Gas chromatography mass spectrometry based metabolic profiling reveals biomarkers involved in rice-gall midge interactions

The Asian rice gall midge（Orseolia oryzae WoodMason） is a serious pest of rice that causes huge loss in yield.While feeding inside the susceptible host,maggots secrete substances that facilitate the formation of a hollow tube-like structure called gall and prevent panicle formation.The present investigation was carried out to get an account of biochemical changes occurring in the rice plant upon gall midge feeding.Metabolic profiling of host tissues from three rice varieties,namely,TN1,Kavya,and RP2068,exposed to gall midge biotype 1（GMB1）,was carried out using gas chromatography mass spectrometry（GC-MS）.TN1 and GMB1 represented compatible interaction,while Kavya and GMB1 as well as RP2068 and GMB1 represented incompatible interactions.The current study identified several metabolites that could be grouped as resistance,susceptibility,infestation,and host features based on their relative abundance.These may be regarded as biomarkers for insect-plant interaction in general and rice-gall midge interaction in particular.

Pyrolysis-Gas Chromatography/Mass Spectrometry for Microstructure and Pyrolysis Pathway of Polyester-Polyether Multiblock Copolymer

The composition and sequence distribution of monomeric units in polyester polyether multiblock copolymer were studied by pyrolysis? gas chromatography (PGC) and pyrolysis gas chromatography/mass spectrometry (PGC/MS). PGC was applied to study the F t curve of the multiblock copolymer and PGC/MS was used to separate and identify the pyrolyzates. DTA experiment was used to study the decomposition temperature. The results show that the beginning point of elastomer’s decomposition was about 300?℃ and the decomposition temperature of most of the sample was 550?℃. Many pyrolyzates were produced because of the breaking of weak bonds in the sample. The possible microstructure was verified and the pyrolysis pathway of the copolymer was investigated.

Extraction of essential oil from shaddock peel and analysis of its components by gas chromatography-mass spectrometry

Essential oil, with more than thirty kinds of compounds separated and identified by gas chromatography-mass spectrometry, was extracted from Shatian shaddock peel and Sweet shaddock peel by squeeze-steam distillation and direct steam distillation method. Among their composition, the main components are terpene compounds, which account for 93.926% (mass fraction, the same below) and 85.843% of essential oils extracted from Shatian shaddock peel and Sweet shaddock peel, respectively. Although nootkatone is the major contributor of shaddock characteristic scent, and its contents are 1.069% and 1.749% of essential oils from Sweet shaddock peel and Shatian shaddock peel, respectively. The results show that squeeze-steam distillation gives higher yield and good quality of essential oil and the compositions of essential oils from two kinds of shaddock peels are different, but the main contributors of the shaddock scent are the same.

Headspace Solid-Phase Micro-Extraction Gas Chromatography/Mass Spectrometry(HS-SPME-GC/MS)-Based Untargeted Metabolomics Analysis for Comparing the Volatile Components from 12 Panax Herbal Medicines

Quality control of ginseng currently is mainly based on ginsenoside analysis,but rarely focuses on the volatile organic components.In the current work,an untargeted metabolomics approach,by headspace solid-phase micro-extraction gas chromatography/mass spectrometry(HS-SPME-GC/MS),was elaborated and further employed to holistically compare the compositional difference of the volatile components simultaneously from 12 Panax herbal medicines,which included P.ginseng(PG),P.quinquefolius(PQ),P.notoginseng(PN),red ginseng(PGR),P.ginseng leaf(PGL),P.quinquefolius leaf(PQL),P.notoginseng leaf(PNL),P.ginseng flower(PGF),P.quinquefolius flower(PQF),P.notoginseng flower(PNF),P.japonicus(PJ),and P.japonicus var.major(PJvm).Chromatographic separation was performed on an HP-5MS elastic quartz capillary column using helium as the carrier gas,enabling good resolution within 1 h.We were able to characterize totally 259 volatile compounds,including 82 terpenes(T),46 alcohols(Alc),29 ketones(K),25 aldehydes(Ald),21 esters(E),and the others.By analyzing 90 batches of ginseng samples based on the untargeted metabolomics workflows,236 differential ions were unveiled,and accordingly 36 differential volatile components were discovered.It is the first report that simultaneously compares the compositional difference of volatile components among 12 Panax herbal medicines,and useful information is provided for the quality control of ginseng aside from the well-known ginsenosides.

ANALYSIS OF VOLATILE CONSTITUENTS OF CHINESE MEDICINAL HERBS BY FLASH DISTILLATION/CAPILLARY GAS CHROMATOGRAPHY/MASS SPECTROMETRY

In present work,the volatile constituents of Curcuma longa L.,A.lancea (Thunb.) DC.,Foeniculum vulgare Mill,and Cinnamomun cassia Presl.have been analyzed by flash distillation/capillary gas chro-matography/mass spectrometry.The results are consistent with those obtained by conventional steam distillation extraction method.The optimum condition of flash distillation has been studied.The experimental results showed that this new technique proved to be a simple,rapid and efficient tool for microanalysis of volatile constituents of Chinese medicinal herbs.

Metabolomic studies of human gastric cancer:Review

Metabolomics is a field of study in systems biology that involves the identification and quantification of metabolites present in a biological system. Analyzing metabolic differences between unperturbed and perturbed networks, such as cancerous and noncancerous samples, can provide insight into underlying disease pathology, disease prognosis and diagnosis. Despite the large number of review articles concerning metabolomics and its application in cancer research, biomarker and drug discovery, these reviews do not focus on a specific type of cancer. Metabolomics may provide biomarkers useful for identification of early stage gastric cancer, potentially addressing an important clinical need. Here, we present a short review on metabolomics as a tool for biomarker discovery in human gastric cancer, with a primary focus on its use as a predictor of anticancer drug chemosensitivity, diagnosis, prognosis, and metastasis.

Prediction of gastric cancer metastasis through urinary metabolomic investigation using GC/MS

AIM:To gain new insights into tumor metabolism and to identify possible biomarkers with potential diagnostic values to predict tumor metastasis.METHODS:Human gastric cancer SGC-7901 cells were implanted into 24 severe combined immune deficiency (SCID) mice,which were randomly divided into metastasis group (n=8),non-metastasis group (n=8),and normal group (n=8).Urinary metabolomic information was obtained by gas chromatography/mass spectrometry (GC/MS).RESULTS:There were significant metabolic differences among the three groups (t test,P < 0.05).Ten selected metabolites were different between normal and cancer groups (non-metastasis and metastasis groups),and seven metabolites were also different between non-metastasis and metastasis groups.Two diagnostic models for gastric cancer and metastasis were constructed respectively by the principal component analysis (PCA).These PCA models were confirmed by corresponding receiver operating characteristic analysis (area under the curve=1.00).CONCLUSION:The urinary metabolomic profile is different,and the selected metabolites might be instructive to clinical diagnosis or screening metastasis for gastric cancer.

Response to weaning and dietary L-glutamine supplementation:metabolomic analysis in piglets by gas chromatography/mass spectrometry

A novel metabolomic method based on gas chromatography/mass spectrometry （GC-MS） was applied to determine the metabolites in the serum of piglets in response to weaning and dietary L-glutamine （Gin） supplementation. Thirty-six 21-d-old piglets were randomly assigned into three groups. One group continued to suckle from the sows （suckling group）, whereas the other two groups were weaned and their diets were supplemented with 1% （w/w） Gin or isonitrogenous L-alanine, respectively, representing Gin group or control group. Serum samples were collected to characterize metabolites after a 7-d treatment. Results showed that twenty metabolites were down-regulated significantly （P〈0.05） in control piglets compared with suckling ones. These data demonstrated that early weaning causes a wide range of metabolic changes across arginine and proline metabolism, aminosugar and nucleotide metabolism, galactose metabolism, glycerophospholipid metabolism, biosynthesis of unsaturated fatty acid, and fatty acid metabolism. Dietary Gin supplementation increased the levels of creatinine, D-xylose, 2-hydroxybutyric acid, palmitelaidic acid, and a-L-galactofuranose （P〈0.05） in eady weaned piglets, and were involved in the arginine and proline metabolism, carbohydrate metabolism, and fatty acid metabolism. A leave-one-out cross-validation of random forest analysis indicated that creatinine was the most important metabolite among the three groups. Notably, the concentration of creatinine in control piglets was decreased （P=0.00001） compared to the suckling piglets, and increased （P=0.0003） in Gin-supplemented piglets. A correlation network for weaned and suckling piglets revealed that early weaning changed the metabolic pathways, leading to the abnormality of carbohydrate metabolism, amino acid metabolism, and lipid metabolism, which could be partially improved by dietary Gin supplementation. These findings provide fresh insight into the complex metabolic changes in response to early weaning and dietary Gin supplementation in piglets.

Qualitative Analysis of A Sulfur-fumigated Chinese Herbal Medicine by Comprehensive Two-Dimensional Gas Chromatography and High-Resolution Time of Flight MassSpectrometry Using Colorized Fuzzy Difference Data Processing

To investigate the chemical transformation of volatile compounds in sulfur-fumigated Radix Angelicae Sinensis. A comprehensive two-dimensional gas chromatography (GCxGC) and high-resolution time-of-flight mass spectrometry (HR-TOF/MS) with colorized fuzzy difference (CFD) method was used to investigate the effect of sulfur-fumigation on the volatile components from Radix Angelicae Sinensis. Twenty-five compounds that were found in sun-dried samples disappeared in sulfur-fumigated samples. Seventeen volatile components including two sulfur-containing compounds were newly generated for the first time in volatile oils of sulfur-fumigated Radix Angelicae Sinensis. The strategy can be successfully applied to rapidly and holistically discriminate sun-dried and sulfur-fumigated Radix Angelicae Sinensis. GCxGC-HR-TOF/MS based CFD is a powerful and feasible approach for the global quality evaluation of Radix Angelicae Sinensis as well as other herbal medicines.

Analysis of nitrobenzene compounds in water and soil samples by graphene composite-based solid-phase microextraction coupled with gas chromatography–mass spectrometry

In this work, solid-phase microextraction coupled with gas chromatography–mass spectrometry was developed to determine trace levels of nitrobenzene compounds in water and soil samples. Graphene was chosen as the extraction material and its composite was coated on a stainless steel wire through sol–gel technique for the solid phase microextraction. The key parameters influencing the extraction efficiency were optimized. Under the optimal conditions, the linearity for the compounds was observed in the range of 0.02–15.0 mg/L for water samples, and 0.2–60.0 mg/kg for soil samples, with the correlation coefficients（r） of 0.9966–0.9987. The limits of detection of the method were 0.0025–0.005 mg/L for water samples, and 0.02–0.04 mg/kg for soil samples. The recoveries for the spiked samples were in the range of 72.0%–113.2%, and the precision, expressed as the relative standard deviations, was less than 12.1%.

Determination of selected semi-volatile organic compounds in water using automated online solid-phase extraction with large-volume injection/gas chromatography/mass spectrometry

A rapid,sensitive,and cost-effective analyticalmethod was developed for the analysis of selected semivolatileorganic compounds in water.The method used anautomated online solid-phase extraction technique coupledwith programmed-temperature vaporization large-volumeinjection gas chromatography/mass spectrometry.Thewater samples were extracted by using a fully automatedmobile rack system based on x-y-z robotic techniquesusing syringes and disposable 96-well extraction plates.The method was validated for the analysis of 30 semivolatileanalytes in drinking water,groundwater,andsurface water.For a sample volume of 10 mL,the linearcalibrations ranged from 0.01 or 0.05 to 2.5μg·L^(-1),and themethod detection limits were less than 0.1μg·L^(-1).For thereagent water samples fortified at 1.0μg·L^(-1)and2.0μg·L^(-1),the obtained mean absolute recoveries were70%-130%with relative standard deviations of less than20%for most analytes.For the drinking water,groundwater,and surface water samples fortified at 1.0μg·L^(-1),theobtained mean absolute recoveries were 50%-130%withrelative standard deviations of less than 20%for mostanalytes.The new method demonstrated three advantages:1)no manipulation except the fortification of surrogatestandards prior to extraction;2)significant cost reductionassociated with sample collection,shipping,storage,andpreparation;and 3)reduced exposure to hazardous solventsand other chemicals.As a result,this new automatedmethod can be used as an effective approach for screeningand/or compliance monitoring of selected semi-volatileorganic compounds in water.

Gas Chromatography–Mass Spectrometry for Quantitative and Qualitative Analysis of Essential Oil from Curcuma wenyujin Rhizomes

Objectives:A rapid and sensitive gas chromatography–mass spectrometry(GC–MS)method for quantitative and qualitative analysis of essential oil from Curcuma wenyujin rhizomes was established.Methods:The essential oil of C.wenyujin rhizomes was extracted by supercritical CO2 extraction(SFE).Six main bioactive compounds(eucalyptol,β-elemene,curzerene,germacrone,curdione,and curcumol)were analyzed in selected ion monitoring mode(SIM).Results:Curzerene is not originally present in C.wenyujin rhizomes,but is a product of the transformation of furanodiene at high temperature.The six target components demonstrated good linearity(R2>0.9979)over a relatively wide concentration range.The interday and intraday variations had relative standard deviation values less than 5%and the average recovery ranged from 96.95%to 100.04%.The limit of quantitation ranged from 0.032 to 0.235μg/mL.The developed method was successfully used to analyze the six compounds in 17 samples collected from different origins.Significant variation was observed for the concentrations of the six compounds.In addition,51 constituents were identified in C.wenyujin rhizome essential oil,consisting of 87.66%of the total essential oil,including curdione,curzerene,dehydrocurdione,germacrone,1,4-bis(2-benzimidazoyl)benzene,neocurdione,curcumenone,andβ-elemene.Conclusions:The proposed method will be useful in the quality control of C.wenyujin rhizome essential oil production.

A Gas Chromatography-Mass Spectrometry‑Based Metabonomic Study on Estimation of Toxicant in Rats

The aim of this study was to develop a gas chromatography‑mass spectrometry(GC‑MS)‑based metabolomics method to distinguish different kinds of poisons in the blood.We examined the changes in blood metabolites using GC‑MS following administration of four different poisons(paraquat,dichlorvos,aconitine,and sodium nitrite).The data were analyzed with orthogonal partial least squares.Then,total and single differential metabolite profiles were evaluated with support vector machine(SVM)models.The results showed that various metabolites(5‑ketone proline,1,5‑anhydrohexitol,lactic acid,glycine 2,2‑furoic acid,and 3‑hydroxybutyric acid)were differential between the experimental groups and the control groups.The accuracy rates of the SVM models established using total and single differential metabolites were 80%and 100%,respectively.In conclusion,we successfully developed a poison screening method.The established SVM models can distinguish four kinds of poisons and could be used to establish a complete poison metabonomic information database.Furthermore,some of the metabolites could be biomarkers of these poisons.Finally,both the models and potential biomarkers may reduce the time required for poison detection and provide direction for solving cases and auxiliary diagnosis.

Determination of Methadone and Eight New Psychoactive Substances in Hair Samples by Gas Chromatography/Mass Spectrometry

Many new psychoactive substances(NPSs)with different chemical structures have emerged in the illicit drug market in the last decade.The present work was aimed at the development of a simple method in gas chromatography/mass spectrometry(MS)for the determination of NPS of different classes,the use of cannabinoids,and,at the same time,the evaluation of methadone therapy in hair matrix,within our routine analysis control for methadone treatment or from autopsy cases.The determination of synthetic cannabinoids and methadone therapy used an extraction method based on incubation in concentrated sodium hydroxide(NaOH)solution,providing a dissolution of the keratin matrix.The described method was applied on 15 authentic specimens from our cases:five showed the presence of methadone and 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine(EDDP).The described method can be useful not only in the forensic investigation of NPS-related addiction histories but also in epidemiological and retrospective studies on the spread of NPS among specific safety-sensitive social workers.The GC instrument was an Agilent 7820A(Agilent Technologies,Santa Clara,CA,USA),and the detection system was an Agilent 5977B single quadrupole MS operating in selective ion monitoring mode.Wlidation parameters such as limit of detections(LODs),limit of quantifications(LOQs),repeatability,accuracy,and linearity were satisfactory for its application on real specimens.LODs,LOQs,2?2,%CY standard deviation,and the mean concentration for the analyzed compounds are reported in Table lb.Accuracy and repeatability were acceptable for all the analytes at their respective LOQs.Recovery experiments varied from 58.3%to 103.0%,thus allowing the application on authentic specimens.The described method can be useful not only in the forensic investigation ofNPS-related addiction histories but also in epidemiological and retrospective studies on the spread of NPS among specific safety-sensitive social workers,such as drivers.

固相萃取-GC-MS法测定饲料中的沙丁胺醇

沙丁胺醇(salbutamol),化学名称1-(4-羟基-3-羟甲基苯基)-2-(叔丁氨基)乙醇(结构式如图1所示),俗称舒喘宁,属于β-兴奋剂类药物的一种,临床上用于治疗支气管哮喘.同时沙丁胺醇同克伦特罗(瘦肉精)一样还具有提高饲料的转化率,促进动物生长的作用.但是,这种药物容易在动物内脏、组织中蓄积残留,有很大的副作用.……

Sex Pheromone Components of the Female Black Cutworm Moth in China: Identification and Field Trials

The sex pheromone blend of a China strain of the black cutworm moth Agrotis ypsilon （Rottemberg） （Lepidoptera： Noctuidae） was investigated. Chemical analysis of pheromone gland extracts of 3-day-old females showed that individual isolated glands contained only very small amounts of pheromone. The high-resolution gas chromatography combined with mass spectrometry （GC-MS） analysis showed the presence of Cis-7-dodecenyl acetate （Z7-12：Ac, A）, Cis-9-tetradecenyl acetate （Z9-14：Ac, B）, Cis- 11-hexadecenyl acetate （Z 11 - 16 ：Ac, C）, Cis-8-dodecenyl acetate （Z8-12：Ac, E） and Cis-5-decenyl acetate （Z5-10：Ac, D） in biologically active pheromone gland extracts. An extract of one gland from a day 3 female gave the following values for the gland components： 0.245±0.098ng for Z7-12：Ac, 0.080±0.031ng for Z9-14：Ac, 0.089±0.033ng for Z11-16：Ac, 0.085±0.031ng for Z5-10：Ac, 0.105±0.065ng for Z8-12：Ac per female. The percentages of Z7-12：Ac, Z9-14：Ac, Z11-16：Ac, Z5-10：Ac and ZS-12：Ac in pheromone gland extracts from individual females were （meaniSE） 40.451±13.66, 13.176±5.279, 14.943±5.142, 14.392±6.10 and 17.225±9.792 respectively, and the percentages of Z7-12：Ac, Z9-14：Ac and Z11-16：Ac were 58.75±9.429, 18.91±7.539 and 22.34±7.209. Field trials indicated that each single component of sex pheromone was non-effective and captured no males. The lures baited with duality compound of AB （3 ： 1） had a certain attraction to males, the mean captured number was 2.6. The attraction ability of the lures baited with ternary compound of ABC （3 ： 1 ：1） to males added significantly, the mean captured number per trap was 7.40, which was 2.8 times of duality compound of AB （3 ： 1）. The contents of sex pheromone could obviously affect its capture ability to males, the mean captured number was the highest at the dosage of 200 μg.

GC-MS测定家犬血浆中银杏内酯A、B的含量

银杏叶制剂作为治疗和预防动脉粥样硬化的有效药物,越来越为人们关注.银杏叶成分复杂,其中银杏黄酮具有扩张血管,降血脂,改善微循环的作用;银杏内酯是血小板活化因子强拮抗剂,对免疫系统,中枢神经系统,缺血损伤有保护作用,并有抗休克、抗过敏及抗炎作用.由于银杏内酯含量较低,对其进行的药动力学研究较少,且多采用的是非特异性的生物测定方法.……

广防己挥发油的GC-MS指纹图谱研究

防己药材主要分粉防己和木防己两类,木防己包括广防己和汉中防己.广防己为马兜铃科植物广防己Aristolochia fangchi Y.C.WuexL.D.Chou.et S.M.Hwang的干燥根[1],习称"木防己"、"水防己",主产于广东、广西,具有祛风止痛、清热利水之功效[2].……

自动固相微萃取(SPM E)GC-MS、GC-MS-MS法检测环境水中有机磷杀虫剂的研究

固相微萃取(solid-phase microextraction,SPME)是20世纪90年代发展起来的一种样品前处理技术,与传统的液-液提取、液-固提取相比,SPME更适用于提取、浓缩液态或气态的挥发性和半挥发性物质,SPME技术可将采样、萃取、浓缩和样本引入集中于一个步骤完成,尤其随着自动SPME与GC-MS等联用技术的日益完善,使SPME技术优点得到更充分的发挥.……

衍生固相萃取GC-MS检测牛可食组织中克伦特罗的残留量

盐酸克伦特罗(clenbuterol,CLB),俗名"瘦肉精",化学名为"2-[(叔丁氨基)甲基]-4-氨基-3,5-二氯苯甲醇盐酸盐"(相对分子质量313.5),是一种β-兴奋剂[1].近年来动物性产品中CLB残留对人类健康造成的危害和对生态食物链所造成的破坏已经引起高度重视.……