Morphology and crystallization of blends of linear low density polyethylene with a semiflexible liquid crystalline polymer

The morphology and the crystallization behavior of blends of linear low density polyethylene (LLDPE) with an experimental sample of a semiflexible liquid crystalline polymer (SBH 112 by Eniricerche, Italy) have been studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM) and scanning electron microscopy (SEM). The blends possess a two-phase morphology, due to immiscibility of the two components. SEM observations show that dispersion of the minor SBH phase is favored at low (相似文献   

Autocatalytic oxidation of Fe(Phen)3 2+ by bromate in water-in-oil reverse micelles of AOT

Autocatalytic oxidation of ferroin by bromate in water-in-oil reverse micelles of AOT has been studied experimentally and theoretically. The simplest models for this process have been constructed. Analytical solutions for these models were found for some limiting cases. It has been shown that the autocatalytic reaction runs much more slowly in reverse micelles than in water. The dependencies of the maximum reaction rate, _max, the exponent of the increase in ferriin concentration, , and induction period, , on micelle concentration have been obtained at =[H₂O]/[AOT]=4.6. It was found that there is only one theoretical model which can explain the experimental data. The values of the elementary reaction rate constantsk _i were estimated on the basis of the theoretical dependencies of _max and on the constantsk _i . All elementary rate constants turned out to be two or three orders of magnitude smaller than the corresponding constants for the reaction proceeding in water. The decrease in the rate constants is explained by the increase in viscosity and pH in a micellar water core at low .Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1401–1407, August, 1993.This work was supported by the Russian Foundation for Fundamental Investigations through Research Grant 93-03-4090.     

Nonequilibrium dynamics of a diffusion-limited reaction driven by a cluster-memory mechanism

The diffusion-limited reaction A+AA+B is studied in general dimension. The asymptotic decay of the system is found to depend nontrivially upon the initial concentration of A particles for certain ranges of the diffusion constant, backward reaction rate, and total concentration of particles. This nonequilibrium behavior is due to the formation of clusters centered about the initial A particles. A perturbative analysis ind=1 shows that the transition to the nonequilibrium dynamics is sharp and is quite similar to another previously studied reaction A+AA. Ford>1, a scaling argument is presented which describes the dependence of the asymptotic decay on the initial concentration of A particles and the equilibrium concentration for large backward reaction rates. Monte Carlo data are shown which confirm the analytic work ind=1, 2, and 3.     

CHARACTERISTICS OF THE PRIMARY REACTION OF HYPOCRELLIN A PHOTOSENSITIZATION

The primary reaction of photosensitization of Hypocrellin A (HA) has been studied byusing techniques of ESR, spin-trapping and spin-counteraction. The experiments show thatHA is able to generate not only ~1O_2,but also O_2~-·OH and HA~- which are observed for thefirst time. The conversion of generating active oxygen into generating nonoxygen free rad-ical is confirmed as well. Based on the characteristics of the primary reaction which gene-rates these active substances (transient products), it is proposed that the photosensitized dam-age for the biological system by HA is probably related to not only ~1O_2 itself, but also amultiple effect from ~1O_2 as well as O_2~-,·OH and HA~+ free radical.     

Lewis酸催化高区域选择合成对位柑菁醛的研究

Ｌｅｗｉｓ酸催化高区域选择合成对位柑菁醛的研究尹笃林，银董红，李谦和（湖南师范大学精细催化合成研究所，长沙４１００８１）关键词月桂烯，丙烯醛，对位柑菁醛，Ｄｉｅｌｓ－Ａｌｄｅｒ反应，Ｌｅｗｉｓ酸，络合催化。１．前言可从松节油资源中制取的月桂烯（ｍｙｒ...     

含氮亲核试剂在2-甲磺酰基-5-(3,4,5-三甲氧基苯基)-1,3,4-噁二唑环上取代反应的研究

2,5—二取代—l,3,4—噁二唑化合物具有消炎,抗菌,调节植物生长,杀虫门等广泛的生物活性。作者曾研究了取代胺在2—甲磺酰基—5—(2—苯基—4—喹啉基)—1,3,4—噁二唑化合物环2—位上的亲核加成消去反应,制得了一系列新的2—取代基—5—(2—苯基—4—喹啉基)—1,3,4—噁二唑衍生物,并发现它们具有一定的抗菌活性。在此基础上,我们又研究了含氮亲核试剂在 2—甲磺酰基—5—(3,4,5—三甲氧基苯基)—1,3,4,—噁二唑环2—位上的亲核加成消去反应,制得一系列新的2—取代基—5—(3,4,5—三甲氧基苯基)—1,3,4—噁二唑衍生物。作者用3,4,5—三甲氧基苯甲酰肼在KOH催化下与CS_2反应得到2—巯基—5—(3,4,5—三甲氧基苯基)—l,3,4—噁二唑1,1在NaOH溶液中与Me_2S0_4作用得到2—甲硫醚—5—(3,4,5—三甲氧基苯基)—1,3,4—噁二唑2,2在冰醋酸水溶     

Salt effects in the mercuration of unsaturated compounds. Kinetic evidence for the formation of ion pairs and a solvated ion

The kinetics of mercuration of bornylene and cyclohexene in different solvents in the presence of NaOAc and LiClO₄ has been investigated. Addition of NaOAc sharply decreases the rate of addition reactions of mercuric acetate to bornylene and cyclohexene in alcohols; the main direction of the mercuration of bornylene is the formation of acetoxy-adducts, and the yield of solvo-adducts decreases from 76 % in the absence of NaOAc, to 19 % in the presence of the salt (4·10^–3 mol L^–1). A reaction scheme involving the participation of intermediate ion pairs and a solvated mercurinium ion is suggested and confirmed by a steady-state concentration method. The influence of NaOAc on the rate of the reaction and on product formation is realized through the common ion effect.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 819–826, May, 1994.     

固体铁系超强酸的制备及催化水杨酸异丙酯的合成

报道固体铁系超强酸作为酯化催化剂，并研究了用此催化剂催化合成水杨酸异 丙酯，实验结果表明：水杨酸与异丙醇的投料比n酸：n醇＝1：6，催化剂的用量占 反应物总投料质量的6％，反应时间为4h,得产物水杨酸异丙酯，其产率达到94．5 ％，同时对催化剂的催化性能进行了讨论。     

The role of radicals in metal-assisted oxygenation reactions

The oxo-functionalization of organic substrates with the aid of metal oxo moieties is of fundamental importance not only in nature but also in academic and industrial research. Nevertheless the corresponding reaction mechanisms remain among the most enigmatic in chemistry and few of them are understood in detail. Recent research efforts have resulted in significantly improved information: in the cases of many oxygenation reactions evidence has been provided for the occurrence radical intermediates, even though the high selectivity observed suggests to a different mechanism. Examples stem from various areas of chemistry and include processes involving molecular metal oxo complexes, gas-phase and matrix-isolated species, metalloenzymes, and solid-state oxide surfaces. This review treats this seemingly wide variety of systems with the aim of providing an overview of common reactivity patterns and principles, as well as open problems.     

An unusual, mild and convenient one-pot two-step access to (E)-stilbenes from hydroxy-substituted benzaldehydes and phenylacetic acids under microwave activation: a new facet of the classical Perkin reaction

A mild and convenient one-pot two-step synthesis of hydroxystilbenes with trans selectivity has been developed through a modified Perkin reaction between benzaldehydes and phenylacetic acids bearing 4- or 2-hydroxy substitution at the aromatic ring, in the presence of piperidine-methylimidazole and polyethylene glycol under microwave irradiation. The observation of a simultaneous condensation-decarboxylation leading to the unusual formation of hydroxystilbenes in lieu of α-phenylcinnamic acid reveals an interesting facet to the classical Perkin reaction. The developed protocol provides a green alternative to the prevalent methods employing a toxic decarboxylating agent in the form of quinoline/Cu salt, and the requirement for harsh protection-deprotection steps for the synthesis of hydroxylated stilbenes.