Functional group analysis during ozonation of sunflower oil methyl esters by FT-IR and NMR

Ozonation of neat sunflower oil (SFO) methyl esters was monitored by FT-IR and 1H and 13C NMR spectroscopy. During the early stage of ozonation, ozone absorption was essentially quantitative. This was accompanied by the formation of 1,2,4-trioxolane. IR and NMR spectra of ozonated samples showed that scission of ozonide to give aldehyde were minimal. 1H NMR analysis revealed that the amount of ozonide relative to aldehyde was more than 90% regardless of the extent of ozonation. Complete ozonation was attained after supplying around 0.20 g O3/ml methyl ester after which ozone absorption suddenly dropped to around 25%. At the latter part of ozonation, ozonide and aldehyde reacted with excess ozone to give carboxylic acid. Reaction products were identified according to Criegee mechanism.     

Nondestructive analyses of unsaturated fatty acid species in dietary oils by attenuated total reflectance with Fourier transform IR spectroscopy

The aim of this study was to develop a nondestructive method to quantitate relative amounts of n-3 and n-6 polyunsaturated fatty acid (PUFA) species in vegetable oils and oil seeds using Fourier transform IR spectroscopy (FTIR). The alkene Cbond;H stretching vibrations of unsaturated fatty acids in oils showed IR absorption bands with various peak positions and intensities at around 3010 cm(-1), depending on the extent of unsaturation and PUFA species. With the aid of partial least-squares regression analysis, the FTIR measurement could practically predict the content of each PUFA species in the oil to be tested. A calculation method was also presented to directly find PUFA species in oils from the FTIR spectra. This technique was applied to dried soybean seeds to demonstrate a nonhomogenous distribution of saturated fatty acids and PUFAs, as well as glycans, in soybean cross sections.     

Influence of exogenous natural oils on the omega-1 and omega-2 hydroxy fatty acid moiety of sophorose lipid produced by Candida bombicola

Candida bombicola can synthesize monohydroxy fatty acid as a moiety of sophorose lipids. The hydroxy fatty acids contained in a major lactone were identified by GC-MS, after culturing with natural oils such as coconut, rapeseed, olive, and soybean oils. Hydroxy fatty acids of C18 and C16 were always synthesized, but differences were observed among the oils regarding the positions of hydroxyl groups, unsaturation, and composition of the fatty acids. A new C17 hydroxy acid was found without addition of oil.     

Influence of Exogenous Natural Oils on the ω-1 and ω-2 Hydroxy Fatty Acid Moiety of Sophorose Lipid Produced by Candida bombicola

Candida bombicola can synthesize monohydroxy fatty acid as a moiety of sophorose lipids. The hydroxy fatty acids contained in a major lactone were identified by GC-MS, after culturing with natural oils such as coconut, rapeseed, olive, and soybean oils. Hydroxy fatty acids of C18 and C16 were always synthesized, but differences were observed among the oils regarding the positions of hydroxyl groups, unsaturation, and composition of the fatty acids. A new C17 hydroxy acid was found without addition of oil.     

薏苡仁油脂的微商热重分析

本文采用热重法比较了薏苡仁油与豆油的稳定性差异.结果表明,热稳定性及氧化稳定性顺序为氢化薏苡仁油>混合薏苡仁油>精炼薏苡仁油>精炼豆油,这主要取决于各自脂肪酸的组成.微商热重法简便、灵敏,还可用于鉴别薏苡仁油质量.     

高含游离脂肪酸的香果树籽油制备生物柴油的方法

目前生物柴油因其环保和可再生利用资源的特性备受关注。多数生物柴油是通过甲醇和碱催化食用油得到的,而大量非食用油也可以制备生物柴油。本文报道用高含游离酸脂肪油快速高效低成本制备成其单酯的二步法工艺。先用1% H2SO4以少于1.5%量对甲醇和云南特产香果树（Lindera communis）籽的粗原料油以10∶1摩尔比组成的混合液酸催化酯化游离脂肪酸;之后再对醇和得到的油脂产品按摩尔比15∶1的混合液碱催化转化为单甲酯和甘油。本方法是一个直接甲脂化制备生物柴油的工艺简洁、降低成本的新技术。文中还讨论了该工艺影响转化效率的主要因素,如摩尔比,催化量,温度,反应时间和酸度。香果树生物柴油不重蒸,而其生物柴油的主要特性,如粘度、热值、比重、闪点、冷滤点等与生物柴油标准的匹配度,也做了报道,研究结果将为香果树生物柴油以非重蒸油料制备生物柴油产品,作为潜在的柴油燃料替代产品提供技术支撑。     

Physicochemical properties of cold pressed sunflower,peanut, rapeseed,mustard and olive oils grown in the Eastern Mediterranean region

Fatty acid composition and stability of vegetable oils have taken more attention as an essential source of biologically active compounds in a good balanced diet. The purpose of the study was to determine peroxide value, free fatty acids, unsaponifiable matter, total carotenoid content, iodine value and fatty acid composition of sunflower, rapeseed, mustard, peanut and olive oils. Rapeseed and peanut oils had the highest peroxide values, while sunflower oil had the lowest peroxide values. The free fatty acid value of the tested oils varied between 0.43 and 1.36% oleic. The peanut oil had the highest free acid value and the mustard oil had the lowest one. Total carotenoid contents of mustard and rape seed oil were higher than those of the other oils tested. Palmitic acid (C16:0), oleic acid (C18:1) and stearic acid (C18:0) were the common main fatty acid components of the vegetable oils tested. Followed by linoleic acid, the amount of oleic acid was the highest among other fatty acid components. Mustard oil had the highest erucic acid (C22:1) with the amount of 11.38%, indicating that it cannot be used for human consumption. Among the oils investigated, sunflower and mustard oils were more stable than rapeseed, peanut and olive oils.     

Degradation of polysaccharides and lignin in wood ozonation

Ozonation has been considered as a method for the pretreatment of plant biomass to obtain cellulose and monosaccharides. Ozone consumption by aspen wood with various moisture contents has been investigated. We have considered the gradual transformation of the substrate: wood to ozonated wood to cellulose-containing product (CP) to holocelluloze (HC) and to cellulose. Yields of ozonated wood (OW), the (CP), water-soluble ozonation products, HC, and cellulose have been determined. The lignin content in the CP has been estimated. Both HC and cellulose samples have been studied by IR spectroscopy. The degree of polymerization and molecular mass distribution of cellulose obtained from ozonated wood have been determined. It has been shown that wood destruction by ozone is accompanied by degradation of lignin, hemicelluloses, and cellulose.It has been found that physicochemical properties of cellulose obtained from ozonated wood can be regulated by the variation of the initial moisture content in the substrate. Both molecular ozone and radical species, which are generated in the course of ozone reactions with water present in the substrate structure, participate in wood destruction.     

Synthesis and characterization of polyacids from palm acid oil and sunflower oil via addition reaction

In this study aliphatic polyacids were synthesized using palm acid oil (PAO) and sunflower oil (SFO) via addition reaction technique. The synthesized materials were characterized using Fourier-transform infra-red (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-ToF-MS) and thermo-gravimetric analysis (TGA). Mixing formic acid and hydrogen peroxide with PAO or SFO at the ratio 3:10:1 produced the lowest iodine value of 10.57 and 9.24 respectively, indicating the increase in epoxidization of both oils. Adding adipic acid to the epoxidized oils at a ratio of 1:10 increases the acid values of SFO and PAO to 11.22 and 6.73 respectively. The existence of multi-acid groups present in synthesized polyacid was confirmed by MALD-ToF-MS. This feature indicates a possible value to the biomaterials development.     

我国大豆油、花生油、芝麻油的甘油三酯组成研究

应用高效液相色谱技术,分离分析大豆油、花生油、芝麻油的甘油三酯组成,测试表明,大豆油的主要甘油三酯为LLL、LLO、LLP、OLO和PLO;花生油的主要甘油三酯为OLO、LLO、PLO;芝麻油的主要甘油三酯为LLO、OLO、POO和LLL。     

Estimation of biological kinetic parameters from an analysis of the BOD curve of waste waters–effects of a chemical preoxidation

Urban waste waters were treated with pure ozone or combinations of ozone, hydrogen peroxide and/or UV radiation to study the course of resulting BOD (biological oxygen demand)-time profiles and to propose a kinetic model. BOD-time profiles of chemically treated waste waters show an initial lag period that first order kinetic models cannot describe. A second order kinetic model is then proposed that satisfactorily fits experimental BOD-time profiles, except when hydrogen peroxide has been used. In these cases, BOD-time profiles present the highest lag periods observed. By applying this model, three parameters are determined: the biokinetic constant (k) which is an index of the biological removal rate; the potential amount of biodegradable matter (BOD_T), and the measure of the size of inocula and microbial activities of microoganisms (λ). The model was checked with experimental results of BOD-time profiles corresponding to both untreated and chemically ozonated urban waste waters. Ozonated waste waters showed the highest values of k and BOD_T, which implies an improvement of waste water biodegradability after ozonation. However, values of λ corresponding to ozonated waste waters presented lower values than those of untreated waste waters. This was due to the lag period observed in the BOD-time profile, which was a consequence of a lack of microorganism acclimation to ozonated waste waters. The effect of the ozone does, pH and carbonates during ozonation on COD (chemical oxygen demand) and the above indicated parameters was also studied. There was an optimum ozone dose which was 138 mg/l for this specific system. This led to the highest biodegradable fraction (φ) and the highest biokinetic constant (39% increase in φ and 4.7- fold increase in the value of k, respectively, compared to untreated waste waters.). Another significant fact was that a higher COD reduction was observed in the absence of carbonate during ozonation at basic pH values. In addition, the percentage of variation in the biodegradable fraction (Δφ) of ozonated waste water increased compared to the untreated waste water at acid pH. The results suggest that ozonolysis, the direct molecular ozone way of reaction, due to its selective character, increases the biodegradability of waste water more than other chemically advanced oxidation processes based on hydroxyl radical reactions.     

Synthesis of mixed esters of ascorbic acid using methyl esters of palm and soybean oils

Mixed esters of ascorbic acid were synthesized using methyl esters of palm and soybean oils as acyl donors, in acetone at 50 degrees C, and catalyzed by Novozym 435. A conversion of 62% was obtained with palm oil methyl ester at an ascorbic acid to acyl donor molar ratio of 1:4; the mixed ester contained 45.89% ascorbyl palmitate, 42.59% ascorbyl oleate and 10.1% ascorbyl linoleate. Acylation with soybean oil methyl ester resulted in 17% conversion, yielding a mixed ester containing 10.08% ascorbyl palmitate, 20.68% ascorbyl oleate, and 64.96% of ascorbyl linoleate. The mixed esters of ascorbic acid can find direct use in food and cosmetics.     

Malondialdehyde production and erythrocyte membrane resistance to free radicals, in function of adequate or inadequate protein intake, associated with different oils (sunflower, soybean, coconut, salmon)]

Requirements in polyunsaturated fatty acids (PUFA) of series n-3 and n-6 may be amplified and their metabolism, transport, and utilization may be impaired in the long term, by protein depletion. The aim of this study was to evaluate, in young rats, malondialdehyde (MDA) production and erythrocyte membrane antioxidative defense, when they were fed balanced (20% casein) or depleted (2% casein) protein diet associated with various oils (sunflower, soybean, coconut or salmon). Over a short period (28 days), eight groups of 10 male Wistar rats were fed eight different diets: TOC (20% casein + 5% sunflower oil), TOd (2% casein + 5% soybean oil), SOC (20% casein + 5% soybean oil), SOd (2% casein + 5% soybean oil), COC (20% casein + 5% coconut oil), COd (2% casein + 5% coconut oil), SAC (20% casein + 5% salmon oil), SAd (2% casein + 5% salmon oil). Blood was removed, MDA was assessed in plasma (reaction with thiobarbituric acid). Washed erythrocytes were subjected to organic free radical generator (Kit KGRL 400 Spiral R.D., Couternon, 21560 France). The haemoglobin released was analysed by spectrophotometry. The total anti-radical defense status was expressed as the length of time to reach 50% hemolysis (T 50% in min). Plasma of deficient groups (2% casein) exhibited low concentrations of protein, particularly with coconut and salmon oils; phospholipid and total cholesterol, excepted with diet containing coconut oil; triacylglycerol; and VLDL. Malondialdehyde. In groups fed balanced protein diets, the lowest values were obtained with salmon and coconut oils. MDA contents of groups TOd, COd and SAd were higher than those of their respective control groups, but significantly only in group COd. Antiradical defense status. Total anti-radical defence status in erythrocytes was not modified in the short term by balanced or depleted protein diets which ever oil was used, despite deep changes in fatty acid composition of membrane phospholipids. In particular, phospholipid contents in eicosapentaenoic, docosahexaenoic acids were greatly enhanced by the consumption of salmon oil compared to the values obtained with coconut oil.     

Enhancement of cephamycin C production using soybean oil as the sole carbon source

Vegetable oils were investigated to evaluate their potential to act as the sole carbon source for production of cephamycin C in shake and jar-fermentor cultures. Soybean oil was the best carbon source for cephamycin C production. Bioautography and HPLC analyses showed that cephamycin C was exclusively produced even when soybean oil was used as the sole cabon source. The optimal pH and initial concentration of soybean oil was 7.5 and 7 g/l, respectively. Both pH and the pH-control agent affected cephamycin C production, and among phosphoric acid, acetic acid and sulfuric acid, phosphoric acid was associated with the best production. Soybean oil was slowly consumed after the soluble nitrogen source was consumed. When the initial soybean oil concentration was 7 g/l, cephamycin C production was maximal, 2.0 g/l, which was twice as high as that from starch. The product yield from soybean oil was 4.7 times higher than that from starch. These results show that vegetable oils, which are cheaper than other carbon sources, could be used as the sole carbon source in the production of antibiotics. Correspondence to: M. Okabe     

臭氧处理海水对扇贝卵的孵化及幼虫生长的影响

主要研究了用臭氧处理海水在经过连续充气曝气12、24h、不经充气曝气的处理水及没经臭氧处理的正常海水,进行海湾扇贝、虾夷扇贝受精卵的孵化和幼虫培育实验。结果表明,海湾扇贝受精卵在经过24h曝气的处理水中孵化率最高为92％,其次为没经过处理的正常海水为76％,曝气12h为16％,没经过曝气的为0;虾夷扇贝受精卵在经过24h曝气的处理水中孵化率最高为88%,其次为没经过处理的正常海水为85％,曝气12h为15％,没经过曝气为0。海湾扇贝幼虫培养在没经过处理的正常海水和经24h曝气的处理水中生长较快,曝气12h较慢;虾夷扇贝幼虫则是没经过处理的正常海水生长最快,其次是经24h曝气的处理水,而曝气12h较慢,成活率方面也表现出一定的差异,从而为臭氧处理海水在贝类育苗上的应用提供一定的指导。     

Effect of dietary oils on lipid peroxidation and on antioxidant parameters of rat plasma and lipoprotein fractions.

In order to investigate the influence of fatty acid pattern and antioxidants other than vitamin E on lipid peroxidation and antioxidant levels of plasma very low density and low density lipoproteins (VLDL + LDL), the effects of three diets (equalized for vitamin E) containing soybean oil, olive oil, or an oleate-rich mixture of triglycerides (triolein) were studied in rats. A significantly lower concentration of thiobarbituric acid-reactive substances (TBA-RS) in plasma and lipoproteins was found after the olive oil diet (soybean oil, 3.7 +/- 0.4 nmol/ml; triolein, 2.1 +/- 0.5 nmol/ml; olive oil, 1.5 +/- 0.3 nmol/ml, in plasma) (soybean oil, 0.99 +/- 0.16 nmol/ml; triolein, 0.96 +/- 0.13 nmol/ml; olive oil, 0.38 +/- 0.12 nmol/ml, in the VLDL + LDL fraction). Furthermore, the results from in vitro copper-induced lipid peroxidation, expressed in terms of conjugated dienes, lipid hydroperoxides, and TBA-RS content, showed that VLDL + LDL particles from olive olive oil-fed rats were remarkably resistant to oxidative modification. The results suggest that the fatty acid unsaturation of dietary oils is not the only determining factor of the antioxidant capacity of lipoproteins in this animal model. The maximal protection observed after the olive oil diet may be explained by the presence of other unidentified antioxidants in addition to vitamin E, derived from oil intake. Therefore, the optimal balance between the content of unsaturated fatty acids and natural antioxidants in dietary oils appears to be of major importance.     

Effect of dietary fats on arachidonic acid and eicosapentaenoic acid biosynthesis and conversion to C22 fatty acids in isolated rat liver cells

The desaturation, chain elongation and esterification of [1-14C]eicosapentaenoic acid, [1-14C]arachidonic acid, [1-14C]eicosatrienoic acid, [1-14C]linolenic acid and [1-14C]linoleic acid were studied in isolated liver cells. Rats fed diets with either 15% hydrogenated coconut oil or 15% partially hydrogenated marine oil, both deficient in essential fatty acids, 15% soybean oil or standard pellet diet with 6% fat, were used. The delta 4-desaturation of 22:5(n - 3) and 22:4(n - 6) as well as the delta 6-desaturase activity was distinctly higher in cells from animals fed coconut or marine oil than with soybean oil or standard pellet. The rate of delta 5-desaturation of 20:3(n - 6) and 20:4(n - 3) was nearly the same in cells from rats fed coconut, marine and soybean oils and higher than with standard pellet. The chain elongation of 20:5(n - 3) to 22:5(n - 3) was distinctly more pronounced than the elongation of 20:4(n - 6) with all four diets. 20:5(n - 3) was mainly esterified in the phospholipids with marine and coconut oils, and mainly in triacylglycerol with standard pellet and soybean oils. The proportion of [1-14C]20:4(n - 6) in the phospholipids to that in triacylglycerol decreased in the order marine oil greater than coconut oil greater than standard pellet greater than soybean oil. The different endogenous arachidonic acid content in the phospholipids induced by the different diets increased in the same order. 20:5(n - 3) was rapidly esterified in triacylglycerol and phospholipids, then liberated especially from the triacylglycerol fraction, chain elongated to 22:5(n - 3) and reesterified.     

Observations and experiments on extending shelf-life of 'rockfish' (Sebastes spp.) products with ozone

On a fishing vessel and in the laboratory, trials were undertaken to study the effect of ozonation on rockfish bacteria ( Sebastes spp.) during transport from fishing grounds. At the beginning of the experiment, bacterial loads were the same on ozone-treated and control samples. Fish transported in ozonated water lost some of their bacterial film with surface slime when they were pumped from the boat's hold into the processing plant. Ozonation appears to encourage the detachment of the surface slime and bacterial film by partly oxidizing the excess slime excreted during capture. When ozonated intermittently during transport the fish shelf-life was extended by about 36 h. The same ozonation treatment was simulated in the laboratory which revealed higher bacterial counts on the ozonated fish than on the control samples. Fish used in this trial are believed to have been stored for several days prior to ozonation. This storage may have resulted in changes in the properties of the surface slime, counteracting the effect of ozonation.     

Stimulation of protease production byAspergillus oryzae with oils in continuous culture

Summary The effect of soy sauce oil and various other oils on protease production by Aspergillus oryzae NISL 1913 was studied in chemostat cultures (dilution rate=0.02 h^–1). Soy sauce oil was consumed as a carbon source by the cells and also accelerated protease production. When soy sauce oil was used as sole carbon source, the specific protease production rate was 2.89 protease units·(mg dry weight of mycelium)^–1·h^–1, which was threefold higher than that with starch. The specific protease production rate with linoleic acid, oleic acid, Tween 80 and soybean oil exhibited similar values to that with soy sauce oil but the fatty acids with carbon chains shorter than six, such as caproic acid and acetic acid, did not stimulate protease production. The oils did not cause an increase in other exocellular enzymes such as -amylase, indicating that the protease production was selectively stimulated by the oils. Offprint requests to: Y. Fukushima     

Chemodiversity of Essential Oils from Nine Species of Celastraceae

Extracts and compounds obtained from several species of Celastraceae family are reported as potential sources of drugs due to their diverse pharmacological properties. Nevertheless, essential oil composition from these species is still little known. This work aimed at the analysis of essential oils obtained from different Brazilian Celastraceae species. A total of seventeen oils were obtained using hydrodistillation process and analyzed by gas chromatography/mass spectrometry (GC/MS). Principal component analysis (PCA) allowed the identification of a chemical composition pattern among the analyzed essential oils. Some compounds were more frequent among Celastraceae species, such as cis‐ and trans‐linalool oxide (14/17 oil samples), nerylacetone (13/17), linalool (11/17), β‐ionone (10/17), α‐ionone (9/17), nerolidol (10/17), decanal (10/17), and dodecanoic acid (10/17). These results contribute to the chemophenetics of Celastraceae species.