合成丙交酯中微量水分分析

合成丙交酯中微量水分分析徐溢，柳胜春（重庆大学化工学院分析教研室６３００４４）关键词丙交酯，微量水，定量分析丙交酯是人工合成骨材料聚乳酸的合成中间体，其性能决定着合成产品的品质，要获得高质量的合成材料，对中间体的分析和监测十分重要。一般要求丙交酯中间...     

Infrared study of co adsorbed species on ru/silicalite catalyst

Carbon monoxide adsorbed species on Ru/silicalite and their reactivity towards oxygen have been studied using in situ diffuse reflectance infrared spectroscopy (DRIFT). Four species were detected: a bridge bonded CO on metallic Ru (1980 cm ^-1), a linearly adsorbed CO on metallic Ru (2040 cm^-1), a linearly adsorbed CO on partially oxidized Ru (2081 cm^-1), and a multicarbonyl on oxidized Ru (2081 and 2133 cm^-1). Among the four CO species the most strongly held species was the bridge bonded CO on metallic Ru while the multicarbonyl was the most weakly held species. These four species have different reactivities towards oxygen. Only the linearly adsorbed CO on metallic Ru can be oxidized at room temperature.     

On the maximum modulus of complete trigonometric sums

LetQ _k (p) be a set consisting of all polynomials of degreek with integral coefficientsf(x)=a _k x ^k +...+a ₁ x, wherep×a _k . For givenk andp any polynomialf _k,p (x)εQ _k (p) satisfying ‖S(p, f _k,p )‖=sup ‖S(p, f)‖fεQ(p) is called a maximum modular polynomial inQ _k (p), where $$S(p,f) = \sum\limits_{x = 0}^{p - 1} {e^{2\pi if(x)/p} } $$ Moreover, we definec(k, p)=‖S(p, f _k.p (x))‖. The main results are the following theorems.

1. For k=p?1 and p≥3 we have $$c(k,p) = \sqrt {p^2 - 4(p - 1)\sin ^2 \frac{\pi }{p}} $$ Besides, we may take \(f_{k,p} (x) = \prod\limits_{r = 0}^{p - 2} {(x - r)} \)
2. For k=p?s, 2≤s≤(p+1)/2 and p≥5, we have $$c(k,p) \leqslant p - 4(s - 1)\sin ^2 \frac{\pi }{p}$$ .

In Theorems 3 and 4, an interesting connextion between the present question and the famous problem of Prouhet and Tarry is given, some conditions under which the sign of equality in Theorem 2 holds are given and a method used to construct a maximum modular polynomial inQ _k (p) is also given.     

Coriatone and corianlactone, two novel sesquiterpenes from Coriaria nepalensis

Both coriatone (1). a novel highly oxygenated picrotoxane-type sesquiterpene, and corianlactone (2). with an unprecedented sesquiterpene basic skeleton, named coriane, were isolated from Coriaria nepalensis Wall. The structures of 1 and 2 were determined by analysis of their two-dimensional NMR data, and the structure of 2 was confirmed by X-ray analysis. Compounds 1 and 2 showed no remarkable inhibitory activity toward K(562) cells. They are cytotoxic with IC(50) > 50 microg/mL (cis-platinim: IC(50) = 0.49 microg/mL).     

Calculation of binding energy differences for receptor–ligand systems using the Poisson-Boltzmann method

An approach using the finite difference solution of the Poisson-Boltzmann equation to estimate binding free energy changes for two receptor–ligand systems, arabinose binding protein and sulfate binding protein, is presented. The eight calculated binding free energy changes agree with experiment, showing a correlation coefficient of 0.92 and energy deviations of 1 kcal/mol or less. More importantly, the decomposition of solvation and assembly energies in this approach provides an understanding of binding mechanisms and therefore could suggest directions to alter binding affinities. The method is demonstrated to be useful in analyzing experimental binding structures and predicting binding effects of mutants or modified ligands for macromolecular systems, in which the electrostatic forces dominate the overall interaction and the structural perturbations upon modifications are small. © 1995 by John Wiley & Sons, Inc.     

Syntheses of seven-membered rings: ruthenium-catalyzed intramolecular [5+2] cycloadditions

The Ru-catalyzed intramolecular [5+2] cycloaddition of cyclopropylenynes is investigated with respect to the regio- and diastereoselectivity as well as the functional group compatibility of the reaction. Evidence for the mechanism as occurring through a ruthenacyclopentene intermediate is elucidated from 1) the study of the diastereoselectivity of the cycloaddition; 2) the effect of variation of substituents on the regioselectivity of cyclopropyl bond cleavage in 1,2-trans- and 1,2-cis-disubstituted cyclopropanes and 3) examples that clearly do not involve ruthenacyclohexene as intermediates as products still incorporate the cyclopropyl moiety. The scope and limitations of the Ru-catalyzed cycloaddition are discussed and compared with the Rh-catalyzed reaction. The potential power of this methodology towards natural product total synthesis is demonstrated by the formation of several polycyclic systems with the chosen reaction conditions and readily available cyclopropylenyne substrates.