Studies on the thermotropic liquid crystalline polymer. VII. Synthesis and properties of photocrosslinkable poly(ether-ester) containing cinnamic group

A series of semi-aromatic poly(ether-ester)s containing cinnamic group was prepared from 4,4′-diacrylic acid-α,ω-phenoxyalkanes with diols in the presence of diphenylchlorophosphate (DPCP) and pyridine as a catalyst and solvent. The phase behavior of these polymers was studied by differential scanning calorimetry (DSC), optical polarizing microscopy equipped with a heating stage, and wide-angle x-ray diffraction (WAXD). All of the poly(ether-ester)s, except P3 , show nematic or smectic thermotropic liquid crystalline behaviour under optical polarizing microscopic observation. These polymers can undergo photocrosslinking reaction upon heating, as examined by IR, solubility, and DSC analysis. © 1993 John Wiley & Sons, Inc.     

Oxidative Addition vs. Ligand-Exchange: Fe(II)-Mixed-Phenylchalcogenolate Complexes fac-[PPN][Fe(CO)3(TePh)n(SePh)3-N] (n = 1, 2)

Diphenyldichalcogenides (PhE)₂ (E = Te, Se) react with Fe(0)-phenylchalcogenolate [PPN] [PhEFe(CO)₄] to yield the products of oxidative addition, Fe(II)-mixed-phenylchalcogenolate fac- [PPN][Fe(CO)₃(TePh)_n(ScPh)_3-n] (n = 1, 2). Reactions of [PPN][REFe(CO)₄] (E=Se, R=Me; E=S, R=Et) and diphenyldichalcogenides yielded ligand-exchange products [PPN][PhEFe(CO)₄] (E=Te, Se, S). The compounds [Fe(CO)₃(TePh)(ScPh)₂]^? (l) and [Fe(CO)₃(TePh)₂ (2) crystallize in the isomorphous monoclinic space group C_2/e, with a = 32.035(8), b = 11.708(6), c = 28.909(6) Å, Z = 8, R = 0.048, and R_w = 0.044 (1); with a = 32.089(5), b= 11.745(2), c = 28.990(8) Å, Z = 8, R = 0.048, and R_w = 0.048 (2). The complexes 1 and 2 crystallize as discrete cations of PPN⁺ and anions of [Fe(CO)₃(TcPh)_u(ScPh)_3-n] (n=1, 2), and one half solvent molecule THF. The geometry around Fe(II) is a distorted octahedron with three carbonyl groups and three phenylchalcogenolate ligands occupying facial positions.     

蒙特卡洛模拟退火与距离限制相结合的方法在多肽溶液构象分析中的应用

多维核磁共振技术的飞速发展议得其在生物大分子结构测定方面的应用已经达到可以与【射线晶体学并驾齐驱的地步．蛋白质结构堆积紧密，较适合于用核磁共振方法给出确定的结构．与蛋白质不同的是多肽的柔性较大，在溶液中可能存在多种构象，核磁共振实验给出的只是平均信息＊．利用核磁，（振数据构建分子结构模型常用的方法有距离几何、分子动力学等，在由核磁共振NOESZ得到的距离信息足够多时可以给出较好的结果问．由于多肽本身的特点：柔性较大，由核磁共振得到的距离信息较少等，利用距离几何、分子动力学方法进行构象搜索时容易陷入…     

乙醇酸和DL─乳酸交替共聚物的合成和表征

乙醇酸和ＤＬ－乳酸交替共聚物具有不同于其无规共聚物的理化性能和生物降解性。以ＤＬ－３－甲基－１，４－二烷－２，５－二酮为单体，通过在辛酸亚锡引发下的本体开环聚合，合成了该交替共聚物，并进行了结构表征。     

Kinetic and mechanistic studies of the copolymerization of bis-4-substituted-1,2,4-triazoline-3,5-diones with styrenes

Highly reactive 4-substituted-1,2,4-triazoline-3,5-diones (TDs) have been studied extensively as dienophiles, but little work has been done on their role as enophiles and particularly on their use as propagating species in polymerization studies. The copolymerization between bis-4-substituted-1,2,4-triazoline-3,5-diones (bis-TDs) and styrene has been reported. The purpose of the present work was to synthesize new copolymers derived from a variety of substituted styrenes and bis-TDs and to study the mechanism and kinetics of this novel polymerization. Three bis-TDs were prepared: 3,3′-dimethyl-4,4′-bis[3,5-dioxo-1,2,4-triazoline-4-yl] biphenyl (8), t-1,4-bis[3,5-dioxo-1,2,4-triazoline-4-yl] methyl cyclohexane (9), and 4,4′-bis[3,5-dioxo-1,2,4-triazoline-4-yl] phenyl ether (10). Their structures were fully established by spectroscopic studies, elemental analyses, and indirectly, their quantitative ene reactions with 2,3-dimethyl-2-butene. Copolymerization between bis-TDs and substituted styrenes was carried out in dimethylformamide (DMF), tetrahydrofuran (THF), or dichloroethane (DCE). Polymers formed were characterized by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry (DSC), gel permeation chromatography (GPC), and viscometry. Molecular weights of polymers range from 5000 to 16,000 in most cases. They were stable up to 250°C and higher. Polymers derived from bis-TDs and p-t-butylstyrene, α-methylstyrene, p-nitrostyrene, and p-acetoxystyrene contained only Diels-Alder-ene (DAe) repeating units, whereas those derived from styrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, and 4-vinylbiphenyl contained both DAe and double Diels-Alder (dDA) repeating units. A kinetic study of the copolymerization of 4,4′-bis-(3,5-dioxo-1,2,4-triazoline-4-yl) phenyl ether with α-methylstyrene, p-t-butylstyrene, styrene, p-chlorostyrene, and p-nitrostyrene in DCE was carried out; the copolymerization rate constants were 60.9, 49.8, 8.4, 5.5, and 0.8 (1 mol^?1s), respectively.     

Reactions of fused dihydro-1,2,4-thiadiazoles with isoselenocyanates giving 6aλ4-thia-1,3,4,6-tetraazapentalene derivatives and 5,10-dihydro-1,2,4-thiaselenazolo[4,5-b][2,4]benzodiazepines

3-Methyl-6,7-dihydro-5H-1,2,4-thiadiazolo[4,5-a]pyrimidine (1) reacted with isoselenocyanates with elimination of acetonitrile and concomitant addition of two molecules of the isoselenocyanate to give 2,3-di-substituted-6,7-dihydro-5H-2aλ⁴-thia-2,3,4a,7a-tetraazacyclopent[cd]indene-1(2H),4(3H)-diselones (6a)–(6j). 3-Methyl-5,10-dihydrobenzo[e]-1,2,4-thiadiazolo[4,5-a][1,3]diazepine (3) likewise reacted with alkyl isoselenocyanates to give the 2,3-dialkyl-5-10-dihydro-2aλ⁴-thia-2,3,4a,10a-tetraazapentaleno[3,3a,4-gh]benzocycloheptene-1,4-diselones (9a)–(9h), but reaction of (3) with aryl isoselenocyanates took place with elimination of acetonitrile and incorporation of one molecule of the aryl isoselenocyanate in the product to give 3-arylimino-5,10-dihydro-1,2,4-thiaselenazolo[4,5-b][2,4]benzodiazepines (10a)–(10h). Structure (10) is a new heterocyclic system. The pyrimidine (1) and the diazepine (3) reacted with aryl isoselenocyanates at room temperature in solvents of low polarity to give zwitterion 1:1 addition compounds (7) and (12), respectively. NMR studies reveal that the thiaselenazoles (10) react in solution with aryl isoselenocyanates to give diaryl diselones (11) in a reversible process involving a Dimroth rearrangement. © 1996 John Wiley & Sons, Inc.     

Ruminant pregastric lipases: experimental evidence of their potential as industrial catalysts in food technology

The historical importance of pregastric enzymes in cheese-making is reviewed and the potential for extending their use is discussed in terms of requiring an understanding of their physicochemical parameters. Commericial extracts from the tongues and epiglotti of suckling lambs and calves and adult goats have been processed to yield partially purified samples of the primary pregastric lipase (PGL). The N-terminal sequence and molecular weight of lamb PGL have been determined.

The activity of lamb and goat PGLs against tributyrin has been determined over a range of pH and temperature values. Optimum conditions were pH 6.4, 43°C, and pH 6.0, 52°C, for lamb and goat PGL respectively. The possible influence of the development of a ruminant multi-chambered stomach on the difference in optimal temperature is discussed. A lengthening of the carboxylic acid chain of homoacid triglycerides causes a decrease in hydrolytic activity of lamb PGL but in all cases only a single free fatty acid was released. Against a series of 4-nitrophenylalkanoate esters, maximum activity was observed against the decanoate ester but, in contrast to hydrolysis of the acetate ester which exhibited full Michaelis-Menten kinetics with increasing substrate concentration, activity against the decanoate ester was restricted to the monomeric substrate. Taurocholate inhibits the activity of lamb PGL at concentrations >8 mM. Values of pK₂ equal to 6.69 and 7.92 respectively have been determined for lamb PGL.

Attempts to interesterify coconut oil and cocoa butter, and tributyrin and tricaprylin, catalysed by calf PGL were unsuccessful, although positive results obtained using Candida cylindracea encourage further investigation of alternative methods for immobilizing the PGL. Finally, anhydrous milk fat has been hydrolysed by calf, lamb and goat PGLs and the differences in relative amounts of released free fatty acids have been used to explain the differences in taste which arise when Parmesan cheese is produced using different sources of PGL.