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951.
Micellar shape change and internal segregation induced by chemical modification of a tryptych block copolymer surfactant 总被引:1,自引:0,他引:1
Zhou Z Li Z Ren Y Hillmyer MA Lodge TP 《Journal of the American Chemical Society》2003,125(34):10182-10183
We report the detailed characterization of micelles formed by two nonionic, amphiphilic ABC triblock copolymers. Poly(ethylene oxide)-b-poly(styrene)-b-1,2-poly(butadiene) (PEO-b-PS-b-PB) triblock copolymer "OSB" forms core-corona spherical micelles in aqueous solution, and the two hydrophobic blocks S and B are mixed homogeneously within the micelle core. PEO-b-PS-b-PB:C6F13I triblock copolymer "OSF" was prepared by selective fluorination of the B block in OSB with n-perfluorohexyl iodide. Fluorination of the B block induces internal segregation into an inner F core and an intermediate S shell. Furthermore, the strong incompatibility that results from fluorination drives a shape change into an oblate ellipsoid. These micellar morphologies are confirmed by combined light, neutron, and X-ray scattering measurements, as well as TEM imaging. 相似文献
952.
A novel hypoxanthine (Hx) microsensor was constructed. In this work, Nafion xanthine oxidase (XOD) and Au colloid were immobilized onto the surface of a Pt microelectrode. The enzyme biosensor displayed a quick and sensitive response to Hx. Under physiological conditions, a low detection limit, with high selectivity and sensitivity for Hx determination were obtained. The oxidation current [investigated using current-time (I-t) plots] was linear with Hx concentration ranging from 2.0 x 10(-7) to 2.0 x 10(-5) mol L(-1) with a calculated detection limit of 1.0 x 10(-7) mol L(-1) (S/N of 3). The biosensor should be promising for in vivo measurement of Hx without interferences and fouling. The change of Hx concentration in cardiac myocytes stimulated by L-arginine (L-Arg) and acetylcholine (Ach) was also studied. 相似文献
953.
Heterotrimetallic 4f-3d coordination polymers: synthesis, crystal structure, and magnetic properties
A series of cyano-bridged heterotrimetallic complexes [CuL](2)Ln(H(2)O)(2)M(CN)(6).7H(2)O have been synthesized by the reactions of CuL (L(2)(-) = dianion of 1,4,8,11-tetraazacyclotradecane-2,3-dione), Ln(3+) (Ln = Gd or La), and [M(CN)(6)](3)(-) (M = Co, Fe, or Cr). X-ray diffraction analysis reveals that these complexes are isostructural and have a novel chain structure. The Ln(3+) ion is eight-coordinated by six oxygen atoms of two CuL and two water molecules and two nitrogen atoms of the bridging cyano ligands of two [M(CN)(6)](3)(-), while the [M(CN)(6)](3)(-) anion connects two Ln(3+) using two trans-CN(-) ligands giving rise to a chainlike structure. In the chain, every CuL group tilts toward the CN(-) ligand of adjacent [M(CN)(6)](3)(-) with the Cu-N(cyano) contacts ranging from 2.864(6) to 2.930(6) A. Magnetic studies on the CuGdCo complex (1) indicate the presence of ferromagnetic coupling between Cu(II) and Gd(III). The CuLaCr (5) and CuLaFe (2) complexes exhibit ferromagnetic interaction between paramagnetic Cu(II) and Cr(III)/Fe(III) ions through the weak cyano bridges (Cu-N(cyano) = 2.930(6) A for 2). A global ferromagnetic interaction is operative in the CuGdFe complex (3) with the concurrence of dominant ferromagnetic Cu(II)-Gd(III) and minor antiferromagnetic Gd(III)-Fe(III) as well as the ferromagnetic Cu(II)-Fe(III) interaction. For the CuGdCr complex (4), an overall antiferromagnetic behavior was observed, which is attributed to the presence of dominant antiferromagnetic Cr(III)-Gd(III) coupling and the minor ferromagnetic Cu(II)-Gd(III) and Cu(II)-Cr(III) interaction. Moreover, a spin frustration phenomenon was found in complex 4, which results from the ferro-ferro-antiferromagnetic exchanges in the trigonal Cu-Gd-Cr units. The magnetic susceptibilities of these complexes were simulated using suitable models. The magneto-structural correlation was investigated. These complexes did not show a magnetic phase transition down to 1.8 K. 相似文献
954.
Yizhao Ouyang Miao Zhan Jing Zhou Jiao Jiao Hao Hu Yoichi M. A. Yamada Pengfei Li 《中国化学》2019,37(8):807-810
A rigid C2‐symmetric chiral bipyridine ligand Z‐bpy with a triptycene‐like backbone was designed and synthesized from simple chemicals in a scalable route. Using this new ligand, copper(I) catalyzed cyclopropanation of styrenes with commercial ethyl diazoacetate produced various corresponding cyclopropanes in high yields, diastereoselectivity and enantioselectivity up to 97% ee. 相似文献
955.
Li Xiuzhen Zhou Guimin Bao Miansheng Zhang Yukui Lu Peichang 《Journal of separation science》1981,4(11):569-576
Using a specially designed column system, we have systematically investigated the effect of mobile phase velocity on column efficiency. The performance of small bore columns operated at different linear velocities of mobile phase was examined for three different types of injection system. Using the value of H∞/u or n∞/t as a criterion of a high speed separation, we calculated values of n/t for different solutes according to the equation \documentclass{article}\pagestyle{empty}\begin{document}$ {{\rm n}\mathord{\left/ {\vphantom {{\rm n} {{\rm t}_{\rm r}^ \circ }}}\right. \kern-\nulldelimiterspace} {{\rm t}_{\rm r}^ \circ }} = {{{\rm n}^\infty } \mathord{\left/ {\vphantom {{{\rm n}^\infty } {{\rm t}_{\rm r}^ \circ }}} \right. \kern-\nulldelimiterspace} {{\rm t}_{\rm r}^ \circ }}\left({\frac{{1 + {\rm k'}}}{{{\rm k' + }\beta }}} \right)^2 $\end{document}; the results obtained are in agreement with the experimentally determined values. These systematic investigations culminated in the separation of seven compounds in less than 10 s; the respective chromatogram is shown. 相似文献
956.
Solid phase microextraction (SPME) then capillary gas chromatography with mass spectrometric detection have been used for determination of nine phenyl compounds in snow water in Beijing City. Headspace extraction with a fiber coated with 100 µm PDMS was used to extract the compounds. Extraction and desorption times were optimized at 8 and 2 min, respectively. Relative standard deviation (RSD) of the analytical method was found to be less than 5%. The linear range was wide and limits of detection were less than 5 ng mL−1 for the nine target analytes. Several phenyl compounds at ng mL−1 levels were detected in snow samples in Beijing, indicating the corresponding air pollution. 相似文献
957.
Chen X Zhou L Zhang X Yin X Xu C Shan X Wei Z Xu K 《The Journal of chemical physics》2004,120(17):7933-7938
Electron momentum distributions for outer valence orbitals of CF2Cl2 have been obtained by (e,2e) electron momentum spectroscopy at an incident energy of 1200 eV + binding energy. The experimental electron momentum profiles are compared with Hartree-Fock and density functional theory (DFT) calculations using B3LYP hybrid functional with the 6-31G and 6-311+G* basis sets. Generally, the shapes of the experimental momentum profiles are well reproduced by DFT calculations using larger basis sets 6-311 + G*. An attempt has been made to clarify the ordering of the outer valence orbitals, which have been in controversy, by comparing experimental results with B3LYP/6-311 + G* calculations. 相似文献
958.
Wang Zhong-Ming Lin Hua-Kuan Zhou Zhi-Fen Zhu Shou-Rong Chen Yun-Ti Murmann R. Kent 《Transition Metal Chemistry》2000,25(5):562-567
The kinetics of the reaction of CH2O with a quasi-aromatic metal complex (1,1,2,8,9,9-hexamethyl-4,6-dioxa-5-hydro-3,7,10,14-tetraazacyclotetradecane-2,7,10,12-tetraene)copper(II), [Cu(PnAO)-6H]0 (AH), have been studied spectrophotometrically under neutral conditions in 1/3(v/v) MeOH–H2O. The Cu, 2N, 3C quasi-aromatic heterocyclic ring in AH is highly reactive towards CH2O at the central-aromatic-carbon atom, C(12) and the following reaction mechanism is proposed.
The compounds AH, A—CH2OH and A—CH2—A were isolated and identified by i.r spectroscopy and by elemental analysis. The kinetic data supported the proposed reaction sequence. All reactions were second order overall. The rate constants and corresponding activation parameters for every step were obtained and are discussed. 相似文献
959.
Cα-Tetrasubstituted α-amino acids are ubiquitous and unique structural units in bioactive natural products and pharmaceutical compounds. The asymmetric synthesis of these molecules has attracted a lot of attention, but a more efficient method is still greatly desired. Here we describe the first sequential four-step acylation reaction for the efficient synthesis of chiral Cα-tetrasubstituted α-amino acid derivatives from simple N-acylated amino acids via an auto-tandem catalysis using a single nucleophilic catalyst. The synthetic efficiency is improved via a direct enantioselective C-acylation; the methodology affords the corresponding Cα-tetrasubstituted α-amino acid derivatives with excellent enantioselectivities (up to 99% ee). This step-economic, one-pot, and auto-tandem strategy provides facile access to important chiral building blocks, such as peptides, serines, and oxazolines, which are often used in medicinal and synthetic chemistry.The first four-step sequential reaction for the synthesis of Cα-tetrasubstituted chiral α-amino acid derivatives via auto-tandem catalysis has been developed. 相似文献
960.
Cu以其优异的导电性、导热性和易加工性广泛用于工农业生产中.自然Cu的腐蚀和防腐成为人们很关注的问题.人们已经注意到,Cl-对Cu的腐蚀有影响,并进行过一些研究.但目前使用光电化学方法研究这一问题的文章尚不多见,特别是利用测量开路光电压及其瞬态波形这一现场的、无损的、灵敏的监测方法研究户对Cu电极腐蚀全过程的文章尚未见到.本文正是利用如上方法及XPS,AES方法,研究了Cl-对Cu电极腐蚀的全过程,取得了一些有意义的结果.1实验方法Cu电极用99.99%(质量分数)的Cu制成,面积约为39mm2;电极底部由Cu导线焊接引出,… 相似文献