Gas chromatographic study on high-temperature thermal degradation products of methyl linoleate hydroperoxides

Chromatographic techniques were used to separate secondary products generated by thermal degradation of methyl linoleate hydroperoxides (MLHP). The MLHP were obtained by oxidation, selected, and concentrated by solid-phase extraction (SPE) and thin-layer chromatography (TLC). The purified MLHP were then thermo-degraded in the gas-chromatographic glass liner and analyzed on-line by gas chromatography-mass spectrometry (GC-MS). The MLHP were also thermodegraded and collected in a short silicic acid-packed column, eluted, separated by TLC, and then analyzed by GC. By considering the elution in TLC, the GC retention times and the GC-MS analyses, it was possible to characterize the mono- and the dioxygenated secondary products, particularly those having a boiling point higher than methyl linoleate. The peaks that corresponded to the mono-oxygenated products (epoxy, hydroxy, and keto) were identified, and, on the basis of their MS spectra, molecular structures were proposed. A specific elution order was suggested for keto derivatives: 9-keto,Δ^10,12- and 13-keto,Δ^9,11-octadecadienoate. The hydroxy derivatives, which show the typical fragmentations of 9-hydroxy,Δ^10,12- and 13-hydroxy,Δ^9,11-octadecadienoate, were also identified. On the other hand, identification of the di-oxygenated compounds was more difficult, and, therefore, it was not possible to indicate each positional isomer; however, their elution order could be epoxy-hydroxy and epoxy-keto derivatives.     

Antioxidant efficacy of amino acids in methyl linoleate at different relative humidities

Antioxidant efficacy of the amino acids methionine, tryptophan, aspartic acid, serine, alanine and arginine in methyl linoleate were compared to a methyl linoleate control at 2,50 or 79% relative humidity (RH) at 37°C. Antioxidant efficacy varied with RH and the individual amino acids. Arginine had the highest antioxidant efficacy at all RH values compared to the control. The efficacy of alanine was equal to that of arginine at RHs of 50 and 79% but was lower at 2% RH. The presence of aliphatic, alkaline amino, hydroxyl or thiol groups in the side chain of the amino acids increased the antioxidant efficacy at high RHs.     

Moderate antioxidative efficiencies of flavonoids during peroxidation of methyl linoleate in homogeneous and micellar solutions

The relative reactivities as well as the stoichiometric coefficients for a number of flavonoids, catechols, and—for comparison—standard phenolic antioxidants were determined by analyzing the kinetics of oxygen consumption in organic and micellar systems, with peroxidation initiated by lipid- and water-soluble azo initiators. The results demonstrated that the flavonoids did not behave as classic phenolic antioxidants such as α-tocopherol, but showed only moderate chain-breaking activities. The results were in line with other structure-activity relationship studies on the importance of the B-ring catechol structure, the 2,3-double bond, and the 3,5-hydroxy groups. The data are discussed in view of possible explanations of the deviations flavonoids reveal in their behavior compared with regular phenolic antioxidants.     

Oxidation of methyl linoleate in the presence of lignin

The overall aim of this study is to develop new wood modifications using vegetable oils to obtain improved durability of wood materials in an environmentally friendly way. Nuclear magnetic resonance (NMR) and Fourier-transform infrared (FT-IR) spectroscopies were used to study oxidation and possible chemical coupling reactions between polyunsaturated fatty acids and model lignin compounds in order to better understand the interactions between oxidatively drying systems such as vegetable oils or alkyds with the lignin part in wood. This was done by studying mixtures of different model lignin compounds and methyl linoleate. The oxidation process was analyzed at 70 °C both in methyl linoleate alone and in combination with 20 wt% of lignin model compounds. The effects of those compounds on the oil polymerization processes were monitored by NMR (both ¹³C and ¹H experiments) and the domain specific reactivity and patterning were then combined with FT-IR data. No covalent bonds having formed between the oil and the model compounds were detected by combination of several ¹³C/¹H 2D NMR methods. From the spectra, the oxidation degrees of model compounds were calculated, and for some lignin model compounds alcohols were oxidized to carbonyls during the process. Those results were in excellent agreement with FT-IR data and oxidation mechanisms were proposed. The combination of both analytical techniques was necessary to have a better understanding of these systems: NMR demonstrated the absence of chemical bond and quantified oxidation degree of model lignin molecules while FT-IR focused on oil oxidation.     

Effect of thioanisole and trimethylene sulfide on the oxidation and yellowing of methyl linolenate

The effect of thioanisole and trimethylene sulfide on the autoxidation and yellowing of methyl linolenate has been investigated by nuclear magnetic resonance (NMR) and ultraviolet visible spectroscopy, respectively. The progress of autoxidation was followed by measuring the NMR integration of vinylic protons with respect to methoxy protons, which served as the internal standard, as a function of time. The degree of yellowing was determined by measuring the difference in absorbance at 400 nm and 450 nm as a function of time. Both thioanisole and trimethylene sulfide enhanced the autoxidation of methyl linolenate. Inhibition of yellowing was observed only with trimethylene sulfide.     

Effect of PbII on the secondary structure and biological activity of trypsin

The effects of Pb(II) on the secondary structure and biological activity of trypsin have been examined by monitoring changes in its conductivity and IR and circular dichroism (CD) spectra. The results show that Pb(II) reacts with trypsin, and that the binding sites might be -OH and -NH groups in pepsin. The CD spectra indicate that interaction with Pb(II) significantly affects the secondary structure of trypsin, the beta-sheet-structure content being increased by about 42%, whilst those of alpha-helix and beta-turn structures are decreased by 13% and 21%, respectively. The results clearly demonstrate that Pb(II) affects the biological activity of trypsin by modifying its secondary structure. Most interesting is that Pb(II) up-regulates the activity of trypsin at low concentrations while down-regulating it at high concentrations.     

居住小区管网系统二次给水污染的研究

对西安市部分住宅楼二次供水系统进行分析,对比了4种不同供水方式及不同管材和水力停留时间对用户水质的影响。结果表明,以水箱供水的影响较大,气压给水二次污染较小;室内供水系统中钢塑复合管优于镀锌管;停留时间以不超过6h为宜。针对小区管网系统二次污染状况,提出管网系统二次污染的防治改造对策。     

Performance of lipid‐based moisture barriers in food products with intermediate water activity

Nine lipid‐based barrier films (three chocolates, acetomonopalmitine, white beeswax, and four commercial blends: two acetoglycerides/beeswax blends, two hydrogenated and fractionated vegetable oils) were characterised using classical water‐related and physical properties of edible barriers, such as water vapour permeability, moisture adsorption isotherm, moisture effective diffusivity, surface hydrophobicity, firmness and solid fat content (20 °C). Classifications based on these properties were established and compared to the barrier efficiency under real conditions of use, i.e. in a model food product (cereal‐based component – intermediary a_w gel). Moisture migrations were performed using self‐supported barriers (300 µm) and fitted with a predictive model based on Fick's Second Law. White beeswax and acetoglycerides enabled the best extensions of the dry‐component shelf life from 2 h to between 100 and 330 h. Moisture effective diffusivity and calculated water vapour permeability combined to a mechanical property evaluation of the barrier were more discriminating to assess the barrier efficiency in the model food than the moisture sorption and experimental water vapour permeability. The importance of combining both water‐related and physical characteristics of the barrier and the advantages of an integrated approach through the simulation of the material behaviour under its real conditions of use with the model are highlighted.     

动物肝脏中超氧化物歧化酶活性的测定

本文采用微量连苯三酚自氧化法测定动物肝脏中超氧化歧化酶活性,方法操作简单,精密度好,灵敏度高,可广泛应用于动物肝脏中超氧化歧化酶活性的测定。     

One-step formation of ethyl methyl ketone from 1-butene and water on ultrastable Y-type zeolite catalyst

Proton exchanged ultrastable Y-type zeolite with silica/alumina = 40 showed a pronounced catalytic activity for the formation of ethyl methyl ketone directly from 1-butene and water. The formation rate of ethyl methyl ketone was much higher than those on MoO₃-based catalysts in the oxidation of 1-butene by oxygen. It was suggested that the basic site necessary for the formation of ethyl ketone directly from 1-butene and water would be the pentacoordinated Al.     

国产水分散型助分散剂在氯乙烯聚合中的应用

通过对国内外各种助分散剂的应用对比,针对PVC生产中存在的问题,在油溶性PVA生产技术基础上,添加VAC共聚单体,研制开发出一种水分散型助分散剂,其各项性能达到国外同类产品水平,现已工业化生产,应用于国内部分PVC厂家。     

DSC studies on states of water in crosslinked poly(methyl methacrylate-co-n-vinyl-2-pyrrolidone) hydrogels

Mixtures of methyl methacrylate (MMA) with N-vinyl-2-pyrrolidone (VP) of various composition in the presence of fixed concentration of ethylene glycol dimethacrylate (EDMA) have been copolymerized to 100% conversion by γ-irradiation. The resultant solid xerogels were swollen in water to yield hydrogels of equilibrium water contents ranging from 15 to 76wt%. The state of water in the poly(MMA-co-VP) hydrogels has been studied by differential scanning calorimetry (DSC) and the percentages of free freezing, freezable bound and nonfreezing water were found to vary with the xerogel composition, i.e. the degree of hydration of the hydrogels. At low equilibrium swelling, most of the water exists as a non-freezing type, whereas at higher equilibrium swelling the majority of water exists as free freezing water. The maximum number of non-freezing water molecules per VP unit in the hydrogel is about 7.5.     

木质纤维素超临界水解糖化产物分析的研究

在超临界条件下水解桉木,探讨了反应时间对液体产物分布的影响。结果表明:反应时间对葡萄糖、纤维二糖、木糖、5-羟甲基糠醛(5-HMF)的产率影响明显,最大分别为17.17%、2.58%、6.82%、12.70%。同时,低聚糖的种类会随着反应时间的延长而变化。水解液的主要组分为:低聚糖、纤维二糖、葡萄糖、木糖、5-HMF、糠醛、酚类物质,以及呋喃、酮、醛、醇、有机酸、芳香族和脂肪类化合物等,且产物种类和浓度受反应时间的影响。在超临界水中,桉木的水解和热解反应同时发生。另外,木质素的存在影响桉木超临界水解的产率。     

The effect of interfacial tension on secondary drop formation in electro-coalescence of water droplets in oil

The coalescence of water droplets in oils may be enhanced by application of an electric field. This approach is commonly used in the crude oil and petroleum industry to separate water from crude oil. However, the process could lead to the formation of fine secondary droplets during the process of coalescence. This is obviously undesirable, as it becomes more difficult to separate finer water droplets. In this work the effects of interfacial tension, manipulated by the use of surfactants, and electric field strength on the formation of secondary droplets are investigated. Two competing processes of necking and pumping determine whether secondary droplets are formed. The dimensionless groups Weber Number (describing droplet deformation and necking due to the electric field) and Ohnesorge Number (describing the pumping of water into the continuous phase in the process of coalescence) may be coupled to give a new dimensionless group WO, describing the volume fraction of secondary droplets that are formed. WO Number describes the ratio of the electrical stress energy that causes necking over the energy required for pumping the viscous fluid out of the droplets. For a wide range of interfacial tensions, brought about by the use of non-ionic and anionic surfactants and electric field strengths, a good unification of data is obtained. The outcome of this work will be useful for optimizing the design of the electro-coalescence systems.     

Clinacanthus nutans Lindau: Effects of drying methods on the bioactive compounds,color characteristics,and water activity

The application of solar drying (SD) and heat pump-assisted solar drying (HPSD) on the retention of flavonoid components, total color changes, and water activity of Clinacanthus nutans Lindau leaves were investigated. Analysis of data shows significantly higher extractable yield and flavonoid (orientin and vitexin) percentage during the drying with HPSD. The same drying technique also revealed optimum color values and low water activity. Thin-layer models fitted to the experimental data show that Hii and Law model is suitable for SD, while logarithmic model is able to give a good fit to HPSD.     

水对PAN-DMSO溶液流变性能及纺丝成形的影响

研究了水对聚丙烯腈-二甲基亚砜(PAN-DMSO)纺丝溶液流变性能和初生纤维组成及双扩散系数的影响。随着水含量的增加,PAN-DMSO溶液的表观粘度有所下降,其流动性得以改善,粘流活化能下降,孔口胀大比变大。适量水的加入还降低了纺丝成形过程中溶剂、非溶剂的扩散速率,减少了纤维中水含量,有利于制备高性能PAN原丝。     

Analysis of several methods to determine the activity of water in solutions of strong electrolytes

The methods of Zdanovskii-Stokes-Robinson (ZSR), Reilly-Wood-Robinson (RWR), Pitzer and Correa, to determine water activity in ternary solutions of electrolytes from data for water activity in binary solutions, were analysed. In addition, the first two methods were used to estimate the activity of water in supersaturated binary solutions using data from ternary solutions. Also, the equation of Correa for binary solutions was extrapolated to calculate the activity of water at supersaturation. The methods were tested using the experimental data (at 25°C) for nine ternary systems, with a common ion, involving the following ions: Li⁺, Na⁺, K⁺, Ca⁺⁺, Mg⁺⁺, Cl^? and NO₃^?. Zdanovskii's method gave the best estimations of water activity in ternary systems. The method of Correa gave smaller standard deviations than the methods of Pitzer and RWR with the advantage that its application is simpler. For binary solutions at supersaturation, Correa's method gave better results than the method of ZSR and this, in turn, yielded smaller deviations than the RWR method.     

The effect of hydrothermal dewatering of Pontianak tropical peat on organics in wastewater and gaseous products

This paper describes a study of the effects of hydrothermal dewatering of raw tropical peat from Pontianak, West Kalimantan-Indonesia, on the amounts of organic compounds released into wastewater and gaseous products. Hydrothermal upgrading and dewatering of the peat was carried out in a batch-type autoclave reactor at temperatures between 150 and 380 °C at a maximum pressure of 25.1 MPa for 30 min. It was found that the extent of decomposition of organics during hydrothermal dewatering depended on temperature increase.Wastewater from hydrothermal dewatering was found to contain organic carbon (TOC) ranging from 800 ppm at low temperatures, to 7504 ppm at high temperatures. A number of sugars and furans were detected in the wastewater at 250 °C, and organic acids and alcohols at all temperatures. Phenol and phenolic derivatives were observed at 250 °C, and significant amounts of CO₂, CO and H₂ were detected at all temperatures studied; CH₄ was detected only at 380 °C, but at this temperature CO₂ was no longer detected.A simplified schematic diagram of the decomposition behavior of tropical peat in the hydrothermal dewatering process is discussed with respect to the change in the concentration of organics in wastewater and gaseous products as determined by TOC, GC, GC–MS and ¹³C NMR analyses of the solids produced.     

超声——化学氧化法降解水中甲基橙的研究

用超声波辐射甲基橙溶液,研究了溶液浓度、溶液酸碱度(pH值)、外加H2O2、外加纳米TiO2光催化剂和联合紫外光照射对甲基橙的降解效果。结果表明,甲基橙溶液浓度在10~40 mg/L范围内,其降解率与溶液浓度呈良好的线性关系(相关系数r=0.9917~0.9987);pH=3的酸性条件下甲基橙的降解率是pH=11的2倍;加入3g/L H2O2能使降解率提高40%;加入纳米TiO2和联合紫外光照射使甲基橙的脱色率达100%,超声波、纳米TiO2和紫外光三种作用存在协同效应。     

Impact of extraction method on yield of lipid oxidation products from oxidized and unoxidized walnuts

The objective of this study was to measure and compare differences in oxidized products of oil extracted from unoxidized and oxidized walnuts using five different extraction methods: (i) mechanical pressing, or solvent extraction with (ii) hexane, (iii) methylene chloride, (iv) chloroform/methanol, or (v) supercritical carbon dioxide (SC−CO₂). Of the extraction methods evaluated, only chloroform/methanol and methylene chloride provided reasonable results for all parameters measured (total lipid yield, FA profile, PV, conjugated dienes, FFA content, and volatile content); however, chloroform/methanol extracted significantly greater levels of volatile compounds. The SC−CO₂ extraction with purified gas was simple and accurate for all data except collection of volatile compounds, as these materials are lost during the lipid extraction. Pressing was neither quantitative nor qualitative, and hexane extraction retrieved significantly lower levels of volatiles than the other methods, except for SC−CO₂.