高效液相色谱法测定共轭亚油酸甘油酯

正共轭亚油酸甘油酯产品是以红花籽油为原料,通过共轭化反应将其中的亚油酸转化成共轭亚油酸[1-2],然后与甘油进行酯化反应,生成共轭亚油酸甘油酯[3-4]。卫生部2009年第12号公告批准其作为新资源食品,可以直接服用或者添加到脂肪、食用油和乳化脂肪制品中。目前,国内外对共轭亚油酸甘油酯的研究大多集中在制备、萃取和合成方面[5]。而共轭亚油酸甘     

高效液相色谱法测定共轭亚油酸甘油酯北大核心CSCD

共轭亚油酸甘油酯产品是以红花籽油为原料,通过共轭化反应将其中的亚油酸转化成共轭亚油酸[1-2],然后与甘油进行酯化反应,生成共轭亚油酸甘油酯[3-4]。卫生部2009年第12号公告批准其作为新资源食品,可以直接服用或者添加到脂肪、食用油和乳化脂肪制品中。目前,国内外对共轭亚油酸甘油酯的研究大多集中在制备、萃取和合成方面[5]。     

共轭亚油酸制备方法的研究进展

依据反应机理和原料对具有生理活性的共轭亚油酸的制备与纯化方法进行了综述。详细讨论了共轭多烯酸(尤其是共轭亚油酸)的合成方法的研究进展，依据目标产物的收率、纯度及成本对合成或制备方法进行了比较和评价。     

酶催化合成共轭亚油酸甘油酯的溶剂效应

研究了以共轭亚油酸(CLA)和甘油为原料,利用脂肪酶Novozym 435在异辛烷和无溶剂两种反应体系中采用直接酯化法催化合成共轭亚油酸甘油酯,并探讨了温度和时间对溶剂效应的影响.结果表明:在65℃,n(甘油):n(CLA)=2:1,酶添加量为体系总质量的1%的条件下,反应24 h后,不同反应体系中共轭亚油酸的转化率相近,分别为83.44%和88.24%,而所得共轭亚油酸甘油酯的组成有显著差别,分别形成W/O型和O/W型微乳液,前者以单甘酯和二甘酯为主产物,后者以三甘酯为主产物.     

中空纤维两相液相微萃取技术用于芝麻中共轭亚油酸的测定

基于中空纤维两相液相微萃取提取新技术,建立了芝麻中共轭亚油酸的液相微萃取/高效液相色谱测定的新方法。通过研究萃取剂pH值、萃取时间和搅拌速率的影响,确定了最优化的液相微萃取条件:pH11.0的KOH溶液为萃取剂,萃取时间为30 min,搅拌速率为1 000 r/min。采用高效液相色谱法对共轭亚油酸进行定性和定量测定,结果表明,该方法的线性范围宽,相关系数(r2)为0.993,检出限(S/N=3)为17μg/L,相对标准偏差(n=6)为4.9%,共轭亚油酸的富集倍数为12.4倍。用于3种不同品牌芝麻中共轭亚油酸的分析,回收率为81.4%～94.8%。本法为植物中共轭亚油酸的分析检测提供了一种简捷有效的方法,可为乳品、植物油等其他复杂基质样品中共轭亚油酸的检测提供有效参考。     

南瓜子油的气相色谱-质谱分析

黑龙江产白皮南瓜子油脂含量约为27％，从提取的南瓜子油中检测出大量的共轭亚油酸、磷脂、角鲨烯、环烷烃、共轭不饱和醛酮、植物甾醇等化学成分，其中植物甾酵的含量约占南瓜子油的1％，能确定结构的甾醇有6种。     

应用QuikPrep HSCCC系统实现共轭亚油酸及其异构体的分离

综述了高速逆流色谱(HSCCC)技术的原理,溶剂系统选择原则,影响因素以及应用范围,并应用该技术对共轭亚油酸(CLA)异构体进行分离。发现HSCCC可以对CLA实现高度的纯化。     

毛细管气相色谱法测定乳脂中的cis-9,trans-11-共轭亚油酸

建立了测定乳脂中cis-9, trans-11-共轭亚油酸(CLA)的毛细管气相色谱方法。样品经正己烷-异丙醇提取、甲醇-甲醇钠甲酯化后,进行气相色谱分析;采用程序升温,以保留时间定性,外标法定量。采用该方法测得共轭亚油酸的回收率为100.26%,相对标准偏差（RSD）为1.9%(n=6),检测限为1 mg/L。该方法样品用量少,前处理简单,建立的实验条件准确可靠,不仅可以用来测定cis-9,trans-11-CLA的含量,而且对于乳制品中所含的其他脂肪酸的分析测定也具有指导意义。     

聚共轭亚油酸基网状纳米金的制备及表面增强拉曼散射和催化性能

以天然不饱和脂肪酸共轭亚油酸(CLA)为绿色单体, 通过简单的分子自组装和可控自交联反应制备聚共轭亚油酸(PCLA)聚集体. 透射电子显微镜(TEM)结果显示, PCLA聚集体的形貌呈现独特网状结构, 其联结单元为来自于CLA胶束的膨大颗粒. 采用氯金酸在极性聚合物表面原位还原, 2 d后在网状PCLA基底上制备得到以CLA胶束为核(20 nm)的网状纳米金结构, 而且网状PCLA的原位还原作用与模板作用相结合是获得PCLA基网状纳米金的充分必要条件. 与普通球形胶态金纳米颗粒[(5±1) nm]相比, PCLA基网状纳米金对苯硫酚具有更好的表面增强拉曼散射(SERS)效应, 对对硝基苯酚具有更好的催化还原效果.     

有序介孔Ru-MgZr复合氧化物合成及催化亚油酸异构化性能

筛选高效、高选择性多相催化剂异构化亚油酸是共轭亚油酸(CLA)研究的重点。 本文采用溶剂挥发自组装改进的溶胶-凝胶法,合成有序介孔Ru掺杂的MgO-ZrO₂固体碱催化剂。 考察了催化剂中不同Mg物质的量对催化剂孔径、比表面积和表面碱性以及Ru等的结构和性能对催化性能的影响。 对比了催化剂的形貌、表面碱性及Ru组分对催化性能的影响程度。 结果表明,n(Zr)∶n(Mg)=3∶1时,Ru掺杂的MgO-ZrO₂固体碱催化剂具有高度有序的介孔结构和高的比表面积。 而n(Zr)∶n(Mg)=1∶1时, MgO-ZrO₂固体碱催化剂合成CLA产率较高,反应时间4 h,产率达到85%,催化效率为0.099 g(CLA)·L^-1(solvent)·min^-1,并且催化产物主要为具有生物活性的3种共轭亚油酸异构体。 催化剂的强碱性位点和晶格Ru是催化异构化反应的两个活性位点,强碱性位点是提高催化性能的关键。 固体碱复合氧化物催化效率高、制备方法简单、反应产物生物活性高等优点,具有较好的应用前景。     

Conjugation of linoleic acid over a hydrogen pre-activated heterogeneous catalyst

Development of a new heterogeneous catalytic pathway for isomerization of linoleic acid to conjugated linoleic acids at mild reaction conditions over Ni/H-MCM-41 in a soluted system.     

Identification of radicals spin-trapped in autoxidized linoleic acids: A high performance liquid chromatography and electron spin resonance study

Radicals generated in linoleic acid and deuterated linoleic acid have been trapped by the spin trap 2-methyl-2-nitroso-propane (MNP) and identified by electron spin resonance (ESR) and ENDOR spectroscopy. The formation of two distinct secondary alkyl radical adducts (one conjugated, the other non-conjugated, as shown by their UV absorption spectra) was demonstrated by 11, 11-dideuterio-9-cis-12-cis-linoleic acid using HPLC and ESR spectroscopy.     

Polyunsaturated but not conjugated linoleic acid supplementation of leukemic U937 cells can act as an amplification factor for photofrin-mediated photodynamic therapy

Polyunsaturated fatty acids located in leukemia cell membranes are excellent targets for peroxidation. They can significantly enhance the effectiveness of Photofrin-mediated photodynamic therapy (PDT)-induced cell killing. In this study, the peroxidizability of conjugated fatty acid isomers (9c,11t-linoleic acid and 9c,11c-linoleic acid) and polyunsaturated fatty acids (PUFAs; linoleic acid, gamma-linolenic acid and arachidonic acid) with 2,2'-azo-bis(2-amidinpropane)dihydrochloride, soybean lipoxygenase and photomediated peroxidation are compared with each other. Peroxidation was determined using different methods: by means of gas chromatography to estimate the fatty acid (FA) consumption, by photometry for the level of FA peroxides or phospholipid peroxides and by definition of the content of malondialdehyde for thiobarbituric acid reactive substances (TBARS). The results suggest that the generation of oxidation products from individual FAs indicate a different formation rate of oxidation products. Radical FA peroxides were produced most by polyunsaturated arachidonic acid, followed by linoleic acid and gamma-linolenic acid, whereas conjugated FA isomers did not generate peroxides. Accordingly, the levels of lipid peroxides and TBARS were substantially increased after incorporation and oxidation of polyunsaturated FAs into U937 cells and could significantly enhance the effectiveness of Photofrin-PDT-induced cytotoxicity. The results showed that PUFA, but not conjugated FA supplementation of U937 cells, can act as a PDT amplification factor.     

Involvement of type I and type II mechanisms in the linoleic acid peroxidation photosensitized by tiaprofenic acid

Analysis of the photomixtures resulting from irradiation of aqueous solutions of linoleic acid sensitized by tiaprofenic acid (TPA) or its major photoproduct (DTPA) by HPLC has shown the formation of all the four possible conjugated dienic hydroperoxides. According to laser flash photolysis experiments the rate constants for hydrogen abstraction from linoleic acid by the excited triplet states of TPA and DTPA are 2 x 10(5) and 3.2x 10(5) M(-1) s(-1), respectively. These data, together with the known rate constants for oxygen quenching of triplet (D)TPA and for the reaction of singlet oxygen with linoleic acid, show that the mechanism is mixed type I/type II. Finally, typical radical scavengers such as BHA and singlet oxygen quenchers such as DABCO and sodium azide are efficient quenchers of the triplet excited state of DTPA. This shows the risk of assigning mechanisms based on indirect 'evidences' using 'specific' additives.     

Influence of Mg/Al Molar Ratio on the Structures and Properties of Ru-Mg Alx Catalysts for Isomerization Linoleic Acid

With the knowledge on the significant effect of basic site and Ru on the catalytic performance of heterogeneous catalysts in the isomerization of linoleic acid to conjugated linoleic acid,a series of Ru-Mg Alx compounds with different basicity have been prepared by controlling the Mg/Al molar ratio. The results showed the catalysts with different basicity markedly influence the structure,the Ru dispersion,properties and catalytic performances for the isomerization reaction. The strong basic site is conductive to the high yield of CLA products. The strong basic site and the well-dispersion RuO_2 synergetic catalysis for the isomerization reaction,basic site and the well-dispersion RuO_2 synergetic effect are possibly via a Mg-O-Ru linkage.     

Gas chromatography and silver-ion high-performance liquid chromatography analysis of conjugated linoleic acid isomers in free fatty acid form using sulphuric acid in methanol as catalyst

This study used GC and silver-ion HPLC to examine the effects of temperature and time on methylation of individual and mixtures of conjugated linoleic acid (CLA) isomers in free fatty acid form using sulphuric acid as catalyst. In the conditions tested (temperatures between 20 and 50 degrees C and times between 10 and 60min) methylation was complete while avoiding isomerization of conjugated dienes and the formation of artefacts that could interfere with chromatographic determinations. An analytical method using solvent extraction of the lipids followed by selective elution of the free fatty acids from aminopropyl bonded phase columns and methylation with H(2)SO(4) in mild conditions was then applied to determine the CLA isomers in free fatty acid form in rumen fluid, and the results were evaluated.     

Linoleic Acid Isomerase from <Emphasis Type="Italic">Propionibacterium acnes</Emphasis>: Purification,Characterization, Molecular Cloning,and Heterologous Expression

Propionibacterium acnes strain ATCC 6919 catalyzes the isomerization of the double bond at the C9 position in linoleic acid (c9,c12, 18:2) to form t10,c12 conjugated linoleic acid (CLA, 18:2). CLA has significant health benefits in animal and human. The linoleic acid C9 isomerase was purified to an apparent homogeneity by successive chromatography on diethylaminoethyl (DEAE) anion exchange, hydrophobic interaction, and chromatofocusing columns. Two degenerated oligonucleotide primers were synthesized according to the N-terminal peptide sequence to clone, by polymerase chain reaction (PCR), a short nucleotide sequence (62 bp) of the isomerase gene. The linoleic acid isomerase gene (lai) was subsequently cloned by inverse PCR. The amino acid sequence deduced from the lai coding sequence predicts a protein of 424 amino acid residues (48 kDa), excluding the N-terminal methionine, which was absent in the polypeptide purified from the native host. The isomerase shares no significant sequence homology to other enzymes except a flavin-binding domain in the N-terminal region. The recombinant isomerase purified from Escherichia coli showed a typical ultraviolet spectrum for FAD-bound proteins. The recombinant enzyme produced a single isomer of t10,c12-CLA from linoleic acid, as demonstrated by gas chromatography and gas chromatography-mass spectrum analysis. The recombinant isomerase protein was expressed at high levels in E. coli, but it was almost totally sequestered in inclusion bodies. The level of active isomerase was increased 376-fold by medium and process optimization in bench-scale fermentors.     

GC Analysis of the Fatty Acid Composition of Yak Kidney

To obtain valuable information for development of potential commercial products from yak kidney, which is usually treated as waste, the fatty acid composition of kidneys from yak reared in Gansu province, China, was investigated by gas chromatography. Fifteen different fatty acids were identified. The major fatty acids are oleic acid (33.3%), stearic acid (20.2%), and palmitic acid (18.4%). More interestingly, several important and essential fatty acids were also identified, including conjugated linoleic acid (2.94%), omega-3 fatty acids, for example docosahexaenoic acid (1.47%), eicosapentaenoic acid (1.11%) and alpha linolenic acid (0.37%), and omega-6 fatty acids, for example arachidonic acid (2.86%) and linoleic acid (1.98%). The results show that the fatty acid composition of yak kidney is of reasonable value and is suitable for further development of possible commercial products. This is the first report of the fatty acid profile of yak kidney.