双酰亚胺型均苯四甲酸及复合酸镧盐的合成与应用

采用水热法制备了4,4'-亚甲基-二苯基-二-(1″,2″)-酰亚胺-二-(4″,5″)-苯二甲酸酐(简称酰亚胺四酸酐)以及双硬脂酸单4,4'-亚甲基-二苯基-二-(1″,2″)-酰亚胺-二-(4″,5″)-苯二甲酸二镧(简称复合酸镧盐La-1),应用红外光谱与热失重法对其结构进行表征,并将La-1应用于聚酰胺66(PA 66)以改善PA 66热氧化稳定性,且与硬脂酸镧(La-2)、均苯四甲酸镧(La-3)、双硬脂酸单均苯四甲酸二镧(La-4)进行比较。结果表明:通过正交实验得出,酰亚胺四酸酐合成的最优反应条件为酰亚胺化反应温度135℃,时间5 h,二甲苯与产物水质量比6∶1,均苯四甲酸酐(PMDA)与4,4'-二氨基二苯甲烷(DDM)摩尔比2.3∶1.0;傅里叶变换红外光谱表征所合成的酰亚胺四酸酐和La-1为目标产物;La-3的热分解温度大于550℃,高于PA 66的热分解温度,La-1,La-2,La-3的热稳定性均弱于纯PA 66;La-3,La-4对PA 66的抗黄变性效果比La-1,La-2的要好,这是由于硬脂酸长链热稳定性差及芳香酸镧中的邻苯二甲酸结构中残存羟基量对PA 66热氧化稳定性造成影响的缘故。     

Surface-active properties and thermal behavior of S-alkylthio-carboxylic acids and their potassium salts

S-Alkylthiocarboxylic acids and their potassium salts were prepared by photoaddition of α-olefins (C₁₀, C₁₂, and C₁₄) with mercapto carboxylic acids such as thiomalic acid, thiopropionic acid, and thioglycolic acid. The physicochemical solution properties and thermal stabilities for three series of thiosurfactants were evaluated. S-Alkylthiocarboxylic acids that contain bridged S-bonds provide excellent thermally stable surfactants, and their alkaline salts exhibit good surface activity.     

Sorption behavior of mercuric salts on chemically modified wools and polyamino acids

Wool derivatives with sulfhydryl, thiosulfate, imidazole, pyrrolidone, or pyridine side chains were prepared and tested as potential scavengers for mercury salts in aqueous solution. More mercury is bound by these derivatives than by native wool or by certain commercial ion exchange resins under similar conditions. The presence of chloride ion, but not sulfate ion, in aqueous media decreased the extent of binding of mercuric chloride to both native and modified wools. The relative binding of mercuric chloride by various poly(amino acids) suggest that mercury is taken up by proteins by processes other than (or in addition to) specific combination with free functional groups. Two possibilities are suggested: the protein may act as a solid solvent for the mercurial, or the mercurial may form aggregated deposits within the protein after the specific binding sites have been occupied. These studies are intended to elucidate factors that govern mercury interaction with wool and other proteins and to develop improved scavengers for toxic metals.     

The transfer of free palmitic and linoleic acids across the ovine placenta

Following the injection of³H-16∶0 and¹⁴C-18∶2 (n−6) into the jugular vein of the ewe, the rates of disappearance of these fatty acids from the maternal plasma and their rates of appearance in the fetal plasma have been studied. The rates of disappearance of both labeled acids from the maternal circulation were similar. The appearance of radioactivity in the fetal plasma was rapid and could be detected within 2.5 min after injection into the mother. In contrast to the similar rates of disappearance of the fatty acids from the maternal plasma, the rate of accumulation of³H-16∶0 within the fetal plasma was appreciably greater than that of¹⁴C-18∶2 (n−6). The absolute concentrations of the total lipid and unesterified fatty acid fractions within the fetal plasma were significantly lower than that of the maternal plasma. In comparison to that of maternal plasma, fetal plasma lipid contained an extremely low proportion of 18∶2 (n−6) accompanied by an appreciable accumulation of 20∶3 (n−9). On the other hand, the proportion of 20∶4 (n−6) within the fetal plasma was about twice that present within the maternal plasma. The obvious inability of the placenta to be as freely permeable to the passage of 18∶2 (n−6) as to 16∶0 is discussed in relation to these differences in fatty acid composition between the maternal and fetal plasmas and the known poor essential fatty acid status of the developing fetus.     

Phase behavior of the ternary system solvent: poly(γ-benzyl L-glutemate) and polystyrene

Summary Phase equilibria were investigated at 80°C for a ternary system involving a solvent benzyl alcohol, a rodlike polymer poly(-benzyl L-glutamate) (PBLG), and a flexible polymer polystyrene (PS). The fairly dilute solution of the two polymers was isotropic and monophasic. At greater concentrations, it was separated into two isotropic phases. Above an even higher critical concentration of the two polymers, three phases, a cholesteric (A₁) and two isotropic phases (I₁ and I₂), coexisted at equilibrium. PBLG was contained exclusively in the phases A₁ and I₁, while PS was in the phase I₂. The more concentrated solution was separated into a cholesteric phase and an isotropic phase. The latter contained PS but excluded PBLG, These features were discussed on the ground of the Flory theory by considering the polymer compatibility.     

Use of thermostable Fusarium heterosporum lipase for production of structured lipid containing oleic and palmitic acids in organic solvent-free system

A newly developed 1,3-positionally specific thermostable lipase from Fusarium heterosporum (named R275A lipase) was immobilized on Dowex WBA for the production of structured lipid by acidolysis of tripalmitin (PPP) with oleic acid (OA). The immobilized catalyst was fully activated by pretreatment at 50°C in a PPP/OA mixture containing 2% water. The pretreatment caused concomitant hydrolysis, but the hydrolysis was repressed using a substrate without water in the subsequent reactions. The optimal reaction conditions were determined as follows: A mixture of PPP/OA (1∶2, w/w) and 8% immobilized lipase catalyst was incubated at 50°C for 24 h with shaking at 130 oscillations/min. The acidolysis reached 50% under these conditions, and the contents of triolein, 1,3-dioleoyl-2-palmitoyl-glycerol, 1(3),2-dioleoyl-3(1)-palmitoyl-glycerol, 1(3),2-palmitoyl-3(1)-oleoyl-glycerol, 1,3-dipalmitoyl-2-oleoyl-glycerol, and PPP in the reaction mixture were 8, 36, 4, 28, 1, and 6 mol%, respectively. The stabilities of immobilized R275A lipase catalyst and two immobilized catalysts containing Rhizopus delemar or Rhizomucor miehei lipases were compared under the conditions mentioned above, with the catalysts being transferred to fresh substrate every 24 h. The half-life of the R275A lipase catalyst was 370 d, which was significantly longer than those of Rhizopus and Rhizomucor lipase catalysts.     

Octadecylsulfuric acid. Properties of the acid,amine salts,and salts of amino acids

Summary Octadecanol, hexadecanol, tetradecanol, and dodecanol were sulfated with chlorosulfonic acid, and the corresponding alkylsulfuric acids were isolated in a pure state as white crystalline solids with definite melting points. Octadecylsulfuric acid resembles sodium octadecyl sulfate in detergent and surface-active properties and in stability to hydrolysis at equal concentrations of hydrogen ion. It is more soluble in water than sodium octadecyl sulfate and readily soluble in organic solvents. The critical micelle concentration (0.0387 millimoles/I.) is only about one-third that of the sodium salt. Isolation of octadecylsulfuric acid as a useful chemical intermediate made possible the preparation of a number of salts with amines and amino acids and their rapid screening for useful properties. Presented at the spring meeting, American Oil Chemists' Society, New Orleans, La., April 20–22, 1959. Eastern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Lipase specificity toward some acetylenic and olefinic alcohols in the esterification of pentanoic and stearic acids

The esterification of five medium- and long-chain acetylenic alcohols (2-nonyn-1-ol, 10-undecyn-1-ol, 6-octadecyn-1-ol, 9-octadecyn-1-ol, and 13-docosyn-1-ol), seven olefinic alcohols (cis-3-nonen-1-ol, 10-undecen-1-ol, cis-6-octadecen-1-ol, cis-9-octadecen-1-ol, trans-9-octadecen-1-ol, trans-9, trans-11-octadecadien-1-ol, cis-9, cis-12-octadecadien-1-ol), and four short-chain unsaturated alcohols (allyl alcohol, 3-butyn-1-ol, 3-pentyn-1-ol, and cis-2-penten-1-ol) with pentanoic or stearic acid in the presence of various lipase preparations was studied. With the exception of 2-nonyn-1-ol, where Lipase AY-30 (Candida rugosa) was used as the biocatalyst, the esterification of C₁₁, C₁₈, and C₂₂ acetylenic alcohols with pentanoic acid appeared to be generally unaffected by the presence of an acetylenic bond in the alcohol as relatively high yields of the corresponding esters (78–97%) were obtained. However, medium- and long-chain olefinic alcohols were discriminated by Lipase AY-30, Lipolase 100T (Rhizomucor miehei), and especially by porcine pancreatic lipase (PPL), when esterification was conducted with pentanoic acid. Esterification of medium-and long-chain acetylenic or olefinic alcohols with a long-chain fatty acid, stearic acid, was very efficient except when Lipase AY-30 and Lipolase 100T were used. Short-chain unsaturated alcohols were much more readily discriminated. 3-Pentyn-1-ol and 3-butyn-1-ol were difficult (<5% yield) to esterify with pentanoic or stearic acid in the presence of Lipase AY-30 and PPL, respectively. Very low yields (<26%) of esters were produced when 3-butyn-1-ol and 3-pentyn-1-ol were reacted with pentanoic or stearic acid, when catalyzed by lipase from Candida cylindracea, No reaction took place between 3-butyn-1-ol and stearic acid in the presence of Lipase AY-30. Esterification of short-chain acetylenic and olefinic alcohols was most efficiently achieved with Lipolase 100T (Rhizomucor miehei), Lipozyme IM20 (Rh. miehei), or Novozyme 435 (Candida antarctica) as the biocatalyst.     

PI/NMP/H_2O三元体系相行为与纤维成形研究

介绍了湿法纺丝中凝固剂/溶剂/聚合物三元体系热力学理论及三元相图双节线和旋节线的计算方法;在聚酰亚胺/N-甲基-2-吡咯烷酮/水(PI/NMP/H2O)三元体系中,采用黏度法计算了PI-NMP相互作用参数(χ23),平衡溶胀法测得PI-H2O相互作用参数(χ13),结合NMP-H2O相互作用参数,并根据FloryHuggins溶液理论绘制出不同温度下PI/NMP/H2O三元体系的理论相图,并研究了不同凝固浴温度下PI纤维纺制中的相分离及成形过程。结果表明:在25,40,60℃时,χ23分别为0.489 6,0.480 1,0.473 4,χ13分别为1.52,1.47,1.30;随着凝固浴温度升高至60℃时,纤维表面逐渐变得致密光滑,断面形态由肾形变为规则的圆形;凝固浴温度升高时,相图中亚稳态区域扩大,纤维成形过程更加缓和,有利于制备结构致密的PI纤维。     

The effect of isomerictrans-18∶1 acids on the desaturation of palmitic,linoleic and eicosa-8,11,14-trienoic acids by rat liver microsomes

The inhibitory effects of the positional isomers oftrans-18∶1 acids on the desaturation of palmitic acid to palmitoleic (Δ9-desaturase), linoleic to γ-linolenic (Δ6-desaturase) and eicosa-8,11,14-trienoic to arachidonic acid (Δ5-desaturase) were investigated. Thesetrans-18∶1 acids were found to be inhibitory for the microsomal Δ6-, Δ9- and Δ5-desaturases of rat liver. The position of the double bond in thetrans-18∶1 acids seems to be important in determining the degree of inhibition. At inhibitor/substrate ratio of 3∶1, the Δ6-desaturase was most strongly inhibited bytrans-Δ3,-Δ4,-Δ7 and-Δ15-18∶1 isomers, whereas the Δ9-desaturase was most strongly inhibited bytrans-Δ3,-Δ5,-Δ7,-Δ10,-Δ12,-Δ13 and-Δ16 isomers. At inhibitor/substrate ratio of 6∶1, the Δ5-desaturase was most strongly inhibited by Δ3-, Δ9-, Δ13- and Δ15-isomers. When 18∶0 was added to the incubations of 16∶0, 18∶2 and 20∶3 at the same I/S ratios used for thetrans-18∶1 acids, weak inhibition for Δ9-desaturase and no inhibition for Δ5-and Δ6-desaturases was observed.     

Long-chain carboxylic acids containing ether linkage III. The antibacterial and antifungal activities of the amine salts of someB-alkoxypropionic acids

Octylamine, dodecylamine, octadecylamine and triethanolamine salts ofβ-dodecyloxy- andβ-tetradecyloxypropionic acids, without or with one and with two oxyethylene groups between the alkoxy group and the propionic acid group, were prepared and examined as the growth inhibiting agents againstStaphylococcus aureus andPenicillium. Some of them were also tested againstTrichophyton asteroides, T. interdigitale, T. granulosus, Epidermophyton floccosum andMicrosporum canis. The effects of the alkyloxy, oxyethylene and amine groups on antibacterial and antifungal activities were determined. The dodecyl radical was more potent than the tetradecyloxy radical. The enhancing effect of the oxyethylene group was obscure in the amine salts. The most effective amine was dodecylamine and its salt ofβ-dodecyloxypropionic acid showed almost the same effectiveness as that of its mercury salt againstTrichophyton. As for the soluble amine salts, it was confirmed that their surface activities had nothing to do with their antibacterial and fungicidal powers.     

The thermal decomposition of ammonium nitrate in fused salt solution and in the presence of added salts

The thermal decomposition of ammonium nitrate in a fused equimolar mixture of sodium and potassium nitrates has been studied. It is shown that the reaction is first order with respect to ammonium ions. the rate of decomposition is increased by cations of a highly polarising nature, whereas anions, such as sulphates, phosphates and fluorides, which act as bases in the system, decrease the rate of decomposition. the observations are in accord with an ionic mechanism for the decomposition of ammonium nitrate, involving the reaction of ammonia with the nitronium ion.     

The fungicidal activity of the unsaturated fatty acids and quaternary salts prepared from fish oils

Summary Saturated and unsaturated fatty acids and 10 unsaturated fatty acid fractions and ethyl esters of unsaturated fatty acid fractions prepared from fish oils were tested on their inhibitory activity againstCandida albicans. Oxidation of highly unsaturated fractions from fish oil and ethyl esters of unsaturated fatty acid fractions of menhaden, pilchard, and cod liver oils increases their antifungal activity. Saturated and unsaturated quaternaries were tested for their antifungal activity. Hexadecyltriethylammonium bromide and hexadecylpyridinium bromide showed the highest activity againstCandida albicans, Aspergillus niger, andRhyzopus nigricans. Any lengthening of the carbon chain more than C₁₆ weakened the activity of both saturated triethylammonium bromide and pyridinium bromide. An increase of unsaturation enhanced it. The antifungal activity of quaternaries prepared from fish oils was about 4,000 times stronger than that of oxidized highly unsaturated fatty acid fractions prepared from fish oils. The decisive factor in the highly inhibitory activity of quaternaries against fungi might depend on their positively charged portion since the surface of microorganisms is, as a rule, negatively charged. Aided by a grant from the Collett-Week Company, Ossining, N. Y.     

On the low frequency dielectric behavior of carboxymethyl cellulose and its sodium salt

A dielectric dispersion and frequency loss peak within the low frequency range 0.05–1 kc/s and at temperatures of 283–333 K was observed in the case of the sodium salt of carboxymethyl cellulose and absent in the case of its acid form. The critical frequency of the dielectric absorption was independent of molecular weight and of the presence of low moisture content. The results obtained show that the variation with temperature of the dielectric constant is exponential at low frequency only in the case of the sodium salt of carboxymethyl cellulose. The significance of the results is discussed.     

Application of genetic algorithm in calculation of the phase behavior of binary and ternary polymer solutions

A genetic algorithm as an optimization procedure has been developed to predict the phase behavior of polymer solutions. The phase equilibrium diagrams of binary and ternary polymer solutions have been determined using the appropriate form of Flory–Huggins free-energy function for polymer solutions. A concentration and temperature dependent form of the interaction parameter has been used to reflect the effect of temperature and polymer properties in the free-energy form. The proposed genetic algorithm is applied to compare the phase behavior results of some typical polymer solutions with the results of the classical determination methods and then applied to some conventional ternary polymer solutions as polymer–solvent–nonsolvent systems. The proposed algorithm use a set of individual states as the initial chromosomes and uses the general rules as crossover, mutation, and with use of a fractional objective function determines the binodal points or the phase diagram boundaries of polymer solutions. The properties of an industrially relevant polymer solution, a polystyrene–cyclohexane solution, have been used to emphasize on the industrial application of the proposed algorithm. The algorithm has been used to predict the phase behavior of the two polymer–solvent–nonsolvent systems as polystyrene-butanone-methanol and polystyrene-butanone-propanol at three different temperatures and results show good agreement with the experimental observations. The algorithm also has the capability to predict both the concentration-independent and concentration-dependent interaction parameters among the different components. The genetic algorithm is an easy-to-use, state-of-art, and very fast optimization tool, and has very strong capability to solve nonlinear systems in chemical and polymer engineering topics.     

正庚烷-甲苯-糠醛三元体系液液相平衡数据的测定与关联

在常压条件下测定了正庚烷-甲苯-糠醛三元体系在不同温度(293.15,303.15,313.15 K)下的液液相平衡数据。采用Othmer-Tobias方程对不同温度下的相平衡数据进行可靠性检验,相关性系数接近于1,表明实验数据存在较好的可靠性。用NRTL活度系数模型方程对实验数据进行关联,并使用Aspen Plus模拟软件回归计算出了该三元体系的二元交互作用参数,根据实验值和模拟值绘制不同温度下的三元相图。关联计算结果表明:NRTL方程对该三元体系适用性较好,实验值与模拟值之间的均方根偏差在1%以内,数据准确性高。根据实验数据计算出了萃取剂的选择性,为以后实验提供参考。     

醋酸甲酯-甲醇-水三元物系液液平衡数据的测定与关联

测定了常压下20、30、40、50℃时醋酸甲酯 水二元体系及醋酸甲酯 甲醇 水三元体系的液液平衡(LLE)数据,并与文献中已有的醋酸甲酯 水的液液平衡数据进行比较,证明了测定方法的可靠性。采用二元与三元液液平衡数据相结合的关联方法,并用NRTL和UNIQUAC模型对所测数据进行了热力学关联,得出了相应的模型参数。用该模型对三元体系进行计算,结果令人满意。用VisualBasic6.0语言开发了液液相平衡关联软件,可方便地用于二元和三元液液相平衡的计算。     

有机酸及相关盐类在果蔬护色、防褐变中的应用研究

考察了不同浓度的曲酸、抗坏血酸、乳酸及ZnC l2、CaC l2、乳酸锌、乳酸钙处理苹果和梨的防褐变时间。结果表明,曲酸的护色效果最好。当曲酸浓度>0.1%时,防褐变效果很好,24 h时只有轻微褐变;当乳酸钙浓度>1.0%,抗坏血酸浓度>0.25%,ZnC l2浓度>0.75%,CaC l2浓度>1.0%时,防褐变效果均较好。     

The effects of some organic acids and salts on the setting of gypsum plaster III. citrates

A study has been made of the effects of citric acid, potassium citrate and calcium citrate on the setting of calcium sulphate hemihydrate plaster, in continuation of previous studies on this reaction.^1,2 The citrates showed more complicated effects than the additives previously tested, and the following factors are taken into account in interpreting the experimental results: (i) formation of complexes, (ii) adsorption, (iii) metathesis and (iv) the accelerating effect of an alkali metal ion, if present.