土元素特征对闽西基性脉岩的成岩方式和岩浆演化机制进行探讨. 闽西基性岩脉的稀土元素参数与常量元素的协变关系表明岩浆在上升侵入过程中可能没有发生地壳混染作用,在成岩过程中结晶分异作用可能不明显;多种稀土元素协变关系表明闽西基性脉岩的成岩机制可能为上地幔部分熔融作用,基性脉岩的地幔源区可能曾经遭受过俯冲流体交代富集作用,这种交代可能与古太平洋板块俯冲密切相关,软流圈地幔上涌导致地壳拉张作用的发育.     

Synthesis and magnetic properties of one-dimensional zinc nickel oxide solid solution

A novel facile method has been demonstrated for large-scale synthesis of zinc-oxide-based one-dimensional solid solution with a series percentage of nickel dopant. The obtained Zn1-xNixO nanorods were characterized by X-ray diffraction, transmission electron microscopy, selected area electron diffraction, and energy dispersed X-ray spectroscopy. The result shows that the obtained Zn1-xNixO nanorods are single crystalline with the Ni2+ dopants occupying tetrahedral Zn2+ cation sites of wurtzite ZnO. Moreover, the Zn1-xNixO nanorods exhibit robust high-Curie-temperature (TC) ferromagnetism at 300 K.     

A novel off-on fluorescent probe for specific detection and imaging of cysteine in live cells and in vivo

Cysteine(Cys) plays a pivotal role in many physiological and pathological processes,including detoxification and protein synthesis.The abnormal levels of Cys are linked to many diseases.In this study,a novel red-emitting off-on fluorescent probe Cys-TCF was masterly constructed for discriminative detection of Cys.After a series of experimental assessment,Cys-TCF displayed higher selectivity and sensitivity for Cys over other biothilols with a low detection limit(0.04 μmol/L).More notably,the pro...