Determination of glyceroltriheptanoate in processed animal by‐products by GC‐FID

The European Regulation concerning animal by‐products (ABPs) established rules on safe use, transportation and disposal of these materials. According to the health risks, the products were sorted in three categories, and the materials belonging to category 1 and 2 (high and intermediate health risk) needed to be permanently marked in order to allow full traceability and avoid their entering in the feed and food chain. The selected marker was glyceroltriheptanoate (GTH) with a minimum permissible level of 250 mg/kg fat fraction. This study presents the implementation and validation of an analytical method for the determination of GTH in processed ABPs using GC‐FID. Two injection systems (split–splitless and programmable temperature vaporization injector) and chromatographic columns were evaluated in order to select the best instrumental conditions. The method was in‐house validated by assessing linearity, precision, trueness, and limit of detection (LOD) and quantification (LOQ). The linearity range was tested from 90 to 2800 mg GTH/kg, the relative SD for repeatability and intermediate precision were, respectively, 1.8 and 2.9%. The mean recovery rate was 99% and the LOD and LOQ were 6.8 and 22.8 mg/kg. In addition, the performance characteristics were compared with those of the reference method developed by the Institute for Reference Materials and Measurements (IRMM) with good agreement. A collection of real samples, obtained from different rendering plants in Italy, were subjected to analysis for the determination of GTH for routine quality controls. Practical applications: After the European Regulation (EC) 1432/2007 that established a minimum added level of GTH to processed ABPs belonging to category 1 and 2 has been put in force, a reliable and simple analytical method became necessary. The Institute for Reference Materials and Measurements (IRMM) of the European Commission developed and validated a methodology based on a GC‐MS instrumentations, used by the official control laboratories. The aim of this study was the implementation of an analytical method using a GC‐FID, a widespread and easy to use instrumentation. This analytical protocol found its application in the processed quality control laboratories for the routine analysis of the GTH added to ABPs, and in particular for materials belonging to category 1 and 2.     

Pyrolysis GC‐MS of chlorinated natural rubber

High‐resolution pyrolysis gas chromatography‐mass spectrometry (HRPyGC‐MS) and Fourier transform infrared spectrometry (FTIR) were used to study the structures of the chlorinated natural rubbers (CNR) prepared by two different processes. The results indicate that the fine structures of CNR prepared from “latex” and “solution” processes are different, whereas their basic structures are similar. The molecule of CNR from the “latex” process contains a few carboxyl and carbonyl groups. The rings on CNR molecular chains should be hexatomic rings. The optimum pyrolytic temperature for CNR is 445°C, with an available range from 386 to 590°C. The characteristic pyrolytic products are cyclohexane homologues. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 199–204, 2003     

Characterization of volatile compounds and triacylglycerol profiles of nut oils using SPME‐GC‐MS and MALDI‐TOF‐MS

Several nut oil varieties mainly used as culinary and overall healthy food ingredients were subject of the present study. Headspace solid‐phase microextraction combined with gas chromatography‐mass spectrometry was employed in order to determine the qualitative composition of volatile compounds. Furthermore, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry was used in order to assess the profiles and relative composition of the prevalent triacylglycerols (TAG) within the oils. The headspace of the majority of oil samples was dominated by high contents of acetic acid (up to 42%) and hexanal (up to 32%). As nut oils are typically gained by cold‐pressing from previously roasted nuts, characteristic pyrazine derivatives as well as degradation products of long‐chain fatty acids were detected. TAG analysis of these oils revealed a quite homogeneous composition dominated by components of the C₅₂ and C₅₄ group composed mainly of oleic (18:1), linoleic (18:2), stearic (18:0) and palmitic (16:0) acid residues representing together between 65 and 95% of the investigated nut oils. The TAG profiles showed characteristic patterns which can be used as ‘fingerprints’ of the genuine oils. Nut oils exhibiting quite similar fatty acid composition (e.g. hazelnut, pistachio and beech oil) could be clearly discriminated based on TAG showing significant differences between the oils.     

Evaluation of the Triglyceride Composition of Pomegranate Seed Oil by RP‐HPLC Followed by GC‐MS

Triglyceride composition and fatty acid profiles of pomegranate seed oil were evaluated by newly developed methods in reverse‐phase‐high performance liquid chromatography (RP‐HPLC) and gas chromatography (GC), respectively. Different compositions of the mobile phase (acetone and acetonitrile) and flow rates for the HPLC system were used to obtain better separation for accurate quantitative analysis. Triglycerides with conjugated fatty acids (CLnAs) were eluted in order of the polarity of their geometrical isomers (c, t, c < t, t, c < t, t, t). The dominant triglyceride was found to be PuPuPu (32.99 %) in pomegranate seed oil, followed by PuPuCa and PuCaCa containing punicic acid and catalpic acid with total triglyceridelevels of 27.72 and 10.11 %, respectively. For fatty acid composition analysis, triglyceride fractions were derivatized into their respective methylesters which were injected into gas chromatography‐mass spectrometry (GC‐MS) to identify and gas chromatography‐flame ionization detector (GC‐FID) to quantify the conjugated fatty acids of each fraction of triglycerides. Punicic acid was found to be dominant (76.57 %) followed by catalpic acid (6.47 %) and β‐eleotearic acid (1.45 %). Pomegranate seed contained greater amounts of conjugated linolenic acids. These results showed that the present study provides more information about the composition of the triglyceride and fatty acid profiles of pomegranate seed oil compared to the reported studies. Therefore, the developed methods in this study can be used for the identification of the triglyceride and fatty acid composition for pomegranate seed oils and some such specials edible oils including CLnA isomers.     

Wax ester fraction of edible oils: Analysis by on‐line LC‐GC‐MS and GC×GC‐FID

The wax ester fraction of various plant oils was isolated by normal‐phase HPLC (NPLC) on‐line coupled to GC via the on‐column interface and applying concurrent eluent evaporation. The esters were analyzed by on‐line NPLC‐GC‐MS and by comprehensive two‐dimensional GC with flame ionization detection (GC×GC‐FID) off‐line combined with NPLC‐GC. GC×GC‐FID enables to group the various classes of wax esters, in particular the phytol esters, geranylgeraniol esters and the straight‐chain esters of palmitic acids and the unsaturated C₁₈ acids. Optimization of the GC×GC columns and the conditions must take into account the limited thermostability of the diterpene esters. Chromatograms are shown for a range of oils, with particular focus on the various classes of wax esters in olive oil and the geranylgeraniol esters 22:0 and 24:0 in a variety of oils.     

Detection of oxysterols in oxidatively modified low density lipoprotein by MALDI‐TOF MS

A simple method for the detection of oxysterols in oxidatively modified LDL (Ox‐LDL) has been developed using MALDI‐TOF MS. To identify the ion peaks of oxysterols, seven major oxysterols in Ox‐LDL (7α‐hydroxycholesterol, 7β‐hydroxycholesterol, 7‐ketocholesterol, 5α,6α‐epoxycholesterol, 5β,6β‐epoxycholesterol, 25‐hydroxychokesterol, (25R)‐26‐hydroxycholesterol), and cholesta‐3,5‐dien‐7‐one were analyzed by MALDI‐TOF MS. Among these oxysterols, 7‐ketocholesterol, a very abundant oxysterol in Ox‐LDL, was found to show a characteristic peak of [M + H]⁺ at m/z 401. Cholesta‐3,5‐dien‐7‐one, which is known as a degradation product of 7‐ketocholesterol upon saponification of Ox‐LDL, gave a major peak of [M + H]⁺ at m/z 383. In contrast, other oxysterols showed similar peak patterns at m/z 367 and 385. These results were applied to the analysis of Ox‐LDL by MALDI‐TOF MS after saponification and hexane‐extraction, detecting ion peaks at m/z 367, 383, 385, and 401. This MALDI‐TOF MS method has a potential as a simple tool to show the presence of oxysterols in Ox‐LDL without derivatization and chromatographic separation.     

Determination of Origin of Commercial Flavored Rapeseed Oil by the Pattern of Volatile Compounds Obtained via GC–MS and Flash GC Electronic Nose

Flavored rapeseed oil (FRO) is a typical hot‐pressed oil and is widely consumed in China due to its strong characteristic flavor and intensive color. In this study, volatile profiles of 33 representative commercial rapeseed oils in China are characterized by gas chromatography‐mass spectrometry (GC‐MS) and flash gas chromatography (GC) electronic nose system. 51 volatile compounds are identified and the nitriles (methallyl cyanide and 5‐cyano‐1‐pentene), aldehydes (nonanal, 3‐furaldehyde, and 5‐methyl‐2‐furancarboxaldehyde), alcohols (1,5‐hexadien‐3‐ol, 2‐furanmethanol, and phenylethyl alcohol), and pyrazines (2,5‐dimethyl‐pyrazine and 2,6‐dimethyl‐pyrazine) are the major volatile compounds in FROs. Glucosinolate degradation products account for the highest proportion of these volatiles, which are found to have a positive correlation with the erucic acid content (R² = 0.796, p < 0.01). FRO from Sichuan province in the southwest of China can be characterized by the obvious distinctions in flash GC electronic nose combined with principal component analysis, which indicates that the flash GC electronic nose can be used as a promising method to identify the origins of FRO. Practical Applications: This work is helpful for expanding the knowledge of volatiles of commercial flavored rapeseed oil. The data can also serve as a basis for the quality assessment of hot‐pressed rapeseed oil. Meanwhile, the flash GC electronic nose combined with principal component analysis can be used as a promising method for the classification of flavor rapeseed oil production areas.     

Cholesterol oxidation in some processed fish products

Numerous foods of animal origin are reported to contain considerable levels of cholesterol oxidation products (COP); however, very few reports are available on fish products. Levels of COP were assessed in samples of fish roe, fish oil, and fish meal. Among the fish roe samples, the smoked cod roe had the highest amount of COP, 93 μg/g lipids. Refined and bleached menhaden oil had 8 μg/g, and two experimental alkali-refined, bleached, and deodorized herring fish oil samples contained similar amounts of COP. The range of total COP in the three fish meal samples ranged from 50 to 78 μg/g fish meal. Generally, processed fish roe contained high amounts of COP compared with refined fish oils, which had very low amounts of COP. Fish meal samples had very high amounts of COP.     

Lipid Oxidation and Degradation Products in Raw Materials: Low‐Fat Topical Skin‐Care Formulations

Topical skin formulations with a lipid content below 15% were stored for 6 months at 5, 20, or 40 °C or for 2 weeks at 50 °C in darkness or at 20 °C with exposure to light for 6 months. The volatile lipid‐oxidation compounds formed during this storage period were compared to those formed in the raw materials during 3 months of accelerated stability storage at 40 °C. The volatile compounds were collected by dynamic headspace and analyzed using gas chromatography–mass spectrometry. It was possible to link eight out of nine volatile compounds detected during storage of topical skin formulations to the raw materials. In addition, a possible link between the appearance of butane nitrile and the decomposition of an initiator used for polyacrylate crosspolymer‐6 production was observed. The polymer may originate from texture modifiers added to the topical skin formulation or from plastics used for packaging of topical skin formulations. Furthermore, six well‐known lipid‐oxidation and nonenzymatic browning products were suggested to originate from the two raw materials, tricaprylin/tricaprin and coconut oil.     

Processed animal products with emphasis on polyunsaturated fatty acid content

The fat composition of processed fish and meat varies due to the source of the animal diet and to the fats used during processing. The aim of this study was to analyse the fatty acid profiles in some commonly available fish and meat fast foods. Variation between similar products from different brands indicated the use of different fat sources during processing. Especially in fish products, a high variation was found in the n‐6/n‐3 ratio, being up to more than 400‐fold higher than in plain fish, which might be of special concern in the evaluation of diet‐related health claims. Many products showed considerable differences compared to those included in the official database used for calculation of dietary intake. This leads to the conclusion that the fat sources used during processing of fast food should be reported and available to the consumers. I nterdisciplinary dialogue between all sectors involved in food production, processing and health care is proposed to evaluate optimal development of fast foods with nutritionally favourable fat composition.     

PY‐GC/MS an effective technique to characterizing of degradation mechanism of poly (L‐lactide) in the different environment

The biotic and abiotic degradation of poly (L‐lactide) (PLLA) has been studied with pyrolysis gas chromatography mass spectrometry (Py‐GC‐MS). A mixed culture of compost micro‐organisms was used as the biotic medium. Size‐exclusion chromatography (SEC), gas chromatography‐mass spectrometry (GC‐MS), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) were utilized to monitor the degradation and degradation mechanism. Differences in pH, molecular weight, surface structure, and degradation mechanisms were noted between sample aged in biotic and abiotic medium. Using fractionated Py‐GC‐MS at 400 and 500°C, acetaldehyde, acrylic acid, lactoyl acrylic acid, two lactide isomers, and cyclic oligomers up to the pentamer were identified as thermal decomposition products of PLA as well as some other not completely identified products. The ratio of meso‐lactide to L‐lactide was lower in the sample aged in the biotic media than the abiotic media. This is a result of the preference of the micro‐organisms for L‐form of lactic acid and lactoyl lactic acid rather than the D‐form that in turn influences the formation and the amounts of meso and D,L‐lactide during the pyrolysis. Based on SEM micrographs, it was shown that degradation in the biotic medium proceeded mainly via a surface erosion mechanism, whereas bulk erosion was the predominant degradation mechanism in the abiotic medium. The SEC and Py‐GC‐MS data indicate that degradation was faster in the biotic than in the abiotic sample. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2369–2378, 2000     

MS在测定天然产物中的研究进展

天然产物的使用由来已久,关于其成分的研究也受到了人们的注视。但是其成分复杂,检测困难,因此现代分析仪器的迅速发展为其带来了相当大的方便。本文重点介绍MS在天然产物中的应用及新的研究成果。