Oxidation of Methyl Linoleate in Oil-in-Water Micro- and Nanoemulsion Systems

Oxidation of methyl linoleate in O/W emulsions having droplets of median diameters ranging from 17 nm to 8.0 μm was carried out at 40°C. The oxidation process was analyzed on the basis of a kinetic equation of the autocatalytic type. The induction period was found to be shorter and the oxidation rate constant lower for emulsions with smaller oil droplets. The stoichiometry between methyl linoleate and oxygen was observed to be independent of both the size of oil droplet and the type of the surfactant and was found to be unity during the early stage of the oxidation. However, more oxgen was consumed in the oxidation of the methyl linoleate in the later half of the oxidation process.     

Differences in Oxidation Kinetics Between Conjugated and Non-Conjugated Methyl Linoleate

The oxidation kinetics of conjugated methyl linoleate was compared with that of non-conjugated methyl linoleate under mild oxidation conditions (30 °C in the dark). Samples of methyl 9-cis,11-trans-linoleate, methyl 10-trans,12-cis linoleate and methyl 9-cis,12-cis linoleate were assayed separately and in mixtures. For comparative purposes, methyl α-linolenate and methyl oleate were also used. Two complementary analytical approaches were selected to monitor the progress of oxidation, (1) the traditional follow-up of residual substrate by gas liquid chromatography, and (2) an analytical procedure by high-performance size-exclusion chromatography (HPSEC) for direct measurement of the oxidation compounds formed. The HPSEC method enabled us to quantitate oxidized monomers, dimers and polymers concomitantly in a rapid and direct analysis. Results showed that conjugated methyl linoleate samples oxidized later than their non-conjugated counterparts, and showed a very different oxidation pattern. Thus, formation of oxidized monomers was negligible and the first and major compounds formed were polymerization products. Also, under the conditions used, non-conjugated and conjugated methyl linoleate samples in 1:1 mixtures led to decreased oxidation rate of non-conjugated methyl linoleate and increased oxidation rate of conjugated methyl linoleate. This study supports the view that oxidation kinetics of conjugated dienes differ substantially from that of methylene-interrupted dienes.     

Radical-Initiated Reaction of Methyl Linoleate with Dialkyl Phosphites

The addition of dialkyl phosphite (methyl, ethyl and n‐butyl) to methyl linoleate (MeLin) double bonds was investigated. The reaction proved to be more challenging than the analogous reaction with methyl oleate (MeOl), due to inhibition of the radical reaction by the bis‐allylic hydrogens of MeLin and the lower reactivity of MeLin double bonds. However, we demonstrated that this self‐inhibition problem can be solved by simply keeping the MeLin reagent at low concentrations, while keeping the dialkyl phosphite at high concentrations. For optimization of the reaction, four different radical initiators were investigated: dilauroyl peroxide (LP), 2,2′‐azobis(2‐methylpropionitrile) (AIBN), tert‐butyl perbenzoate (t‐BP), and tert‐butyl peroxide (TOOT). The initiators were used at temperatures that provided a half‐life of 10 h: 64, 64, 104, and 125 °C respectively for LP, AIBN, t‐BP, and TOOT. The tests showed the reaction to be faster at higher temperatures, but transesterification of the ester groups was also observed at elevated temperatures. t‐BP was chosen as an optimal initiator for carrying the reaction. The apparent order of reactivity of the dimethyl, diethyl and di‐n‐butyl phosphites (Me >Et >n‐Bu) towards MeLin was due to differences in their molar volumes. When the concentrations of dialkyl phosphite were kept the same, the order reversed (n‐Bu > Et~Me). GC–MS spectra of the resulting phosphonates are reported and the main fragments assigned.     

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.     

1H NMR Study of Methyl Linoleate Ozonation.

Unsaturated fatty acids are essential components of vegetable oils and cellular membranes and the involved aspect of unsaturated fatty acids ozonation have been widely studied by different authors. In this paper, in vitro ozonolysis of unsaturated fatty acids with addition of water or ethanol has been studied by Proton Nuclear Magnetic Resonance (¹H NMR) at 250?MHz in order to explore the possibility of this technique for the detection of Criegee ozonides in characterizing ozone reaction with these substrates. The ozonolysis of methyl linoleate showed that signal intensities from formed ozonides were increased with ozone concentration increments. However, the signal intensities with addition of water were higher than those in ethanol addition. Signal intensities from olefinic double bonds were found to decrease with the increment in ozonide signals. Thus, a correspondence of the behavior of these signals is observed with a proportional rate reaction between the number of double bonds in the substrate molecule. Signals from aldehyde formation were poorly detected at lower ozone concentration. It was concluded that the evaluation of ozonide and olefinic double bond signals from 250?MHz ¹H NMR can be a useful tool in assessing ozone reaction with biomolecules. The reaction mechanism for the ozone reaction with unsaturated fatty acids in the presence of water or ethanol is analyzed.     

碱法异构化亚油酸甲酯制备共轭亚油酸

该文探索在乙二醇溶剂中以氢氧化钠碱法异构化亚油酸甲酯制备共轭亚油酸的方法,适宜的异构化条件为m(氢氧化钠)∶m(亚油酸甲酯)∶m(乙二醇)=1∶5∶8.4,170℃反应4 h,亚油酸甲酯转化率和共轭亚油酸产率分别为92.4%和89.3%。该法比目前常用的亚油酸原料法的优越之处体现在:以氢氧化钠取代常用碱氢氧化钾,降低成本;以亚油酸甲酯取代亚油酸为原料,避免了原料本身大量消耗碱;反应初期避免原料大量皂化,减小了体系的传质阻力,因而减少了溶剂乙二醇消耗量。     

Hydroxy-, Methoxymercuration and Lewis Acid Catalyzed Formyloxylation of Methyl Linoleate

Methyl linoleate (1) reacts by hydroxymercuration-demercuration to methyl hydroxyoctadecenoates (2) of the ricinolic acid type and tetrahydrofurans 4, 5. Good yields of 4,5 are favored by high concentrations of 1 and reagents and reflux temperature. Methyl ricinolate cyclizes in an analogous reaction nearly quantitatively to 4 with a high diastereoselectivity in favor of the syn-isomer. The methoxymercuration-demercuration leads to mono- and dimethoxy adducts. Mercury(II) acetate can be substituted for nontoxic electrophiles. 1 affords in formic acid with BF₃-etherate or HBF₄ as Lewis acids the mono- and diformiates in a ratio of 1:1 and 77% yield. In contrast to the oxymercuration, however, this addition is fairly regiounselective.     

Effect of Transition Metals on Polysialic Acid Structure and Functions

Polysialic acid (PSA) is one of the most abundant glycopolymer present in embryonic brain, and it is known to be involved in key roles such as plasticity in the central nervous system, cell adhesion, migration and localization of neurotrophins. However, in adult brain, its expression is quite low. The exception to this is in Alzheimer′s disease (AD) brain, where significantly increased levels of polysilylated neural cell adhesion molecule (PSA‐NCAM) have been reported. Here, we confirm the role of PSA as a metal chelator, allowing it to decrease cytotoxicity caused by high levels of transition metals, commonly found in AD brain, and as a regulator of cell behavior. UV‐visible (UV‐vis) and circular dichroism (CD) spectroscopy, atomic force microscopy (AFM), and isothermal titration calorimetry (ITC) techniques were used to investigate the assembly of PSA–metals complexes. These PSA–metal complexes exhibited less toxicity compared to free metal ions, and in particular, the PSA–Cu²⁺ complex synergistically promoted neurite outgrowth in PC12 cells.     

Synthesis and Characterization of Phosphonates from Methyl Linoleate and Vegetable Oils

Phosphonates were synthesized on a medium scale (~200 g) from three lipids—methyl linoleate (MeLin), high‐oleic sunflower oil (HOSO) and soybean oil (SBO), and three dialkyl phosphites—methyl, ethyl and n‐butyl, using a radical initiator. A staged addition of the lipid and the initiator was used to achieve good yields. Good results were observed with MeLin (94–99% conversions of the double bonds, as determined by NMR, and 83–99% isolated yields) and HOSO (99–100% NMR conversions, 87–96% isolated yields) using tert‐butyl perbenzoate as the initiator. With SBO, benzoyl peroxide was used as the initiator, due to its capability to generate radicals at a higher rate at slightly lower temperatures, and thus to shorten the reaction time. Conversions of 91–93% (by NMR) and isolated yields of 80–94% were achieved. The progress of the reaction was monitored with GC–MS. The products were characterized using ¹H, ¹³C and ³¹P NMR, IR and gel permeation chromatography. A prolonged reaction led to some transesterification between the carboxylic and phosphite ester groups. Conditions favoring higher reaction rates led to the formation of more oligomers and benzoate fatty ester byproducts. The benzoate fatty ester byproducts were formed by the attack of a benzoate radical on a double bond. The more double bonds that were present per lipid molecule, the more oligomers were formed: MeLin 2–8%, HOSO 3–9% and SBO 8–29%.     

从棉籽油制备高纯度亚油酸甲酯研究

研究由棉籽油制备高纯度亚油酸甲酯的工艺过程 ,通过尿素包结法找到一种极为有效的分离不饱和脂肪酸的方法。     

Effect of α-Tocopherol During In Vitro Ozonation of Methyl Linoleate: Its Implication in Ozone Therapy

Systemic ozone therapy is widely used as an oxidant therapy to treat many conditions and diseases. It is known that ozone therapy acts through a transient oxidative stress produced by lipid ozonation products. The convenience of supporting patients with antioxidants during systemic ozone therapy applications is now under discussion. We studied the reaction of linoleate (one of the main constituents of cellular membranes and plasma phospholipids) with ozone in presence or absence of α-tocopherol, in order to explore whether the combination of ozone and antioxidant has some effect on fatty acid ozonation products. Proton nuclear magnetic resonance spectroscopy (¹H NMR) was used for following the reaction between 4.8mol mmol of methyl linoleate and 2.08 or 4.32mmol of ozone, with addition of different amounts of α-tocopherol (0.10, 0.18, and 0.26μmol). Ozonide (δ=5.15ppm) and aldehydes (δ=9.63ppm and δ=9.74ppm) intensities from ¹H NMR signals markedly decreased with α-tocopherol addition. When αtocopherol is absent, the intensities from olefinic proton signals diminished with ozone concentration increment; however, with αtocopherol in the mixture a smaller decrement was achieved. No detectable signals were found with the ozonation of α-tocopherol without methyl linoleate in the reaction mixture. These results suggest that α-tocopherol reacts with those products released from the reaction of ozone with methyl linoleate. This fact points out that antioxidant supplementation during systemic ozone therapy (major and minor autohemotherapy, rectal insufflation, and so forth) can be detrimental toward achieving the needed transient oxidative stress responsible for biological activities.     

Effect of Adding Transition Metals to Copper on the Dehydrogenation Reaction of Ethanol

The present work aims to investigate the effect adding Ag, Co, Ni, Cd and Pt to copper on ethanol dehydrogenation. The catalysts synthesized by deposition–precipitation method were characterized using various physicochemical methods such as N₂ adsorption–desorption, TPR, SEM–EDX, XRD, XPS and TGA–DSC-MS. Catalytic evaluation results revealed that the predominant product of the reaction was acetaldehyde. Monometallic copper or mixed with Cd, Ag or Co show good catalytic performances. Adding nickel to copper improves the process conversion but reduces acetaldehyde selectivity, giving rise to methane in produced hydrogen. Pt-Cu/SiO₂ catalyst guides the reaction towards diethyl ether. Time on stream tests performed during 12 h at 260 °C, showed that adding Cd to Cu enhances its stability by over 30% of conversion, this is explained by the reduction of copper crystallites sintering, which makes Cd-Cu/SiO₂ a promising catalyst for the production of acetaldehyde by ethanol dehydrogenation.

Graphic Abstract

     

Effect of Metal Contaminants and Antioxidants on the Oxidation Stability of the Methyl Ester of Pongamia

According to the proposed National Mission on biodiesel in India, we have undertaken studies on the stability of biodiesel from tree-borne non-edible oil seeds like Pongamia pinnata. Neat Pongamia methyl ester (PoME) exhibited an oxidation stability (OS) of 2.54 h and research was conducted to investigate the effect of the presence of transition metals likely to be present in the metallurgy of storage tanks and barrels, on the OS of PoME. It was found that the influence of metal was detrimental to OS and was catalytic, as even small concentrations of metal contaminants showed nearly the same influence on OS as large amounts. Copper showed the strongest detrimental and catalytic effect on OS. The OS of metal-contaminated PoME was found to increase with an increase in the dosage of antioxidant but the dosage required for copper-contaminated PoME became approximately four times than required for neat PoME. The dependence of the OS on the type of metal showed that long-term storage tests in different types of metal containers for examining the influence of container material on OS of biodiesel may be replaced by the significantly faster Rancimat test serving as an accelerated storage test.     

Electrical and Spectroscopic Studies on Some Transition Metal Acrylates Methyl Methacrylate Bulk Co and Terpolymers

Abstract

Copolymers of Fe acrylate-methyl methacrylate (MMA), Mn acrylate-MMA and terpolymer of Fe acrylate-Mn acrylate-MMA were prepared by bulk technique. A thorough investigation of the response of the prepared samples to γ-irradiation has been carried out. The frequency dependence of a.c. conductivity data showed that the relaxation frequency depend on the type and concentration of the metal acrylate units. For a wide distribution of relaxation time, the change of slope at the transition in the plot of log crac Vs. logf is hardly noticable. The change in the position of some absorption bands in the UV-visible spectrum was attributed to the existence of interaction between the transition metal acrylate unit and MMA monomer From the relationship between the absorption intensity and dosage occurred, the data suggested that MMA-Fe acrylate copolymer could be used as plastic dosimeter for γ-rays in the dose range 1.75–6.41 KG y.     

Parallel Reactor Activity Studies of the Preferential Oxidation of CO on Transition Metals Supported on TiO2 and TiO2 Nanotubes

The preferential oxidation of carbon monoxide in the presence of hydrogen (PROX reaction) was studied on Cu catalysts promoted with Fe, Nb, Ce, and Ni supported on TiO₂ and on TiO₂ nanotubes. The surface area of the untreated TiO₂ anatase (150 m²/g) support was increase to 350 m²/g when transformed into TiO₂ nanotubes (NT). XRD and SEM results confirm the formation of nanotubular structures responsible of the increase in BET surface area. The activity results indicate that a 10% Cu/5% Nb/TiO₂-NT catalyst is highly active for this reaction compared to other transition metals and with a catalyst with the same composition supported on untreated TiO₂. We found close to 80% CO conversion and 40% selectivity to CO₂ formation at 170 °C. The higher activity is ascribed to a higher dispersion of Cu on the TiO₂ NT structures.     

Determination of Oxidation of Methyl Ricinoleates

Ricinoleate esters have desirable properties as biolubricants, but their oxidative stability has been questioned. To systematically study the stability of ricinoleate ester and its derivative, methyl esters of castor oil were prepared and methyl ricinoleate was isolated by solvent partitioning. Methyl 12‐acetyl ricinoleate was synthesized from the methyl ricinoleate by interesterification with excess methyl acetate and was then purified by solvent partitioning. The rates of oxidation of methyl linoleate, methyl oleate and the two ricinoleate esters were measured by oxidation of lipid dispersed on glass beads under three temperatures (40–80 °C). The relative amounts of the unoxidized methyl esters were determined periodically by gas chromatography, and the peroxide value of the oils was also determined. The oxidation rates were determined as the peroxide value increase rate, as well as the ester disappearance rate, and the stability of the various esters was compared. Overall, methyl ricinoleate was much more oxidatively stable than methyl oleate at mildly elevated temperatures, and the acetylation of the hydroxyl group on the 12th carbon decreased the stability.     

The Influence of Tocopherols on the Oxidation Stability of Methyl Esters

Tocopherols were found to be the principal natural antioxidants in biodiesel grade fatty acid methyl esters. The stabilising effect of α-, γ- and δ- tocopherols from 250 to 2,000 mg/kg was evaluated by thermal and accelerated storage induction times based on rapid viscosity increase, in sunflower (SME), recycled vegetable oil (RVOME), rapeseed (RME) and tallow (TME) methyl esters. Both induction times showed that stabilising effect is of the order of δ- > γ- > α-tocopherol, and that the stabilising effect increased with concentration. The correlation between the two induction times however was poor, which is probably due to the fact that the time they correspond to two different stages of oxidation. Tocopherols were found to stabilise methyl esters by reducing the rate of peroxide formation while present. The deactivation rates of tocopherols increased with unsaturation of the particular methyl ester and in the present work they were of the order of SME > RME > RVOME > TME. While α-tocopherol was found to be a relatively weak antioxidants, both γ- and δ- tocopherols increased induction times significantly and should be added to methyl esters without natural antioxidants.     

甲基橙的催化氧化降解工艺研究

分别采用紫外光照射、超声波辐射、纳米NiO催化3种方法及其相互协同作用对模拟印染废水甲基橙溶液进行催化氧化降解研究.结果表明,超声波辅助纳米NiO催化氧化降解模拟印染废水甲基橙溶液的效果显著优于紫外光照射、纳米NiO催化及其相互协同作用.     

Synthesis and Physicochemical Properties of Partially and Fully Epoxidized Methyl Linoleate Derived from Jatropha curcas Oil

Partial epoxidation of methyl linoleate was carried out at room temperature (30 °C) using a methyltrioxorhenium catalyst in the presence of pyridine and urea‐hydrogen peroxide. Full epoxidation of methyl linoleate was carried out using the Prilezhaev method. The reactions were monitored using the oxirane oxygen content value. The products from partial and full epoxidation were analyzed using GC‐FID, FTIR, NMR and GC–MS. Methyl 9,10‐epoxy‐12Z‐octadecenoate and methyl 12,13‐epoxy‐9Z‐octadecenoate were obtained as the major products from partial epoxidation, with a percent yield of 46 %. The product from full epoxidation afforded 97 % yield with methyl 9,10‐12,13‐diepoxyoctadecanoate as the major component. Physicochemical properties such as kinematic viscosity, viscosity index, crystallization temperature and oxidative stability were examined. Fully epoxidized methyl linoleate exhibits superior kinematic viscosity and oxidative stability due to the complete conversion of double bonds to epoxy groups. Partially epoxidized methyl linoleate exhibits intermediate kinematic viscosity, viscosity index, crystallization temperature and oxidative stability.