植物油的质谱分析：1.蓖麻油

运用一种植物油的系统分析方法测定蓖麻油的精细组分，这包括皂化，ＢＦ３－ＭｅＯＨ甲基化，ＧＣ－ＣＩＭＳ法测定脂肪酸碳链长度和不饱和度，ＡＭＰ衍生化，ＧＣ－ＥＩＭＳ测定不饱和脂肪酸的双链位置，分析了蓖麻油的十一种脂肪酸组分，有五个为未知组分，并测定了其中三个组分的双链位置。     

Determination of Arsenic Species in Fish Oil After Acid Digestion

Arsenic speciation is of increasing interest to the food industry, as concerns about high total arsenic concentrations in food can often be alleviated to a great extent if the ratio of toxic, less toxic and non-toxic arsenic compounds in the sample is known. The lipid matrix of fish oil is a challenge in the determination of arsenic species, as current methods for this type of analysis require the analyte to be water-soluble. In this study, two sample preparation techniques were applied. One the one hand water-soluble species were extracted with methanol/water, on the other, acid digestion was applied to release lipid-soluble arsenic compounds into the aqueous phase. Ion chromatography – inductively coupled plasma mass spectrometry (IC-ICP-MS) was used for separation and sensitive element-specific detection of arsenic compounds. Additional experiments, including alkaline hydrolysis, were carried out to find out more about the type of lipids arsenic is bound to in fish oil. Up to eight different arsenic species were detected and quantified in fish oil with dimethylarsinate being the major compound both in the aqueous extract and in the acid digest. No inorganic arsenic was detected in the aqueous extract, and the maximum concentration of arsenate determined in the acid digest was 0.05 μg g⁻¹. The total arsenic concentration determined by ICP-MS ranged from <0.1 to 5 μg g⁻¹. With regard to the mass balance, approximately 1% of the total arsenic content was extractable with methanol/water, whereas the sum of arsenic species quantified after acid digestion yielded 85–100% of the total arsenic content. It was confirmed that the large fraction of arsenic in fish oil not extractable on an aqueous basis consists of organoarsenic compounds. This new approach in sample preparation makes the complete characterization of the arsenic content in the sample possible with regard to the respective species, providing necessary information required for risk assessment.     

Bond interchange reactions in functionalized triglyceride oil/poly(ethylene terephthalate) compositions

Naturally functionalized triglyceride oils are renewable resources which contain reactive chemical groups, hydroxyl in the case of castor oil, and epoxide in the case of vernonia oil. In this article, the reaction of these groups, and the ester linkages between the glycerol and acid residue portions of the oil molecule with poly(ethylene terephthalate) (PET) is investigated through a variety of means. Multiple reactions are possible in the triglyceride–PET system, some of which form a copolymer that increases miscibility, and if allowed to continue, forms a completely random copolymer mixture. Among the numerous reactions possible, PET–ester exchange with the hydroxyl or epoxide functionality of the triglyceride oils is found to be the most significant, and the effects of these and other reactions are observed and structural implications discussed. © 1993 John Wiley & Sons, Inc.     

混合溶剂火焰原子吸收法直接测定原油中的镍

混合溶剂火焰原子吸收法直接测定原油中的镍刘广东袁存光张丙华刘文钦（石油大学（华东），山东东营２５７０６２）彭力（中国石油天然气总公司环保处，北京１００７２４）关键词原油，混合溶剂，无机盐标准，原子吸收法，镍测定原油中，微量元素镍、钒、铁、铜的存在对...     

Analysis of free and esterified sterols in vegetable oil methyl esters by capillary GC

The introduction of quality standards for vegetable oil methyl esters is gaining in importance due to their increased use as diesel fuel substitutes and as technical products. Free and esterified sterols, the main constituents of the unsaponifiable matter in vegetable oils, are recovered in vegetable oil methyl esters and may influence the technical properties of vegetable oil methyl ester products. A rapid gas chromatographic method for the qualitative and quantitative determination of free and esterified sterols in vegetable oil methyl esters has therefore been developed. The concentration of the free sterols as well as their qualitative and quantitative composition and the concentration of the sterol esters have been determined in rape seed oil methyl ester samples by GC–FID. Prior to analysis, the free sterols were silylated with N,O-bis(trimethylsilyl)trifluoroacetamide with 1% of trimethylchlorosilane; betulinol was used as an internal standard. Calibration was performed by analysis of standard solutions containing β-sitosterol, cholesteryl stearate, and betulinol. The reproducibility of the quantitative results has been evaluated by repeated injections of the same test solution and by repeated complete analysis of the same sample.     

Increase in removal of polycyclic aromatic hydrocarbons during bioremediation of crude oil-contaminated sandy soil

A 2³ full factorial experimental design was adopted to estimate the effects of three variables on the biodegradation of oil during soil bioremediation: bioaugmentation seeding a mixed culture, addition of fertilizer or mineral media, and correction of initial pH of the soil to 7.0. The tests were carried out in polyvinyl chloride reactors with 5.0 kg of crude oil-contaminated soil at 14 g/kg. After screening the variables, soil bioremediation tests were conduced with varied C:N ratios, yielding an increase in biodegradation of the oil heavy fraction from 24 to 65%, consumption of total n-paraffins, and a remarkable decrease in the concentration of residual polycyclic aromatic hydrocarbons of the soil.     

Stimultaneous quantitative analysis using dual capillary columns of different polarities

Complex organic mixtures, such as coal liquefaction and oil shale products and by-products, are comprised of hundreds or thousands of individual components. State-of-the-art high resolution gas chromatography does not always provide sufficient resolution to allow accurate quantitation or identification of many compounds of interest. The concept of dual capillary column chromatography combines the different resolving characteristics of two capillary columns coated with different stationary phases into a single chromatographic run. In this approach, both columns are connected to the same injection port. Analysis of complex mixtures in this fashion can confirm the identification and quantitation of components on two columns of different polarity with little increased analysis time, can provide a means of obtaining quantitative data for individual components which are known to coelute on any one column, and can alert one to unknown coelution problems that would be undetected by gas chromatographic analysis on a single capillary column. Simultaneous dual column analysis was applied to three samples, the neutral polycyclic aromatic hydrocarbon (PAH) fraction of a Solvent Refined Coal-II (SRC-II) heavy distillate, the nitrogen-containing polycyclic aromatic compound (N-PAC) fraction of an SRC-II heavy distillate, and the basic fraction from a shale oil process water. Fused silica capillary columns coated with SE-54 and Durawax 3 were used for the analyses of the heavy distillate, while SE-54 an Carbowax 20M capillary columns were used for the analysis of the process water.     

Enhancement of the static SIMS secondary ion yields of lipid moieties by ultrathin gold coating of aged oil paint surfaces

Static secondary ion mass spectrometry (SIMS) is a powerful technique for identification and localization of pigments and binding media present in traditional paintings. Coating the surface of a cross‐section with a 20 Å thick gold layer improves the yields of secondary ions from the fatty acids and diacids. A chalk tablet containing 1% stearic acid, which was partially covered during gold deposition, is used as a test system to investigate the increase of the organic secondary ion yields upon gold deposition in SIMS imaging. A comparative study of a native and gold‐coated aged surface of a lead white‐containing linseed oil paint demonstrates the enhancement of the organic ion yields on a sample relevant for painting studies. The yields of oil paint‐derived negative ions increase by a factor of 3 whereas the yields of positive ions increase by a factor of 2–4. The different types of charged functional groups determine the degree of improvement in yield. Gold coating improves the ionization process of the fatty acids and does not influence their fragmentation. The dissociation of the lead white by the primary ion beam is reduced due to the gold coating. Copyright © 2004 John Wiley & Sons, Ltd.     

Chemical Constituents of the Essential Oil of <Emphasis Type="Italic">Nepeta oxyodonta</Emphasis>

Water-distilled essential oil from the aerial parts of Nepeta oxyodonta Boiss. was analyzed by GC/MS for the first time. Fifty-eight components were identified. The major components were (E)-caryophyllene (12.6%), spathulenol (8.5%), β-bourbonene (8.1%), germacrene-D (7.4%), α-cadinol (7.3%), germacrene-D-4-ol (6.8%), T-cadinol (5.6%), and caryophyllene oxide (5.3%).__________Published in Khimiya Prirodnykh Soedinenii, No. 2, pp. 141–142, March–April, 2005.     

A nanoscale vesicular polydiacetylene sensor for organic amines by fluorescence recovery

We report a nanoscale lipid membrane-based sensor of conjugated polydiacetylene (PDA) vesicles for fluorescence detection of organic amines. The vesicle sensor was constructed by incorporation of a BODIPY fluorescent dye into the PDA vesicles. The fluorescent properties of the resulting vesicles can be manipulated by adjusting lipid components, and are controlled by environmental and solution conditions. The fluorescence of the BODIPY dye was significantly quenched in the polymerization of diacetylene lipid vesicles by a UV irradiation process. However, it was sufficiently recovered by external stimuli such as a hike of solution pH. The fluorescence recovery process was reversible, and a decrease in solution pH resulted in repeated quenching. The reported system transforms an external stimulus into a large fluorescence intensity change, demonstrating great potential in developing new signal reporting method for biosensor design. The quench-recovery phenomenon of the BODIPY-PDA is believed to be related to the energy transfer between the dye and the PDA conjugate backbone. The vesicle sensor was applied for detecting an organic amine, triethylamine (TEA) and a large linear relationship was obtained between the increase in fluorescence intensity and the concentrations of TEA. The detection limit of TEA by vesicle sensors using fluorescence recovery was found to be 10 μM.