Chemistry of mandibular and Dufour's gland secretions of ants in genusMyrmecocystus

Males of several species ofMyrmecocystus produce mandibular gland secretions that contain 2,4-dimethyl-2-hexenoic acid and a variety of monoterpenes that include neral, geranial, citronellol, limonene, and 2,6-dimethyl-5-hepten-1-ol. Other components identified include methyl anthranilate, octanal, octanol, octyl octanoate, and 2-hexyl-2-decenal. Methyl salicylate has been identified as a mandibular gland constituent of workers of several species in addition to mellein and monoterpenes such as cymene, limonene, and the isomers of citral. The Dufour's gland secretions of workers and females of 14 species contain typical formicine alkanes (e.g., undecane), 2-alkanols (e.g., 2-tridecanol), and 2-alkanones (e.g., 2-tridecanone). Two species in the subgenusEremnocystus produce secretions that are distinguished by the presence of significant quantities of tridecyl esters. The functions of these compounds as well as their possible chemosystematic significance in the genusMyrmecocystus are discussed.     

Analysis of epoxidized soybean oil by gas chromatography

A fast and cost-effective procedure to quantitate epoxidized soybean oil by means of an external standard method is reported. This procedure is applicable to commercial epoxidized oils, polymer additive packages and polymers—polyvinyl chloride (PVC)—containing epoxidized oils. The epoxidized soybean oil is converted into fatty acid methyl esters with tetramethylammonium hydroxide, and analyzed by capillary gas chromatography with flame-ionization detection. In PVC samples, the epoxidized soybean oil was extracted with toluene and followed by derivatization prior to analysis. The methyl esters of monoepoxyoctadecanoic, diepoxyoctadecanoic and triepoxyoctadecanoic acid were separated with a short capillary column.     

Aerobic biodegradation of di-n-butyl phthalate by Xiangjiang River sediment and microflora analysis

Di-n-butyl phthalate (DBP), one of phthalate acid esters (PAEs), was investigated to determine its biodegradation rate using Xiangjiang River sediment and find potential DBP degraders in the enrichment culture of the sediment. The sediment sample was incubated with an initial concentration of DBP of 100 mg/L for 5 d. The biodegradation rate of DBP was detected using HPLC and the degraded products were analyzed by GC/MS. Subsequently, the microbial diversity of the enrichment culture was analyzed by polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP). The results reveal that almost 100% of DBP is degraded after merely 3 d, generating two main degraded products: mono-butyl phthalate (MBP) and 9-octadecenoic acid. After a six-month enrichment period under the pressure of DBP, the dominant family in the final enrichment culture is clustered with the Comamonas sp., the remaining are affiliated with Sphingomonas sp., Hydrogenophaga sp., Rhizobium sp., and Acidovorax sp. The results show the potential of these bacteria to be used in the bioremediation of DBP in the environment.     

蔗糖酯对精炼大豆油氧化稳定性的影响

以不含抗氧化荆的精炼大豆油为原料,研究了加入蔗糖酯对其氧化稳定性的影响,结果表明：在低温时（烘箱法）,HLB13的蔗糖酯具有一定的延缓大豆油氧化的作用,其中0．5‰添加量（质量分数）时延缓氧化效果最好;高温条件下（110℃）HLB13、HLB11、HLB9的蔗糖酯在不同浓度条件下有一定的加速氧化作用．     

二亚磷酸二(2,6-二叔丁基对甲酚)季戊四醇酯的合成

以亚磷酸三乙酯、季戊四醇和2,6-二叔丁基对甲酚为原料合成了抗氧剂二亚磷酸二（2,6-二叔丁基对甲酚）季戊四醇酯。探讨了物料配比、催化剂的种类及用量、反应时间等反应条件对产率的影响,并通过正交试验法确定了最佳工艺条件。实验结果表明：催化剂为无水碳酸钾,其用量为0.6 g;物料配比（n（季戊四醇）∶n（亚磷酸三乙酯）∶n（2,6-二叔丁基苯酚））为1.0∶2.12∶2.04;反应Ⅰ温度为130~140℃,反应Ⅰ时间为2 h,反应Ⅱ温度为170~180℃,反应Ⅱ时间为4 h。在最佳工艺条件下所制得的产品为白色粉末状固体,熔点为67~69℃,产率为87%左右。此外,通过元素分析、红外光谱分析对产品进行了物性和结构表征。     

Hydroformylation of functional alkenes with heterodonor phosphine rhodium catalysts: substrate or ligand directed regioselectivity?

The catalytic activity and selectivity of heterodonor phosphine rhodium catalysts prepared in situ were tested in the hydroformylation of functional alkenes (ethyl acrylate, methyl methacrylate, styrene, 4-vinyl-1-cyclohexene, dicyclopentadiene and cis-1,2,3,6-tetrahydrophthalic anhydride). Systematic variation of the heterodonor atom in the ortho position of the ligand showed that the heterodonor atom has a significant influence on the activities and selectivities of the reaction. However, the activity seems to depend mainly on the modifying ligand, and the regioselectivity mainly on the substrate (i.e., the structure and functionality of the alkene). Nevertheless, regioselective control is only obtained through synergy between the substrate and the catalyst. Clear regiocontrol was observed in the hydroformylation of ,-unsaturated esters and styrene with an in situ formed o-(thiomethylphenyl)diphenylphosphine rhodium catalyst.     

Study of the influence of reaction conditions on the degree of substitution,intrinsic viscosity,and yield of oxidized cellulose acetate by factorial experimental design

A half‐fraction, two‐level, four‐factor factorial experimental design was used to study the effects of the acetic anhydride concentration, reaction temperature, reaction time, and sulfuric acid concentration on the degree of substitution, intrinsic viscosity, and yield of oxidized cellulose acetate (OCA). Oxidized cellulose containing 20% (w/w) carboxylic acid was used as the starting material. The data were fitted by multiple regression analysis with SAS software. The correlation coefficients obtained from plots of the predicted and observed values for the degree of substitution, intrinsic viscosity, and yield were 0.985, 0.993, and 0.991, respectively. Residual normal plots of the regression models showed a linear relationship. Lenth and main‐factor‐effect plots revealed an increase in the degree of substitution of OCA with an increasing concentration of acetic anhydride. The latter had no effect on the intrinsic viscosity and yield of OCA. An increase in the reaction temperature led to an increase in the degree of substitution and a decrease in the intrinsic viscosity and yield of OCA. The influence of the reaction time on the degree of substitution and intrinsic viscosity followed a trend similar to that observed with the reaction temperature, but the yield of OCA was unaffected. Increasing the concentration of sulfuric acid reduced the degree of substitution, intrinsic viscosity, and yield of OCA. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 696–705, 2005     

In situ esterification of rice bran oil with methanol and ethanol

In situ esterifications of high-acidity rice bran oil with methanol and ethanol and with sulfuric acid as catalyst were investigated. In the esterification with methanol, all free fatty acids (FFA) dissolved in methanol were interesterified within 15 min, and it was possible to obtain nearly pure methyl esters. The amount of methyl esters obtained from a given rice bran was dependent on the FFA content of the rice bran oil. In the esterification with ethanol, it was not possible to obtain pure esters as in methanol esterification, because the solubilities of oil components in ethanol were much higher than those in methanol.     

Surface disposition and stability of pest-interactive,trichome-exuded diterpenes and sucrose esters of tobacco

The precise physical location of trichome-exudate biochemicals on the plant surface is undoubtedly important in plant-pest interactions, perhaps particularly those involving fungal and bacterial pathogens that invade the plant through the epidermal layer. The chemical stability of exuded compounds is also important in this regard. Here we have studied these two aspects of trichome biology using the highly exuded tobacco line,Nicotiana tabacum, T.I. 1068. Particularly under high relative humidity growth conditions, sucrose esters (SE) were found to migrate from the exudate droplet around the gland down the trichome stalk to the epidermal cells below. Six days after labeling leaf midveins on plants grown in a high humidity environment, 29 and 71% of label found in SE were recovered with trichome glands and below gland regions, respectively. Corresponding disposition in the moderate humidity environment was 40 and 60%, respectively. Migration of less polar duvatrienediols (DVT) was less marked. Staining of SE with rhodamine B showed the occurrence of more extensive and physically different migration in the high humidity versus moderate humidity case. Both SE and DVT were stable between six and 18 days postlabeling, the period encompassing the time of maximum exudate formation through the beginning of tissue senescence. Our results suggest that even under conditions that avoid mechanical disturbance of tissue, SE and DVT are chemically stable, at least until senescence, and appear to migrate from the gland region to the epidermal surface, apparently according to their relative polarity.     

二乙基羟胺-臭氧体系降解邻苯二甲酸二甲酯的机理学研究

本研究采用二乙基羟胺（DEHA）促进臭氧（O3）降解水中邻苯二甲酸二甲酯（DMP）,并建立了强化O3氧化能力的O3/DEHA体系。主要探索了在O3/DEHA体系中pH、DEHA投量、臭氧通量和DMP投量对该体系的影响及体系的氧化机理,并通过气相色谱/质谱（GC/MS）对DMP的降解产物进行了分析。结果表明：DEHA能够有效促进臭氧的分解且在酸性条件下（pH=3）明显提高DMP的降解率,DEHA投量为25μΜ时促进效果最佳;DMP降解速率随臭氧通量的增加而增加,随DMP浓度的增加而减小,通过动力学计算,该反应符合拟一级动力学反应;投加叔丁醇（TBA）能够明显抑制DMP的降解,验证了在酸性条件下,·OH对DMP的降解起主要作用;通过产物分析可推导出O3/DEHA体系中DMP 的降解途径主要从苯环上碳链的断裂开始,中间生成酸类和脂类化合物,最终矿化为水和二氧化碳。