Raman spectroscopic study of conformational changes in the amorphous phase of poly(lactic acid) during deformation

The conformational distribution change of amorphous poly(lactic acid) (PLA) induced by deformation has been studied using Raman spectroscopy. Spectroscopic features associated with the rotational isomeric states (ttt, ttg′, tg′t, tg′g′) have been established experimentally and supported by normal coordinate analysis. Deformation induced a significant increase in the most favorable tg′t conformation. Based on the relative intensities of Raman-active skeletal modes, a quantitative method has been developed that can be used to elucidate structural changes in a variety of deformed polymer samples. For biaxially oriented PLA films, the overall tg′t conformation increased from the 76% in undeformed sample to a value as high as 92%. The change in conformational distribution in the amorphous phase follows a different trend (76-88%) as compared to the increase in sample crystallinity (0-43%). A large change in amorphous chain conformation occurred at relatively low draw ratios. In contrast, the large change in the degree of crystallinity occurred at higher draw ratios.     

Eicosapentaenoic acid (20∶5n-3) from the marine microalgaPhaeodactylum tricornutum

Eicosapentaenoic acid (EPA, 20∶5n-3) was obtained from the marine microalgaePhaeodactylum tricornutum by a three-step process: fatty acid extraction by direct saponification of biomass, polyunsaturated fatty acid (PUFA) concentration by formation of urea inclusion compounds, and EPA isolation by semipreparative high-performance liquid chromatography (HPLC). Alternatively, EPA was obtained by a similar two-step process without the PUFA concentration step by the urea method. Direct saponification of biomass was carried out with two solvents that contained KOH for lipid saponification. An increase in yield was obtained because the problems associated with emulsion formation were avoided by separating the biomass from the soap solution before adding hexane for extraction of insaponifiables. The most efficient solvent, ethanol (96%) at 60°C for 1 h, extracted 98.3% of EPA. PUFA were concentrated by the urea method with a urea/fatty acid ratio of 4∶1 at a crystallization temperature of 28°C and by using methanol and ethanol as urea solvents. An EPA concentration ratio of 1.73 (55.2∶31.9) and a recover yield of 78.6% were obtained with methanol as the urea solvent. This PUFA concentrate was used to obtain 93.4% pure EPA by semipreparative HPLC with a reverse-phase, C₁₈, 10 mm i.d.×25-cm column and methanol/water (1% acetic acid), 80∶20 w/w, as the mobile phase. Eighty-five percent of EPA loaded was recovered, and 65.7% of EPA present inP. tricornutum biomass was recovered in highly pure form by this three-step downstream process. Alternatively, 93.6% pure EPA was isolated from the fatty acid extract (without the PUFA concentration step) with 100% EPA recovery yield. This two-step process increases the overall EPA yield to 98.3%, but it is only possible to obtain 20% as much EPA as that obtained by three-step downstream processing.     

微波法合成复合氨基酸亚铁的工艺研究

以鸡羽毛为原料,正交实验法探讨了微波法制备复合氨基酸与亚铁螯合的最佳条件。结果表明,复合氨基酸微波水解优化条件为:固液比1∶5 g/mL,水解时间3 h,硫酸浓度3 mol/L,微波功率500 W,在该优化条件下,复合氨基酸转化率为63.6%;复合氨基酸亚铁微波合成优化条件为:复合氨基酸与铁的配位比2∶1,反应时间40 m in,微波功率400 W,在该优化条件下,复合氨基酸亚铁螯合率为83.4%。     

光学纯去氢枞酸的制备与表征

用化学方法由歧化松香制得光学纯去氢枞酸，并以ＵＶ、ＩＲ、＾１ＨＮＭＲ、ＭＳ、元素分析和旋光对其结构进行了表征。     

建龙化工新建150 kt/a硫磺制酸装置的几个特点

为保证原有4 500 kW发电机组满负荷运行的蒸汽供给及考虑当地硫酸市场的需求,新建一套150 kt/a硫磺制酸装置.该装置以原120 kt/a硫磺制酸装置的设计为蓝本,进行一定改进.在装置设备的选型配套、熔硫工序的挖潜改造、严冬季节土建施工、风机噪音消除等方面采取了相应措施.装置开车以来运行良好,达到设计要求.     

微波辐射活性炭负载磷钨酸催化环己醇脱水制环己烯

研究了在微波辐射条件下，活性炭负载磷钨酸脱水制环己烯的反应。考察了催化剂的负载量、催化剂用量、微波辐射时间和功率对反应的影响。结果表明：在催化剂负载量为25．4％，催化剂用量为3g，环己醇用量为20mL，微波辐射功率为600W，辐射时间为6min时，环己烯收率达84．3％，催化剂可重复使用。     

Lipase-catalyzed synthesis and properties of estolides and their esters

Eight lipases were screened for their ability to synthesize estolides from a mixture that contained lesquerolic (14-hydroxy-11-eicosenoic) acid and octadecenoic acid. With the exception ofAspergillus niger lipase, all 1,3-specific enzymes (fromRhizopus arrhizus andRhizomucor miehei lipases) were unable to synthesize estolides.Candida rugosa andGeotrichum lipases catalyzed estolide formation at >40% yield, with >80% of the estolide formed being monoestolide from one lesquerolic and one octadecenoic acyl group:Pseudomonas sp. lipase synthesized estolides at 62% yield, but the product mixture contained significant amounts of monoestolide with two lesquerolic acyl groups as well as diestolide. ImmobilizedR. miehei lipase was chosen to catalyze the esterification of mono-and polyestolide, derived synthetically from oleic acid, with fatty alcohols or α,ω-diols. Yields were >95% for fatty alcohol reactions and >60% for diol reactions. In addition, the estolide linkage remained intact through the course of the esterification process. Esterification of estolides improved the estolide’s properties—for example, lower viscosity and higher viscosity index—but slightly raised the melting point. Estolides and, particularly, estolide esters may be suitable as lubricants or lubricant additives.     

肠溶型药物包衣用丙烯酸树脂的制备工艺

采用乳液聚合法制备肠溶型药物包衣用丙烯酸树脂,采用甲基丙烯酸与甲基丙烯酸甲酯作为共聚单体、过硫酸钾作为引发剂、十二烷基硫酸钠及OP-10复配作为乳化剂、苯乙烯的二聚体作为分子量调节剂、碳酸氢钠作为pH值调节剂,考察了乳化剂配比及用量、引发剂及分子量调节剂的用量、反应温度、加料方式、相比等因素的影响,最终确定了实验制备药物包衣用丙烯酸树脂的最佳条件。利用乌氏粘度计测定其相对分子量,并作了红外光谱测试,结果表明,乳液符合国家药典要求。该制备过程避免了有机溶剂的使用,有明显的经济和环保效益。     

6-氟-3,4-二氢-2H-1-苯并吡喃-2-甲酸的合成

6-氟-3,4-二氢-2H-1-苯并吡喃-2-甲酸是制备新型抗高血压药奈必洛尔的关键中间体.今以4-氟苯酚为起始原料,经酯化、Fries重排、环化、氢化等6个步骤得到目标产物,总收率27%.4-氟苯酚Ⅰ与乙酸酐酯化得4-氟苯基乙酸酯Ⅱ,Ⅱ在AlCl3催化下Fries重排得4-氟-2-乙酰基苯酚Ⅲ,比从4-氟苯酚的Friedel-Crafts酰化收率更高,二步总收率58%;Ⅲ与酰化试剂乙二酸二乙酯经酯化、环合及碱性水解得到6-氟-4-氧代-4H-1-苯并吡喃-2-甲酸Ⅵ,用一种试剂完成了酰化、环化并引入羧基;Ⅵ在乙酸介质中,以10%Pd/C催化加氢得外消旋6-氟-3,4-二氢-2H-1-苯并吡喃-2-甲酸Ⅶ.以上所述的方法具有条件温和、试剂常见易得、易于工业化的优点,并首次给出了关键中间体及目标产物的光谱图,表明产物结构正确.     

乙醛酸和草酸的高效液相色谱分析

采用高效液相色谱法测定了草酸电合成乙醛酸中乙醛酸和草酸的含量,方法简便,成本低廉,效果良好。色谱柱为VP-ODS(150 mm×4.6 mm),流动相为稀磷酸水溶液(pH=2.7),流速为0.5 mL/min,柱温40℃,检测波长为212 nm。探讨了pH值及其它条件对色谱分离的影响。乙醛酸的线性方程为:Y=1.226×102X-7.053×102,线性相关系数R=0.999 6,相对标准偏差为1.5%,检出限为3.0×10-9g;草酸的线性方程为:Y=1.670×103X-5.563×104,线性相关系数R=0.999 9,相对标准偏差为0.8%,检出限为2.3×10-10g。