有机金属络合物用于高分子富氧膜的研究进展

本文介绍了能够可逆吸附分子氧的有机金属络合物用于高分子富氧膜的研究进展，以及以双重吸附理论进行的膜的促进输送机理。     

MODIFICATION OF TRANSITION METAL CATIONS TO POLYMER-STABILIZED PLATINUM COLLOIDAL CLUSTERS IN ENANTIOSELECTIVE HYDROGENATION OF METHYL PYRUVATE

Modification of transition metal cations to polymer-stabilized Pt colloidal clusters modified with cinchonidine was studied in enantioselective hydrogenation of methyl pyruvate. Compared to the enantiomeric excess (e.e.) value (71.4%) obtained without the presence of metal cations, obvious e.e. enhancement (up to 82.5%) was resulted from the addition of Zn^2 but with a certain decrease in activity. The reaction parameters in the presence of Zn^2 were also studied. It was found that the Pt colloidal catalysts in the presence of metal cations performed very differently from that in the absence of metal cations.     

Application of recoverable nanosized palladium(0) catalyst in Sonogashira reaction

In the absence of ligand, copper and amine, a recoverable nanoparticle palladium(0) catalyzed Sonogashira reaction of aryl iodides and bromides with terminal alkynes was developed. The protocol involved the use of an environmental-friendly reaction system with ethanol as the solvent, potassium carbonate as a base, and poly(vinylpyrrolidone) (PVP) supported nanosized palladium metal colloids as the catalyst. The palladium metal was recovered and recycled by a simple decantation of the reaction solution and used for eight consecutive trials without significant loss of its reactivity.     

Effect of operating parameters on selective separation of heavy metals from binary mixtures via polymer enhanced ultrafiltration

Performance of continuous polymer enhanced ultrafiltration (PEUF) method was investigated for removal of mercury and cadmium from binary mixtures. This method includes the addition of polyethyleneimine (PEI) as a water soluble polymer to bind the metals, which was followed by ultrafiltration operation performed on both laboratory and pilot scale systems. The influence of various operating parameters such as temperature, metal/polymer ratio, presence of calcium ions and pH on retention of metals and permeate flux was investigated. To investigate the possibility of selective separation of mercury and cadmium, experiments were conducted for binary solutions at different pH and loading ratios. It was seen that the retention of mercury decreased and permeate flux increased when the temperature increased. The increased pH and decreased metal/polymer ratio, loading (L), resulted in higher retention of both metals. Shapes of retention vs. pH or L curves were very similar for both metals. Retentions stay almost constant at a value very close to unity until a critical L or pH value was reached, then, R decreases almost linearly with L or pH. However, retention of cadmium was affected more than that of mercury as the pH decreased and L increased. This leads to the selective separation of mercury and cadmium. At low pH values (about 5) and at high L values (about 0.3), mercury was removed by ultrafiltration operation while almost all cadmium passed through the membrane. At pH 5.5 and cadmium/polymer ratio about 0.35 and mercury/polymer ratio about 0.39, the highest separation factor was obtained as 49.     

聚合物载体－稀土金属络合物的研究ⅩⅤ．聚（苯乙烯－丙烯酰胺）载体－氯化钕络合物对异戊二烯聚合的催化行为

研究了聚（苯乙烯－丙烯酰胺）（ＰＳＡＣ）载体－氯化钕（ＮｄＣｌ３）络合物对异戊二烯（Ｉｐ）聚合的催化行为．ＰＳＡＣ·ＮｄＣｌ３络合物保留了小分子稀土催化剂对双烯烃聚合的催化规律和高度的定向效应．络合物的催化活性随着Ｎｄ／Ｉｐ和Ａｌ／Ｎｄ比的增加而增加，所得聚异戊二烯的特性粘数［η］却随之下降．聚异戊二烯的顺式－１，４结构含量达９５％．此外，ＰＳＡＣ·ＮｄＣｌ３络合物的活性受ＰＳＡＣ和ＰＳＡＣ·ＮｄＣｌ３的组成与结构的影响．在一定的条件下，络合物的活性随着ＰＳＡＣ中功能团含量的增加而下降．ＰＳＡＣ中单体链节交替分布的程度越低，络合物的活性越高     

XPS and AES characterization of hydrolysed γ‐mercaptopropyltrimethoxysilane deposited on Al,Zn and Al–43.4Zn–1.6Si alloy‐coated steel

In this paper Al, Zn and Al–43.4Zn–1.6Si (AlZn) alloy‐coated steel have been treated with the organofunctional silane γ‐mercaptopropyltrimethoxysilane (γ‐MPS). The influence of different metal substrates on the structure and composition of the silane films was investigated with XPS and AES. The films were obtained by dipping the substrates in the silane solution followed by a blow‐dry procedure in nitrogen gas. The results show that the surface concentration of the deposited silane is independent of the metal substrate and that the thickness of the silane film is non‐uniform. The AES measurements indicate that the silane film covers the entire substrate surface and XPS analysis of the silane‐treated substrate surfaces at different take‐off angles indicates that the γ‐MPS molecule is randomly orientated. Also, the results show that the silane is well hydrolysed under the solution conditions used. Finally, in the zinc‐containing silane‐metal systems, i.e. the silane‐treated AlZn and Zn substrates, the results indicate that the γ‐MPS molecules can bond to the substrate surfaces via the thiol group of the molecule. Copyright © 2004 John Wiley & Sons, Ltd.     

Chiral Recognition in π Complexes of Alkenes,Aldehydes, and Ketones with Transition Metal Lewis Acids; Development of a General Model for Enantioface Binding Selectivities

Prochiral alkenes, aldehydes, and ketones constitute the most frequently used starting materials for enantioselective organic syntheses. Protocols often involve chiral binding agents or Lewis acids that can give two diastereomeric adducts, the ratios of which are measures of chiral recognition. With π adducts, the diastereomers differ in the enantioface of the C?C or O?C group bound to the Lewis acid. This review provides the first comprehensive analysis of such equilibria and related binding phenomena with chiral transition metal Lewis acids. An extensive body of data from the authors' laboratory for complexes of the pyramidal rhenium fragment [(η⁵?C₅H₅)Re(No)(PPh₃)]⁺ ( I ) affords particular insight. Literature data for other complexes are also summarized. A general model for chiral recognition based upon the relative steric properties of four quadrants is presented. This enables binding selectivities to be individually and rationally optimized for different classes of ligands. Electronic effects are also identified and correlated with specific structural properties. Relationships between binding equilibria, reactivity, and product configurations are discussed.     

Synthesis of macrocyclic tetraamides derived from α-amino acids and their investigations using ESI-MS technique

Chiral α,ω-diesters react under high-pressure conditions (10 kbar) with α,ω-diamines to give chiral cyclic tetraamides of C₂-symmetry. The complexation properties of tetraamides towards alkali metal cations (Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺) were estimated on the basis of ESI-MS spectra.     

过渡金属离子对HPAsMoVO杂多酸的氧化性能的影响

用H2-TPR方法研究了过渡金属离子及其含量对杂多酸-HxPAs0.2Mo10VOy的氧化性能的影响,并在固定床反应器上考察了M0.2HxPAs0.2Mo10VOy(M=Fe3 、Co2 、N i2 和Cu2 )催化剂对异丁烷选择性氧化的催化性能.研究结果表明用过渡金属离子取代杂多酸中的质子,可以在较大程度上增强杂多酸的低温氧化能力,其中Fe3 对增强杂多酸的催化活性最为明显,而Cu2 却有利于提高目的产物甲基丙烯酸的选择性.     

Kinetics of formation of a linear polymer-polymer network system in the presence of 3d metal chelates

For semi-interpenetrating polymer networks (semi-IPNs) based on an incompatible polyurethane network/linear polymethylmethacrylate pair formed in situ in the presence of 3d metal chelates, we have studied the effect of the system composition on the kinetics of formation of the components and the nature of complex formation between the metal compound and the polymer matrix. The ratio of the system components has been shown to have an effect on the selection of the macroligand in formation of complexes of the metal chelate with the polar groups of the semi-IPN, where the general character of the kinetic behavior for the formation of the network and the linear polymer is preserved. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 6, pp. 351–356, November–December, 2006.