Fatty Acid Composition in Ergosteryl Esters and Triglycerides from the Fungus Ganoderma lucidum

Free and esterified ergosterols are detected almost solely in fungi and are often employed as a biomarker of living fungi. In this work, the fatty acid composition and δ¹³C values of major fatty acids in triglycerides and ergosteryl esters from the fungus Ganoderma lucidum were analyzed by gas chromatography–mass spectrometer and gas chromatography–isotopic ratio mass spectrometer, respectively. The results showed that the fatty acid profiles varied in triglycerides and ergosteryl esters. The percentage of saturated fatty acids in ergosteryl esters was remarkably higher than that in triglycerides, where C_18:1^Δ9c was the predominant fatty acid and constituted 61.26 % of the total fatty acids. In contrast, C_16:0 was the predominant fatty acid and constituted 71.88 % of the total fatty acids in ergosteryl esters. The study suggests that, after fungal death, free ergosterols in the cell membrane of the dead fungus were esterified with preferentially saturated fatty acids, mainly C_16:0, from triglycerides and then stored in lipid particles for a longer period while free ergosterol markedly decreased. The δ¹³C values of C_16:0, C_18:0, C_18:1 and C_18:2 in ergosteryl esters exhibit a pronounced depletion in ¹³C compared with that in triglycerides within the range of ?1.3 to ?0.9 ‰, supporting the above inference. It is again suggested that free ergosterol in the cell membrane should be used as an indicator of living fungi, and ergosteryl esters in the lipid particles should not be included in the measurement of living fungal biomass.     

汽车罩光漆的同位素比值分析及保存条件影响研究

本文通过检验汽车油漆最外层罩光漆的同位素实现不同样品的区分,并考察保存条件对样品同位素的影响。实验共收集了10种汽车罩光漆样品,分别在室温避光、60℃高温、-20℃低温和强紫外线条件下保存6个月,然后用元素分析仪-同位素比值质谱(EA-IRMS)检测样品的碳、氢、氧同位素比值。结果表明：油漆样品在不同保存条件下发生碳、氢、氧同位素分馏,样品的δ¹³C值在高温和低温保存后向负值偏移,强紫外线照射的影响微弱;δ²H值在3种条件下均向正值偏移,受紫外线照射影响最大;δ¹⁸O值在3种条件下均向负值偏移,但不同种类树脂样品之间δ¹⁸O值的偏移幅度不同,在3类样品中,聚甲基丙烯酸甲脂类树脂样品分子中由于氧含量最少其偏移值最小。稳定同位素分析方法可为油漆样品分析提供高区分度的三维指纹,在油漆识别与区分方面具有较大的潜力,可用于油漆物证的溯源分析。     

C、H、O同位素分析在葡萄酒产区鉴别中的应用

为有效鉴别产区葡萄酒,利用点特异性天然同位素分馏核磁共振技术和同位素比质谱仪技术对葡萄酒中C、H和O同位素进行研究。通过收集2010-2012年河北昌黎、山东烟台蓬莱、宁夏贺兰山东麓和河北沙城四大产区的60 个样品,发现（D/H）i、（D/H）ii、R、δ13C、δ18O、酒精体积分数的范围分别为95.68×10－6～99.15×10－6、115.99×10－6～126.39×10－6、2.38～2.59、－28.35‰～－23.00‰、－1.94‰～－0.05‰和11.3%～12.9%,总体上含量范围分布广泛,但同一地区较为集中。研究发现,单一使用任何一种元素都只能区分环境差异很大的地区,当结合3 种元素,采用线性判别分析能100%有效鉴别四大产区葡萄酒。基于沙城产区的数据库和酒精体积分数,结合t检验法,分3 步可判定出产区酒的真实性。待测的5 个盲样中只有1 个样品属于沙城产区的真实葡萄酒。     

SNIF-NMR和IRMS技术在葡萄酒质量评价中的初步研究

利用SNIF-NMR和IRMS技术测定葡萄酒中稳定性同位素D/H和18O/16O的比值。结果表明,通过测定乙醇分子中甲基位(D/H)Ⅰ和次甲基位点(D/H)Ⅱ的含量,可判断葡萄酒在酿造前是否进行了加糖操作,而通过测定葡萄酒水分中18O/16O的比值,可鉴别全汁葡萄酒和半汁葡萄酒。研究结果为中国葡萄酒的质量评价提供了一种新的技术手段。     

碳-4植物糖超标蜂蜜样品的多维分析

本文从124份市面蜂蜜样品中筛选出21份C-4植物糖超标蜂蜜样品,应用元素分析-同位素质谱联用技术（EA-IRMS）、液相色谱-同位素质谱联用技术（LC-IRMS）、液相色谱测定蜂蜜还原糖含量等检测方法,对C-4植物糖超标蜂蜜样品进行多维分析。结果表明：C-4植物糖超标样品在市面上仍占有一定比例,本批次检出超标率为16.94%,且存在少量严重超标样品,最高达到82.35%。C-4植物糖超标蜂蜜样品大致可归纳为以下三类：一是源于生产操作不规范的轻微超标型,该类样品的碳-4植物糖含量为7~10%之间,△δ13CF-G、△δ13Cmax跟真实蜂蜜要求相差不远;二是人为掺入碳-4植物源淀粉转化产物型,该类样品寡糖含量较高,△δ13Cmax较大。三是人为掺入碳-4植物源果葡糖浆型,该类样品本身不含寡糖,δ13CF、δ13CG完成丧失碳-3植物特征。     

Tissue turnover in ovine muscles and lipids as recorded by multiple (H,C, O,S) stable isotope ratios

Multiple stable isotope ratios (δ²H, δ¹³C, δ¹⁸O and δ³⁴S) were measured in muscle, muscle lipids and lipid fractions collected from 28 lambs, subjected to a diet-switch and raised on two energy allowances (EAs), to determine tissue turnover and diet-tissue fractionation. The diet-muscle fractionations prior to the diet-switch were estimated to be −44.0‰, +1.9‰ and 0‰ for H, C and S, respectively, while the drinking water was demonstrated to be the main source of muscle O and thus δ¹⁸O variation. The diet-intra-muscular lipid fractionations prior to the diet-switch were estimated to be −172.7‰, −1.3‰ and −11.5‰ for H, C and O, respectively. The C half-lives of muscle were determined to be 75.7 and 91.6 days for animals receiving the high and low EA, respectively. Extracting temporally resolved pre-slaughter dietary information from meat by analysing bulk muscle, muscle lipids and muscle lipid fractions appeared to be not practicable due to possible incomplete turnover of lipids.     

Stable carbon isotope content in ethanol of EC data bank wines from Italy, France and Germany

In the present work we discuss the usefulness of carbon isotope analysis of wine ethanol for the assignment of origin and the proof of adulteration of Italian, French and German wines. At first the comparability of the results from three laboratories is demonstrated by the results of inter-laboratory comparison measurement and by tests of the distillation procedures applied to the same samples. Furthermore, a close correlation of carbon isotope content in sugars from must and ethanol from the related wine could be found for samples from all countries. Using the ¹³C values of EC data bank wines from 1991 to 1993 for Italy, France and Germany, we describe and discuss the main factors of influence which are responsible for the variation of those values. By examination of spiked samples, the usefulness of the ¹³C analysis in the detection of certain types of wine enrichment is demonstrated; especially if the carbon isotope analysis by¹³C-8 isotope ratio mass spectrometry is employed as an additional tool for improving the security of the already officially performed determination of the site-specific hydrogen isotope content in wine ethanol by²H-NMR.     

Conversion of oxygenated and hydrocarbon molecules to particulate matter using stable isotopes as tracers

Fuels are continuing to be derived from fossil sources, but as production technology improves, biofuels and synthetic fuels are expected to emerge as scalable long-term sources of liquid fuels. Efforts are being made to ensure that this next-generation of fuels is cleaner burning than the last. In order to inform the production and processing of cleaner burning fuels, more needs to be known about how molecular structure influences the formation of pollutant emissions. Reducing airborne quantities of particulate matter (PM) is of particular interest for human health and the environment. This publication presents a ¹³C labelling technique, which has been developed and applied to identify the influence of local molecular structure on the formation of PM. The paper applied the technique based on the ¹³C stable isotope to trace the conversion of individual carbon atoms to PM in the case of several oxygenated and hydrocarbon molecules. A laminar tube reactor facility has been used for generating and collecting samples of PM under pyrolysis conditions. A number of single-component oxygenated and hydrocarbons (ethanol, propanol, pentanol, cyclopentanol, ethyl acetate, and toluene) have been enriched with ¹³C at specific carbon atom locations and the ¹³C/¹²C isotope ratios of PM were measured. The contribution to PM of particular carbon atoms within a molecule was evaluated, and the results shed new light of how individual carbon atoms in a molecule convert to PM. It was found that the conversion to PM of different atoms within a molecule varies widely, depending on the identity of their neighbouring moiety. Furthermore, it was shown that oxygen-containing functional groups have a significant influence on the formation of particulates, partly through a reduction in the conversion to PM of carbon atoms, which are adjacent to oxygen atoms.     

Authenticity control and identification of origin of synthetic creatine-monohydrate by isotope ratio mass spectrometry

Synthetic creatine-monohydrate is consumed as a dietary supplement (DS) worldwide. Up to now no analytical technique for authenticity control or identification of origin of creatine-monohydrate products has been reported. Isotope ratio mass spectrometry (IRMS) of different creatine-monohydrate samples was performed allowing to differentiate between production sites located either in Germany or China. The results obtained indicate that the carbon and nitrogen isotopic composition of industrially synthesised creatine-monohydrate depends on the isotopic composition of the raw materials rather than on different production processes. Statistical pattern recognition of isotope data allowed for classification of most of the creatine-monohydrates sold as DS into German and non-German origin, respectively. Four DS, cross-contaminated with anabolic androgenic steroids (AAS), could not be allocated to a single producer. This suggests that contamination with AAS did not occur during synthesis, but during handling by the distributors.     

Characterisation of authentic Italian extra-virgin olive oils by stable isotope ratios of C,O and H and mineral composition

The paper shows the isotopic ratios (¹³C/¹²C, D/H, ¹⁸O/¹⁶O) in oil and extracted glycerol and the mineral composition of authentic PDO and PGI Italian extra-virgin olive oils, officially collected from 2000 to 2005 (N=539$N=539$) to establish a national databank. ¹³C/¹²C and ¹⁸O/¹⁶O increased from Trentino to Sicily, each year distinguishing Northern Italy from Sicily and Calabria. Significant differences were found among the years and in some cases also between PDOs from the same region. ¹³C/¹²C and ¹⁸O/¹⁶O in bulk oil were significantly correlated with those in glycerol. D/H, measured in 2005 for the first time in oil, showed promising geographical discrimination capability. The content of 26 elements – Li, Rb, Cs, La, Ce and Yb rarely reported in the literature – was measured in well settled 2005 oils after ultrasound acid extraction.