Sterols ofKalanchoe pinnata: First report of the isolation of both C-24 epimers of 24-alkyl-Δ25-sterols from a higher plant

Eighteen sterols were isolated from the aerial parts ofKalanchoe pinnata (Crassulaceae) including four novel sterols,viz. (24R)-stigmasta-5,25-dien-3β-ol (24-epiclerosterol), (24R)-5α-stigmasta-7,25-dien-3β-ol, 5α-stigmast-24-en-3β-ol, and 25-methyl-5α-ergost-24(28)-en-3β-ol. 24-Epiclerosterol and its Δ⁷-analog occur together with their 24S/β-epimers in the same plant making this the first report of the isolation of both C-24 epimers of Δ²⁵-unsaturated 24-alkylsterols from a non-marine organism. Iodine-catalyzed isomerization of stigmasta-5,24-dien-3β-ol (24-ethyldesmosterol), the main sterol ofK. pinnata, yielded 24-epiclerosterol among other products.     

Fractionation and enrichment of CLA isomers by selective esterification with Candida rugosa lipase

A commercial product of CLA contains almost equal amounts of cis-9,trans-11 (c9,t11)-CLA and trans-10,cis-12 (t10,c12)-CLA. We attempted to enrich the two isomers by a two-step selective esterification using Candida rugosa lipase that acted on c9,t11-CLA more strongly than on t10,c12-CLA. An FFA mixture containing CLA isomers was esterified with an equimolar amount of lauryl alcohol in a mixture of 20% water and the lipase. When the esterification of total FA reached 50%, two isomers were fractionated in a good yield: t10,c12-CLA was enriched in FFA, and c9,t11-CLA was recovered in lauryl esters. The FFA were esterified again to enrich t10,c12-CLA. At 27.3% esterification of total FA, the t10,c12-CLA content in FFA increased to 64.8 wt% with 89.3% recovery: The ratio of the content of t10,c12-CLA to that of two isomers was 95.9%. Lauryl esters obtained by the single esterification were employed for enrichment of c9,t11-CLA. After the esters were hydrolyzed, the resulting FFA were esterified again with lauryl alcohol. At 62.0% esterification of total FA, the c9,t11-CLA content in lauryl esters increased to 73.3 wt% with 79.4% recovery: The ratio of the content of c9,t11-CLA to that of two isomers was 95.6%. In a 600-g-scale purification, molecular distillation was effective in separating the reaction mixture into lauryl alcohol, FFA, and lauryl ester fractions.     

Supercritical fluid extraction of fungal oil using CO2, N2O,CHF3 and SF6

The extraction of oil from fungi (Mortierella ramanniana var.angulispora) was studied using carbon dioxide (CO₂), nitrous oxide (N₂O), trifluoromethane (CHF₃) and sulfur hexafluoride (SF₆) under supercritical conditions. The oil solubility was highest in SC-N₂O followed by SC-CO₂, while both SC-CHF₃ and SC-SF₆ showed poorer solvent power. The recorded oil solubilities at 333 K and 24.5 MPa were 2.3 wt% in N₂O, 0.48 wt% in CO₂, 0.0099 wt% in CHF₃ and 0.0012 wt% in SF₆. The oil solubilities in SC-N₂O and SC-CO₂ were measured over the pressure range 15.7–29.4 MPa and at temperatures ranging from 313–353 K. N₂O always showed greater solvent power than did CO₂ at the same temperature and pressure. The solvent power of a supercritical fluid increases with density at a given temperature, and increases with temperature at constant density. The change in neutral lipid composition of the extracted oil with the extraction ratio was measured. Free fatty acids or diglycerides were extracted more easily than triglycerides or sterol esters. The change in fatty acid composition was also measured. The proportion of γ-linolenic acid in the extract remained constant throughout the extraction.     

Preparation of regioisomers of structured TAG consisting of one mole of CLA and two moles of caprylic acid

TAG (MLM) with medium-chain FA (MCFA) at the 1,3-positions and long-chain FA (LCFA) at the 2-position, and TAG (LMM) with LCFA at the 1(3)-position and MCFA at 2,3(1)-positions are a pair of TAG regioisomers. Large-scale preparation of the two TAG regioisomers was attempted. A commercially available FFA mixture (FFA-CLA) containing 9-cis, 11-trans (9c, 11t)- and 10t,12c-CLA was selected as LCFA, and caprylic acid (C₈FA) was selected as MCFA. The MLM isomer was synthesized by acidolysis of acyglycerols (AG) containing two CLA isomers with C₈FA: A mixture of AG-CLA/C₈ FA (1∶10, mol/mol) and 4 wt% immobilized Rhizomucor miehei lipase was agitated at 30°C for 72 h. The ratio of MLM to total AG was 51.1 wt%. Meanwhile, LMM isomer was synthesized by acidolysis of tricaprylin with FFA-CLA: A mixture of tricaprylin/FFA-CLA (1∶2, mol/mol) and 4 wt% immobilized R. miehei lipase was agitated at 30°C for 24 h. The ratio of LMM to total AG was 51.8 wt%. MLM and LMM were purified from 1,968 and 813 g reaction mixtures by stepwise short-path distillation, respectively. Consequently, MLM was purified to 92.3% with 49.1% recovery, and LMM was purified to 93.2% with 52.3% recovery. Regiospecific analyses of MLM and LMM indicated that the 2-positions of MLM and LMM were 95.1 mol% LCFA and 98.3 mol% C₈ FA, respectively. The results showed that a process comprising lipase reaction and short-path distillation is effective for large-scale preparation of high-purity regiospecific TAG isomers.     

Preparation of Aragonite Whiskers

A simple synthetic method for preparing aragonite whiskers has been developed. A suspension of CaCl₂-MgCl₂-Mg(OH)₂ with pH ∼9 has been prepared by adding Ca(OH)₂ to MgCl₂ aqueous solution. CaCO₃ whiskers (aragonite phase) have been prepared easily by blowing CO₂-containing gas into the suspension. The whiskers have high aspect ratios ranging from 20 to 80 with diameters of 0.5–1 μm .     

Sterols,methylsterols, and triterpene alcohols in threeTheaceae and some other vegetable oils

The unsaponifiables from threeTheaceae (Camellia japonica L.,Camellia Sasanqua Thunb., andThea sinensis L.) oils and alfalfa, garden balsam, and spinach seed oils and shea fat were separated into four fractions: sterols, 4-methylsterols, triterpene alcohols, and less polar compounds by thin layer chromatography. While the sterol fraction was the major one for the unsaponifiables from alfalfa and spinach seed oils, the triterpene alcohol fraction was predominant for the unsaponifiables from all other oils. The sterol, 4-methylsterol, and triterpene alcohol fractions were analyzed by gas chromatography. All the sterol fractions were alike in their compositions, consisting exclusively of Δ⁷-sterols, such as α-spinasterol and Δ⁷-stigmastenol as predominant components together with Δ⁷-avenasterol and 24-methylcholest-7-enol. Obtusifoliol, gramisterol (occasionally accompanied with cycloeucalenol), and citrostadienol, together with several other unidentified components, were found in the 4-methylsterol fractions from all of the oils except shea fat. The 4-methylsterol fraction from shea fat showed a characteristic composition containing a large proportion of unidentified components which had relative retention time greater than that of citrostadienol, while no citrostadienol was detected. β-Amyrin, lupeol, and butyospermol were major components of the triterpene alcohol fractions from most of the oils, but the fraction from spinach seed oil contained cycloartenol and 24-methylene-cycloartanol as predominant components. There is a close similarity in the compositions of unsaponifiables (sterols, 4-methylsterols, and triterpene alcohols) of the threeTheaceae oils. Two sterols, α-spinasterol and Δ⁷-stigmastenol, and five triterpene alcohols were isolated from tea seed oil. Moreover, five unidentified components beside parkeol, butyrospermol, α-amyrin, and lupeol were isolated from the triterpene alcohol fraction of shea fat.     

Additional kernel observer: privilege escalation attack prevention mechanism focusing on system call privilege changes

International Journal of Information Security - Cyberattacks, especially attacks that exploit operating system vulnerabilities, have been increasing in recent years. In particular, if administrator...     

MQL深孔钻削中关键因素的最适化研究

采用了微量润滑技术的钻削在长距或小孔径的条件下有必要对所供给的油雾和压缩空气进行最佳化分析.本文首先对切削变形与切削热分布的总能量进行了分析,并在把普通钻削过程中油雾假设为稳态可压缩绝热紊流状态的假设条件下,通过分析得到油膜厚度、气流速度、压缩空气温度和刀具平均温度等重要影响参数的相互关系.最后,给出微量润滑钻削条件下,切削过程中所需的油膜和压缩空气的最佳容量.     

不锈钢在扭转/拉伸复合载荷下近门槛值的疲劳裂纹扩展行为

研究了带环状预裂纹的奥氏体不锈钢圆棒试样在循环扭转／拉伸复合载荷下，门槛值附近的疲劳裂纹扩展行为，分析了复合加载时不同载荷比对裂纹扩展的影响，对裂纹扩展的初始阶段进行了详细研究，用应力强度因子表征了裂纹扩展开始的门槛值．提出了椭圆方程表达的疲劳裂纹扩展开始的门槛值模型，该方程可在裂纹尖端位移准则的基础上导出．疲劳裂纹扩展停止的门槛值条件也可用椭圆方程表达．