Preparation of fatty 3,5-disubstituted isoxazole compounds from FA esters

Long-chain fatty compounds containing an isoxazole heterocyclic ring system substituted at the 3- and 5-ring positions were prepared in moderate to good yields (40–64%) in one pot by condensing FA esters such as methyl palmitate, stearate, oleate, or linoleate with the lithiated anion of N-(isopropylidene)isopropylamine followed by dehydrative cyclization. This approach allows readily available FA esters to be utilized and incorporated into the construction of the isoxazole ring system. These novel products were isolated then characterized by NMR, IR spectroscopy, GC-MS, and m.p. Mass spectra of the fatty isoxazole compounds, derived utilizing EI ionization, showed distinctive cleavage patterns that occurred uniformly along the fatty alkyl chain allowing the position of double bonds to be readily located. Two prominent ions at m/z 97 and 110 were common to all the fatty isoxazole compounds examined and were presumably from a McLafferty rearrangement and a cyclization displacement reaction, respectively.     

Effect of Spray-Dried Flavonoid Microparticles on Oxidative Stability of Methyl Linoleate as Lipid Model System

Microencapsulated quercetin (Q) and epicatechin (E) were prepared by spray-drying using inulin (IN) as encapsulating agent (Q–IN and E–IN) as well as with Capsul (C) as channelizing agent (Q–IN–C and E–IN–C). Microparticles were added to methyl linoleate (ML) and results showed that Q microparticles markedly improved its oxidative stability by increasing the induction period values and delaying the formation of oxidation compounds, as determined by high-performance size-exclusion chromatography, with respect to E microparticles, thus suggesting the importance of flavonoid C-ring substitution. Remaining levels of Q in the lipid system throughout oxidation of ML added with Q microparticles seemed to show two releasing zones: the first one corresponds to the equilibrium zone, when Q released from microparticles replaces Q that is being degraded; the second zone corresponds to the degradation of Q, when the release rate of the encapsulated Q is slower than its degradation rate. In contrast, E microparticles showed only one zone corresponding to the release of surface E. The end of the induction period was in line with the exhaustion of Q and E and the initiation of formation of advanced oxidation products (polymers). In conclusion, Q microparticles have a potential application to extend the shelf-life of lipid matrixes.     

Natural polyphenols as chain‐breaking antioxidants during methyl linoleate peroxidation

A technique based on monitoring oxygen consumption was applied to study 11 natural and model polyphenols (PP, QH₂) as well as four typical monophenolics as a chain‐breaking antioxidant during the controlled chain oxidation of methyl linoleate (ML) in bulk at 37°C. The antioxidant activities of QH₂ were characterized by two parameters: the rate constant k₁ for reaction of QH₂ with the peroxy radical ${\rm LO}_{2}^{{\bf .}} $ : (i) QH₂ + ${\rm LO}_{2}^{{\bf .}} $ → ${\rm QH}^{{\bf .}} $ + LOOH and the stoichiometric factor of inhibition, f, which shows how many kinetic chains may be terminated by one molecule of QH₂. The rate constant k₁ were reduced significantly by factor of 4 –28 as compared to these determined during the oxidation of styrene in bulk; the effect was typically more pronounced for catechol derivatives than for pyrogallol derivatives. At the same time, f for QH₂ was found to be close to two independent of the number of active OH groups, similar to that determined earlier during the inhibited oxidation of styrene. The formation of H bond between OH group of QH₂ and carboxyl group of ML is suggested as a reason for reducing effect of ML on k₁. Practical applications : This work reports rate constants for the reaction of lipid peroxyl radical with phenolics and stoichiometric coefficient of inhibition, which characterize the antioxidant activity (AOA) of 15 natural and model PP, QH₂ during the controlled peroxidation of ML. The reactivity of PP, QH₂ during the oxidation of ML is routinely lower than the reactivity during the oxidation of non‐polar model hydrocarbons. This information may be useful to estimate the AOA of natural PP, QH₂ in real systems of practical significance including plant oils, fats, food‐stuffs, biological objects, and similar.     

共轭亚油酸钠胶束的自交联行为研究

以高纯度天然亚油酸为原料,通过碱催化异构化反应制得一种阴离子可聚合脂质——共轭亚油酸钠。在水溶液中使共轭亚油酸钠分子自组装成球状胶束,再经自由基引发剂引发胶束内部共轭亚油酸钠分子间自交联反应,最终获得共轭亚油酸钠的球状自交联胶束。探索了引发剂种类和用量、反应时间和温度等因素对共轭亚油酸钠分子自交联程度的影响,并采用TEM技术直观表征所获自交联组装体的形貌。结果表明,以过硫酸铵为引发剂,80℃下使pH=13的共轭亚油酸钠水溶液交联反应10 h可以得到平均粒径为20 nm的球状自交联胶束,这是一种潜在的稳定性纳米药物载体或微反应器。     

Antioxidative potential of cashew phenolics in food and biological model systems as affected by roasting

The effect of different roasting conditions on antioxidant capacity of phenolics of cashew nuts and their testa was evaluated using several food and biological model systems. Total phenolic content (TPC) of cashew extracts was determined and accelerated oxidative stability of stripped corn oil in the presence of cashew extracts evaluated. In addition, the antioxidant activity of the extracts was assessed in a β-carotene-linoleate and a cooked comminuted pork model system. Inhibition of oxidation of human low density lipoprotein (LDL) cholesterol and stand breaking of supercoiled deoxyribonucleic acid (DNA) was also investigated. The TPC ranged from 5 to 791 mg gallic acid equivalents/g crude extract. In general, whole cashew nuts and testa extracts demonstrated stronger antioxidant activity than that of the cashew kernel. The inhibition percentage of LDL cholesterol oxidation, as evaluated by conjugated dines formation, of cashew kernels was higher than that of testa and was 69% at the end of 24 h incubation. Extracts of roasted cashew nut showed considerable antioxidative efficiency in model systems employed in this study, however, the effect was not significantly (P ? 0.05) different from that of their raw counterparts, except for the accelerated oxidative stability assay. The results suggest that whole cashew nut and testa extracts could be used as a potential source of natural antioxidants in certain food applications and for disease risk reduction.     

Formation of headspace volatiles by thermal decomposition of oxidized fish oilsvs. oxidized vegetable oils

To understand the reasons for differences in oxidative stability among edible oils, the temperature dependence was investigated for the development of volatile lipid oxidation products in fish oils and in vegetable oils. A rapid headspace capillary gas chromatographic method was developed to determine volatile oxidation products of omega-6 (n-6) polyunsaturated fats (pentane and hexanal) and omega-3 (n-3) polyunsaturated fats (propanal) at different decomposition temperatures. Headspace gas chromatographic analyses of partially oxidized menhaden, bonita and sardine oils could be performed at 40°C, whereas soybean, canola, safflower, high-oleic sunflower and high-oleic safflower oils required temperatures greater than 100°C. Volatile formation by thermal decomposition of oxidized oils had lower apparent activation energies in fish oils than in vegetable oils, and significantly higher apparent activation energies in high-oleic oils than in polyunsaturated oils. The activation energy data on headspace volatiles provided another dimension toward a better understanding of the thermal stability of flavor precursors in unsaturated fish and vegetable oils. Presented at the ISF/AOCS joint meeting, Toronto, Canada, May 10–14, 1992.     

Effects of sesamol, sesamin, and sesamolin extracted from roasted sesame oil on the thermal oxidation of methyl linoleate

This study investigated the effects of lignan compounds extracted from roasted sesame oil, which were sesamol, sesamin, and sesamolin, on oxidation of methyl linoleate (ML) during heating. These compounds were added at 500 or 1000 mg/kg to ML, and α-tocopherol was used as a reference antioxidant. The ML added with lignans or α-tocopherol was heated at 180 °C for 60 min. Thermal oxidation of ML was evaluated by conjugated dienoic acid (CDA) contents, p-anisidine value (PAV), and ML retention. Contents changes of lignan compounds or α-tocopherol in ML during heating were monitored by high-performance liquid chromatography. CDA contents and PAV of samples increased and ML decreased with heating time at 180 °C. Samples added with lignan compounds showed lower CDA contents and PAV but higher ML retention than samples without lignan compounds. The antioxidant activity of sesame oil lignan compounds in ML oxidation during heating tended to be higher than that of α-tocopherol. The contents of lignan compounds in samples decreased with heating time due to their degradation, but the degradation rates were lower than that of α-tocopherol. This study suggested that sesame oil lignan compounds be used as antioxidants in oil at high temperatures for deep-fat frying due to their higher effectiveness and stability than α-tocopherol.     

植物乳杆菌ZS2058中亚油酸异构酶的定位研究

植物乳杆菌ZS2058是本实验室从泡菜中筛选到的一株具有亚油酸异构酶活性的乳酸茵.本文对植物乳杆茵ZS2058中亚油酸异构酶的部分粗酶性质进行了考察,建立了初酶活性检测方法,在此基础上对此亚油酸异构酶在细胞中的定位进行了研究,这将为后续分离纯化此亚油酸异构酶提供理论依据与指导.考察的结果是超声波破碎获得亚油酸异构酶初酶液的最佳条件为破碎功率400W,破碎时间7.5min(破碎5s,间歇9s).初酶活性测定时的最适亚油酸底物浓度为0.08 mg/mL;EGTA等金属螯合剂及Ca2+对亚油酸异构酶活性的影响均不显著;粗酶液经超高速离心分级沉淀和加入去垢剂Triton X-100提取的实验结果表明,该亚油酸异构酶为细胞膜结合酶.     

两种乳酸杆菌超声破碎提取亚油酸异构酶条件的研究

本文利用超声波对两种乳酸杆菌细胞进行破碎,以提取细胞中的亚油酸异构酶,并就超声波破碎条件对亚油酸异构酶释放的影响进行了研究。通过单因素试验和正交试验得出嗜酸乳杆菌的最佳超声破碎条件为:间歇破碎次数80次(每次破碎3s,中间间隔4s),破碎菌液体积50ml,菌悬液浓度20g/60ml,破碎时的抽提缓冲液最佳pH值4.0,NaCl浓度0.2mol/L;保加利亚乳杆菌的最佳超声破碎条件为:间歇破碎次数80次(每次破碎3s,中间间隔4s),破碎菌液体积60ml,菌悬液浓度15g/50ml,破碎时的抽提缓冲液最佳pH值4.8,NaCl浓度0.3mol/L。