Investigation of polymer-protected noble metal nanoparticles by transmission electron microscopy: control of particle morphology and shape

 Noble metal nanoparticles were prepared by the in situ reduction of the respective metal salt precursors in the presence of various protective polymers. Transmission electron microscopy (TEM) has been used to determine the particle shapes and morphologies. These are strongly influenced by the reduction methods and conditions chosen, but the choice of the protective polymer is equally important for controlling the particle morphologies and for the stabilization of the colloids. A whole spectrum of nanoparticle morphologies and shapes was obtained, ranging from nanoagglomerates which are nevertheless well-defined and well-stabilized to nanosized single crystals with triangular shape. Received: 2 February 1998 Accepted: 29 May 1998     

N-（4＇-取代嘧啶-2＇-基）-取代苯氧基磺酰脲的合成及除草活性

光谱;N-（4＇-取代嘧啶-2＇-基）-取代苯氧基磺酰脲的合成及除草活性     

Experimental and computational studies of intracomplex reactions in Mg+(primary, secondary alkylamine) complexes induced by photoexcitation of Mg+

We report herein a comprehensive study of photoinduced reactions in complexes of Mg+ with primary (n-propyl- and isopropylamine) and secondary amines (dipropyl- and diisopropylamine) in the spectral range of 230-440 nm. Similar to the methyl- and ethylamine complexes studied previously, N-H bond activation of these complexes is very unfavorable. Instead, the C(alpha)-C, C-N, and C(alpha)-H bond-cleavage photoproducts are observed after photoexcitation of the Mg+ complexes (3(2)P<--3(2)S). For Mg+(primary amine) complexes, for example, Mg+-NH2CH2CH2CH3, and Mg+-NH2CH(CH3)2, the photoproducts resulting from C(alpha)--C rupture prevail after P(z) and charge-transfer excitations, whereas the Mg+ photofragment is predominant upon P(x,y) excitation. However, with further N-alkyl substitution, as in Mg+(secondary amine) complexes, for example, Mg+-NH(CH2CH2CH3)2 and Mg+-NH[CH(CH3)2]2, a novel intracomplex C-C coupling photoreaction dominates on P(x,y) excitation of Mg+, which is believed to arise from Mg+* insertion into the C-N bond. With P(z) and charge-transfer excitation, the Mg-R elimination photoproducts, arising from C(alpha)-C bond cleavage, predominate. The energetics and possible mechanisms of the intracomplex photoreactions are analyzed in detail with the help of extensive quantum mechanics calculations.     

钒、铬、锰磷桥络合物中31P NMR化学位移的研究

ISSIe山和W6flSChllh山子1960年首次用pdCI。和二苯基磷合成出黄色的二聚络合物，后被H。yieY＊确认为具有pRZ的桥式结构．此后一系列该类结构的化合物被合成并引起了广泛的兴趣．磷可以和两个甚至多个金属原子络合构成多核金属络合物，在催化反应中有重要应用．磷原子存在多种电子态，其3d空轨道也能参与成键．P乃1的NMR谱是研究含磷化合物立体结构的有力工具．P－31与其它核素之间的耦合常数以及P－31的化学位移对阐明化合物的立体构象以及电子结构具有重要作用．近年来，West饲用计算机神经网络技术预测P－：if的化学位移，但仅…     

Coupling Cloud Point Extraction to Instrumental Detection Systems for Metal Analysis

The purpose of this article is to review and evaluate cloud point extraction of metals and its coupling to different contemporary instrumental methods of analysis. This review covers a selection of the literature published on this topic over the period mainly between 1997 and September 2005 (consisting of 50 publications). The current state of the art for CPE concerning metals and metal chelates is presented with special emphasis on the hyphenation of this interesting extraction/preconcentration approach mediated by surfactants to spectrophotometry, atomic spectroscopy and separation techniques. We present contemporary CPE developments concerning metal speciation and determination and their application to different environmental, clinical, geological and food samples. Strategies for method development as well as future perspectives are also covered.     

二价金属离子萃取速率常数与软硬酸碱规则

用上升液滴法测定了２－乙基己基膦酸单（２－乙基己基）酯－正辛烷从硝酸介质中萃取镁、钙、锌、镍、铜和铅等二价金属离子的正向初始速率，建立了速率方程，计算出正向萃取反应的速率常数、活化能及活化熵，首次将软硬酸碱规则与金属溶萃取速率常数关联。结果表明，在萃取机理相同时，萃取速率常数的大小与金属离子的软硬酸碱标度一致，即萃取过程中，作为酸的被萃取金属离子，其硬度越大，萃取速率常数亦越大，萃取反应的活化能…     

锚联膦,胺配体对胶体钯的配位俘获及其负载催化剂的催化性能

本文继采用含硫配体(-SH,-SR)对高分子保护金属胶体的配位俘获之后,采用锚联在SiO_2表面的较含硫配体配位能力弱的P,N配体分别与聚乙烯吡咯烷酮(PVP)保护的胶体钯在室温下反应,在P/Pd大于3.5,N/Pd大于7时,可以实施对保护金属胶体的配位俘获,证实了配位俘获法是一种具有普遍意义的方法,经原子吸收光谱分析,溶液中残留的金属钯的量小于0.36 ppm(P/Pd=3.5)。经电子能谱证实,锚联膦胺配体与金属钯之间存在配位作用,这是实施保护胶体负载化的关键。透射电镜分析表明,在整个配位俘获的过程中,无论是在载体上或是在溶液中,胶体钯的颗粒大小与分布均保持不变。因此,配位俘获法是一种能控制多相催化剂中金属颗粒大小与分布的有效方法。由此合成的钯催化剂具有很高的催化活性,良好的选择性和稳定性,在对Cis,Cis-1,3-环辛二烯的选择性加氢中,其活性仅比均相的PVP-Pd胶体催化剂稍低,选择性达100％。在周转数达12,000次/个钯原子后,其催化活性仍保持不变,随着P/Pd比的增大,催化活性迅速下降。     

Synthesis of a novel rigid molecule family for the investigation of electron and energy transfer

Three new rigid bridging ligands for metal complexation (7=bmb, 8=bqb and 11=btb) were prepared from a rigid triptycene spacer connected to two bipyridine ligands using a Horner–Emmons type reaction. The triptycene spacer is substituted by methoxy groups in the case of bmb and in the case of bqb by a benzoquinone substituent. The corresponding metal complexes (ruthenium and/or osmium) were synthesised and the different luminescence behaviour was tested. They show great potential for the investigation of intramolecular electron and energy transfer reactions. The dinuclear metal complex Ru---bqb---Os is an interesting system in which the bridging ligand bqb acts as a redox switch, able to tune the conductivity for energy or electrons across the bridge.     

Polarography in solution of some problems in organic chemistry: recent applications

Applications of chromatographic and atomic absorption methods are compared with those of electroanalytical techniques. The limitations of electroanalytical procedures and their advantages, such as speed, sensitivity and speciation are discussed. Among applications of polarography and voltammetry to a solution of basic problems, attention has been paid to the possibility to distinguish the degree of conjugation (e.g. of compounds containing the grouping CNNC), to a contribution to understanding of solution chemistry of mitomycin C and to processes involved in the reduction of cephalosporins. Among practical applications, the possibility to analyze suspensions, which can be carried out without separation offers advantages. Examples are interactions in suspensions of bile salts in the presence of metal (II) ions, adsorptions of various pesticides and other toxic materials on lignin and the possibility to follow alkaline cleavage of lignin in buffers pH 8-12 at 25 °C. Most of these studies would not be possible to carry out using other techniques.     

DSC Investigations of DDAB,DTAB and DHAB Vesicle Aqueous Solutions in Presence of SDS

Interactions of anionic surfactant sodium dodecyl sulphate (SDS) with vesicles formed by synthetic dialkyldimethylammonium bromides i.e. didodecyldimethylammonium bromide (DDAB), ditetradecyldimethylammonium bromide (DTAB), dihexadecyldimethylammonium bromide (DHAB) have been examined by using differential scanning microcalorimetry and electron transmission microscopy. The temperatures and standard enthalpies characterising gel to liquid-crystal transitions increase significantly with increase of SDS concentration for all investigated systems. It means that incorporation of SDS monomers in these vesicular bilayers significantly stabilises their gel states. Moreover, in case of DDAB and DTAB vesicle systems added SDS limits kinetic features of recorded isobaric heat capacity dependencies on temperature observed earlier for the pure vesicular solutions. This revised version was published online in July 2006 with corrections to the Cover Date.