Determination of 14 Organophosphorus Pesticide Residues in Mutton by Gel Permeation Chromatography-Gas Chromatography-Mass Spectrometry(GPC-GC-MS)

[Objectives]This study was conducted to purify mutton samples by gel permeation chromatography(GPC).[Methods]Fourteen organophosphorus pesticide residues in samples were qualitatively and quantitatively analyzed by gas chromatography-mass spectrometry(GC-MS)in selective ion scanning mode(SIM).[Results]The organophosphorus pesticide standard solutions showed good linearity in the mass concentration range of 0.1-10.0μg/ml with correlation coefficients(r)not lower than 0.999,and the detection limits(S=3 N)ranged from 0.01 to 0.05 mg/kg.The average recovery values were in the range of 80.2%-99.7%,with relative standard deviations(RSDs,n=3)in the range of 1.8%-6.3%,at the addition levels of 0.5,1.0 and 2.0 mg/kg.[Conclusions]The method is simple,sensitive and accurate,and can be used for the determination of organophosphorus pesticide residues in mutton.

Chemical profiling of bioactive compounds in the methanolic extract of wild leaf and callus of Vitex negundo using gas chromatographymass spectrometry

BACKGROUND The investigation of plant-based therapeutic agents in medicinal plants has revealed their presence in the extracts and provides the vision to formulate novel techniques for drug therapy.Vitex negundo(V.negundo),a perennial herb belonging to the Varbanaceae family,is extensively used in conventional medication.AIM To determine the existence of therapeutic components in leaf and callus extracts from wild V.negundo plants using gas chromatography-mass spectrometry(GCMS).METHODS In this study,we conducted GC-MS on wild plant leaf extracts and correlated the presence of constituents with those in callus extracts.Various growth regulators such as 6-benzylaminopurine(BAP),2,4-dichlorophenoxyacetic acid(2,4-D),α-naphthylacetic acid(NAA),and di-phenylurea(DPU)were added to plant leaves and in-vitro callus and grown on MS medium.RESULTS The results clearly indicated that the addition of BAP(2.0 mg/L),2,4-D(0.2 mg/mL),DPU(2.0 mg/L)and 2,4-D(0.2 mg/mL)in MS medium resulted in rapid callus development.The plant profile of Vitex extracts by GC-MS analysis showed that 24,10,and 14 bioactive constituents were detected in the methanolic extract of leaf,green callus and the methanolic extract of white loose callus,respectively.CONCLUSION Octadecadienoic acid,hexadecanoic acid and methyl ester were the major constituents in the leaf and callus methanolic extract.Octadecadienoic acid was the most common constituent in all samples.The maximum concentration of octadecadienoic acid in leaves,green callus and white loose callus was 21.93%,47.79%and 40.38%,respectively.These findings demonstrate that the concentration of octadecadienoic acid doubles in-vitro compared to in-vivo.In addition to octadecadienoic acid;butyric acid,benzene,1-methoxy-4-(1-propenyl),dospan,tridecanedialdehyde,methylcyclohexenylbutanol,chlorpyrifos,n-secondary terpene diester,anflunine and other important active compounds were also detected.All these components were only available in callus formed in-vitro.This study showed that the callus contained additional botanical characteristics compared with wild plants.Due to the presence of numerous bioactive compounds,the medical use of Vitex for various diseases has been accepted and the plant is considered an important source of therapeutics for research and development.

Mechanism of Cinnamomum camphora essential oil for analgesia based on gas chromatography-mass spectrometry integrated network pharmacology

This study aims to explore the analgesic ingredients and mechanism of Cinnamomum camphora essential oil(CCEO).The constituents in CCEO were characterized qualitatively by gas chromatography-mass spectrometry.Targets related to active ingredients were collected by PubChem and Swiss Target Prediction.Targets related to pain were screened by TTD and OMIM database,and compound-target network was established by Cytoscape software.Gene ontology(GO)function and Kyoto encyclopedia of genes and genomes(KEGG)pathway enrichment analysis of targets were carried out by DAVID database.Protein-protein interaction(PPI)network was established and analyzed by STRING database.Molecular docking method was used to verify the interaction between main components and relevant core targets.A total of 13 compounds were identified in CCEO,and 58 related targets were predicted.GO function enrichment analysis revealed that the selected targets were mainly involved in biological processes such as chemical synaptic transmission and molecular function such as neurotransmitter receptor activity;24 signal pathways were screened by KEGG pathway enrichment analysis,including neuroactive ligand-receptor interaction,retrograde endocannabinoid signaling and calcium signaling pathway.Docking results showed that the main constituents had certain affinities with the key targets.The active ingredients in CCEO regulated multiple signaling pathways to ameliorate pain through AR,ACHE,ESR1,GABRG2,PTGS2 and PPARγ.

Simultaneous Determination of 8 Pesticide Residues in Green Tea Based on Gas Chromatography-mass Spectrometry

To improve pesticide residues detection efficiency in tea, simultaneous de- termination of eight pesticide residues in green tea was developed based on gas chromatography-mass spectrometry （GC-MS）. The results showed that, - detected by the GC-MS under following conditions： acetonitrile as extraction and elution solvent, activated carbon and PSA tandem column as the stationary phase, elution volume of 12 ml the relationship between peak area and concentration of each residue （ametryn in the range of 0-100 pg/L, napropamide in the range of 0-10 000 gg/L, other pesticides in the range of 0-1 000 tJg/L） were linearly related, and their corre- lation coefficients were all greater than 0.999. The recovery rate the pesticides added to tea sample at legal concentration limits ranged from 73.6% to 116.8%, and the relative standard deviation from 1.47% to 15.58%. The new method we de- veloped is sensitive, specific and anti-interference, and thus provides test basis for the development of pesticide matrix reference materials in tea.

Simultaneous Determination of Hexoestrol, Diethylstilbestrol, Estrone and 17-Beta-estradiol in Feed by Gas Chromatography-mass Spectrometry

A method was developed for the simultaneous determination of four kinds of estrogens （hexoestrol, diethylstilbestrol, estrone, and 17-beta-estradiol） in feed by gas chromatography-mass spectrometry （GC-MS）. After the sample was extracted by ethyl ether and cleaned-up on HLB phase extraction column, four kinds of estrogens were derived and quantified in gas chromatographymass spectrometry. The results showed that the linear detectable ranged from 2.5 ng· mL-1 to 250 ng· mL-1for hexoestrol and from 5 ng· mL-1 to 500 ng· mL-1 for three other estrogens with the correlation coefficients （R2） were no less than 0.990. The recoveries were in the range of 76.34%-96.33% and the relative standard deviation was no more than 22.7%. The limits of quantitation （LOQ） for all analytics were between 10 ug· kg^-1 and 20 ug· kg^-1. The method was accurate and sensitive and could meet the actual requirements for the analyses of feed samples.

Analysis of volatile chemical components of Radix Paeoniae Rubra by gas chromatography-mass spectrometry and chemometric resolution

The volatile chemical components of Radix Paeoniae Rubra (RPR) were analyzed by gas chromatography-mass spectrometry with the method of heuristic evolving latent projections and overall volume integration. The results show that 38 volatile chemical components of RPR are determined, accounting for 95.21% of total contents of volatile chemical components of RPR. The main volatile chemical components of RPR are (Z, Z)-9,12-octadecadienoic acid, n-hexadecanoic acid, 2-hydroxy- benzaldehyde, 1-(2-hydroxy-4-methoxyphenyl)-ethanone, 6,6-dimethyl-bicyclo[3.1.1] heptane-2-methanol, 4,7-dimethyl-benzofuran, 4-(1-methylethenyl)-1-cyclohexene-1-carboxaldehyde, and cyclohexadecane.

Comparative analysis of essential oils found in Rhizomes Curcumae and Radix Curcumae by gas chromatography-mass spectrometry

A comparison of the volatile compounds in Rhizomes Curcumae （Ezhu） and Radix Curcumae （Yujin） was undertaken using gas chromatography mass spectrometi-y （GC-MS）. Ultrasonic extraction and GC-MS methods were developed for the simultaneous determination of five sesquiterpenes, namely, α-pinene, β-elemene, curcumol, germacrone and curdione, in Ezhu and Yunjin. Good linearity （r〉0.999） and high inter-day precision were observed over the investigated concentration ranges. The validated method was successfully used for the simultaneous determination of five sesquiterpenes in Ezhu and Yujin. The quantitative method can be effectively used to evaluate and monitor the quality of Chinese curcuma in clinical use.

Volatile components of Rhizoma Alpiniae Officinarum using three different extraction methods combined with gas chromatography-mass spectrometry

Volatile components from Rhizoma Alpiniae Officinarum were respectively extracted by three methods including hydrodistillation, headspace solid-phase microextraction （HS-SPME） and diethyl ether extraction. A total of 40 （hydrodistillation）, 32 （HS-SPME） and 37 （diethyl ether extraction） compounds were respectively identified by gas chromatography-mass spectrometry （GC/MS） and 22 compounds were overlapped, including β-farnesene, 7-muurolene, 2,6-dimethyl-6- （4-methyl-3-pentenyl）bicyclo[3.1.1]hept-2-ene, eucalyptol and cadina-1（10）, 4-diene and so forth, varying in relative contents. HS-SPME is fast, sample saving and solvent-free and it also can achieve similar profiles as those from hydrodistillation and solvent extraction. Therefore, it can be the priority for extracting volatile components from medicinal plants.

Rapid and simultaneous determination of ten off-flavor compounds in water by headspace solid phase microextraction and gas chromatography-mass spectrometry

A simple and sensitive analytical procedure for the determination of multi-component compounds in water samples was developed and optimized using the headspace solid-phase microextraction(HSSPME) coupled with gas chromatography-mass spectrometry(GC-MS). Ten off-flavor compounds, including geosmin(GSM), 2-methylisoborneol(2-MIB), 2-isopropyl-3-methoxypyrazine(IPMP), 2-isobutyl-3-methoxypyrazine(IBMP), β-ionone, trans-2,cis-6-nonadienal(NDE), 2,3,4-trichloroanisole(2,3,4-TCA), 2,3,6-trichroloanisole(2,3,6-TCA), 2,4,6-trichloroanisole(2,4,6-TCA), and 2,4,6-tribromoanisole(2,4,6-TBA) were used as the target analytes. The optimization of extraction parameters including fibers types, extraction time, extraction temperature, stirring rate, sample volume, and ionic strength was carried out through the univariate approach. Ten off-flavor compounds were quantified within 50 min under the optimal conditions. Calibration curves with good linearity(r^2=0.990-0.998) were obtained in the range 1.0/2.0-100 ng/L, while the limits of detection for all compounds were lower than or close to the odor threshold concentration. Furthermore, the proposed method was applied to analyzing and determining the off-flavor compounds in real water samples from water-treatment plants.

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.

Metabolomic Fingerprint of the Model Ciliate, Tetrahymena thermophila Determined by Untargeted Profiling Using Gas Chromatography-Mass Spectrometry

The ciliate Tetrahymena is a valuable model organism in the studies of ecotoxicology. Changes in intracellular metabolism are caused by exogenous chemicals in the environment. Intracellular metabolite changes signify toxic effects and can be monitored by metabolomics analysis. In this work, a protocol for the GC-MS-based metabolomic analysis of Tetrahymena was established. Different extraction solvents showed divergent effects on the metabolomic analysis of Tetrahymena thermophila. The peak intensity of metabolites detected in the samples of extraction solvent Formula 1(F1) was the strongest and stable, while 61 metabolites were identified. Formula 1 showed an excellent extraction performance for carbohydrates. In the samples of extraction solvent Formula 2(F2), 66 metabolites were characterized, and fatty acid metabolites were extracted. Meanwhile, 57 and 58 metabolites were characterized in the extraction with Formula 3(F3) and Formula 4(F4), respectively. However, the peak intensity of the metabolites was low, and the metabolites were unstable. These results indicated that different extraction solvents substantially affected the detected coverage and peak intensity of intracellular metabolites. A total of 74 metabolites(19 amino acids, 11 organic acids, 2 inorganic acids, 11 fatty acids, 11 carbohydrates, 3 glycosides, 4 alcohols, 6 amines, and 7 other compounds) were identified in all experimental groups. Among these metabolites, amino acids, glycerol, myoinositol, and unsaturated fatty acids may become potential biomarkers of metabolite set enrichment analysis for detecting the ability of T. thermophila against environmental stresses.

Multiresidue Method for Determination of 67 Pesticides in Water Samples Using Solid-Phase Extraction with Centrifugation and Gas Chromatography-Mass Spectrometry

A new multi-residue method based on solid-phase extraction (SPE) with centrifugation was developed for determination and quantitation of 67 pesticides in water samples. Two SPE cartridges were tested: Chromabond C18 and Oasis HLB. Parameters that influence the extraction efficiency such as the eluent volume, the sample loading volume, the addition of organic solvent to water sample, sorbent drying and elute concentration were optimized. The innovation of this work was the examination of the use of a centrifugation technique in both the drying and elution steps. When combined with centrifugation, the volume of the elution solvent was reduced to 2 mL and the time for sorbent drying decreased also to 10 min under vacuum. Under the optimized conditions, this method showed good recoveries higher than 65% - 68% for the 67 analyzed pesticides using the C18 and HLB cartridges with relative standard deviations lower than 9.7% - 12.3%. Limits of quantification were between 2 and 20 ng.L–1. The simplicity of the described method, use of less of organic solvent, short procedure time, and good recoveries demonstrate the advantages of this environmentally friendly approach for routine analysis of numerous samples.

Gel Permeation Chromatography Purification and Gas Chromatography-Mass Spectrometry Detection of Multi-Pesticide Residues in Traditional Chinese Medicine

The measurement of 23 organochlorine, organophosphorus, and pyrethroid pesticides in typical traditional Chinese medicine (TCM), flos lonicerae, was made using gel permeation chromatography (GPC) purification and gas chroma- tography-mass spectrometry (GC-MS) detection. The pesticides were extracted with ultrasonic device and 5.0 mL mixture of ethyl acetate and cyclohexane (1:1, v/v). Coextractants from sample matrices which may have interfere to the qualitative and quantitative analysis, such as pigments, were removed using GPC purification. Simultaneous full scan and selective ion monitor (scan/SIM) mode for GC-MS was used for qualitative and quantitative analysis, which pro- vided retention time and characteristic fragments ratio for each pesticide so as to positively identify each analyte. Rela- tive standard deviations (RSDs) were within 7.7% (5.0 - 22.5 μg/kg, n = 3). The recoveries of pesticide standards at the spiked concentration of 5.0 - 22.5 μg/kg were between 87.1% and 110.9%. Limits of detection (LODs) for the analytes were 0.16 - 3.2 μg/kg, which could meet the demand of routine analysis and TCM quality control.

Quantitative analysis of trace levels of β-ionone in water by liquid-liquidphase extraction-gas chromatography-mass spectrometry(LLE-GC-MS)

A simple and rapid technique based on liquid-liquid extraction coupled to gas chromatography-mass spectrometric detection(LLE-GC-MS) was developed for analysis of taste and odour compound β-ionone in water. Instrument parameters including programmed oven temperature, injection temperature and ion source temperature were evaluated and optimized. Effects of extraction time, ionic strength and p H on the detection efficiency were investigated and optimum conditions were 8 min of extraction time, without Na Cl addition at p H=9. Good linearity(R2=0.9997) was obtained when the linear range was 10-500 μg/L. The recoveries of β-ionone in ultrapure water and tap water samples were 88%-95% and 110%-114%, respectively. The relative standard deviations(RSD) were less than 10%. The method detection limit(MDL) and rejection quality level(RQL) were achieved at1.98 μg/L and 6.53 μg/L, respectively. LLE-GC-MS was demonstrated to be a rapid and convenient method for the determination ofβ-ionone in water samples.

Analysis of volatile components in a Chinese fish sauce,Fuzhou Yulu, by gas chromatography-mass spectrometry

Volatile components of Fuzhou Yulu, a Chinese fish sauce, were analyzed by gas chromatography-mass spectrometry （GC-MS）, and two pretreatment methods, i.e., purge and trap （P＆T） GC-MS and ethyl acetate extraction followed by GC-MS, were compared. P＆T-GC-MS method determined 12 components, including sulfur-containing constituents （such as dimethyl disulfide）, nitrogen-containing constituents （such as pyrazine derivatives）, aldehydes and ketones. Ethyl acetate extraction fol- lowed by GC-MS method detected 10 components, which were mainly volatile organic acids （such as benzenepropanoic acid） and esters. Neither of the two methods detected alcohols or trimethylamine. This study offers an important reference to determine volatile flavor components of traditional fish sauce through modem analysis methods.

Determination of 8 Diuretics and Probenecid in Human Urine by Gas Chromatography-Mass Spectrometry: Confirmation Procedure

A fast and sensitive method for determination of 8 diuretics (acetazolamide, bendroflumethiazide, bumetanide, chlorthalidone, furosemide, hydrochlorothiazide, metolazone, triamterene) and masking agent (probenecid) in human urine using gas-chromatography with mass spectrometric detection is described. The extraction of the substances as function of the nature of organic solvent, mixing time and pH of aqueous phase was studied. The tandem mass spectrometry was used to increase selectivity of diuretics determination due to elimination of background interferences. Fragmentation reactions were studied for each compound and their collision energies were optimized to obtain the best selectivity. The results of method’s validation demonstrate its suitability in routine analysis for confirmation purposes.

Ultrasonic Nebulization Extraction Coupled with Gas Chromatography-Mass Spectrometry for Analysis of Volatile Components in Traditional Chinese Patent Medicine

The ultrasonic nebulization extraction（UNE） was developed and applied to the extraction of volatile components from traditional Chinese patent medicine Xiaoyao Pills. Several parameters of ultrasonic nebulization extraction including the sample particle size, solvent volume, extraction time and ultrasonic power were studied and selected. As a result, 2.4 g of sample with particle size of 80 mesh was extracted with 15 mL of n-hexane for 20 min at an ultrasonic power of 35 W. The volatile components were analyzed by gas chromatography-mass spectrometry （GC-MS） under the optimal conditions and 57 compounds were identified. The precision, repeatability and stability of the proposed method were also studied. Compared with ultrasonic-assisted extraction（UAE） and hydrodistillation（HD） extraction, the proposed method is more efficient, faster and easier to be operated at room temperature with smaller sample and energy consumption. It is suggested that the ultrasonic nebulization extraction can be used as a novel alternative method for the extraction of volatile components from traditional Chinese patent medicine.

Super Antibiotics, Part II. Hyperforin, Mass Spectroscopy (MS) and Gas Chromatography-Mass Spectrometry (GC-MS), Evidence of Permeability of the Blood-Testis Barrier (BTB) and the Blood-Brain Barrier (BBB) to Hyperforin

In the first article of this series, we presented some evidence of hyperforin as an antibiotic, antiprotozoal, antiviral, anticancer, and immunomodulatory substance. In the present article, evidence of the permeability of the blood-testis barrier (BTB) and blood-brain barrier (BBB) to hyperforin and its distribution in other organs of the domestic pig (Sus scrofa domesticus) are revealed. Seven-month-old male boars with a body mass of 100 kg were fed a diet containing hyperforin. Organs were surgically removed under anesthesia. Organs were suitable prepared and extracted, and then analyzed using gas chromatography-mass spectrometry with supersonic molecular beams (GC-MS with SMB). The presence of hyperforin was recorded in all organs and body fluids. Special attention was paid to the evaluation of the presence of hyperforin in the brain and testes of experimental animals. The presence of hyperforin in the brain and testes of experimental animals was established by GC-MS with SMB. The results are of interest because penicillin and numerous other antibiotics cannot pass through the BTB or BBB if healthy or non-inflamed, which limits their use in patients with meningitis and gonorrhea. The findings are also of interest in cases of penicillin- and multi-antibiotic-resistant bacterial infections.

Determination of Natural Rubber Content in Taraxacum Kok-Saghyz by Pyrolysis Gas Chromatography-Mass Spectrometry

Nowadays,natural rubber(NR)is an indispensable material for industrial production and peoples’daily utilization.The root of Taraxacum kok-saghyz(TKS)contains a large amount of NR,which is potentially to be an alternative rubber source of conventional Hevea brasiliensis(HB).In order to find a convenient,fast and green method for qualitative and quantitative analysis of NR in TKS,a pyrolysis gas chromatography-mass spectrometric(Py-GCMS)method was developed accordingly.The results indicated that the main products of TKS rubber after pyrolysis were isoprene and limonene,respectively,and the limit of detection(LOD)of TKS rubber was 2.603 mg/g.The ratios of NR mass fractions in TKSs by Py-GC-MS ranged from 1.20%±0.20%to 8.61%±0.28%.The developed method has been used for determination of actual TKS samples and can be further applied to the field test for rapid breeding and large-scale cultivation of TKS thereof.

Structure Elucidation of a New Toxin from the Mushroom Cortinarius rubellus Using Gas Chromatography-Mass Spectrometry (GC-MS)

Cortinarius orellanus (Fries) and C. rubellus (Cooke),which were formerly also known as C. speciosissimus, are poisonous mushrooms containing the toxin orellanine and several degradation products of orellanine,includingorelline and orellinine. Mass intoxication by poisonous mushrooms was observed in Poland in 1952-1957 [1]. In 1957, the cause of these outbreaks was described by Grzymala as poisoning by a member of the Cortinarius family. The toxin orellanine was first isolated from C. orellanusby Grzymala in 1962;the chemical structure of orellanine was later determined to be 3,3',4,4'-tetrahydroxy-2,2'-bipyridine-N,N'-dioxide. Poisoning with C. orellanus and C. rubellus has a very specific character. The first symptoms of intoxication usually do not appear until 2-3 days after ingestion, but in some cases intoxication appears after three weeks. The target organ for the toxin is the kidney. Histologically, it is easy to record the specific damage. The presence of degradation products of orellanine in kidney can be confirmed chromatographically, suggesting that the cause of poisoning is orellanine. However, the presence of orellanine in the blood of intoxicated persons has not been directly detected. A specific model was developed by Brondz et al. for the detection of orellanine, orelline, and orellininein animal stomach fluids [2-4]. The hypothesis that the fungal toxin orellanine as a diglucoside can be transported from the digestive system by the blood to the kidney could not be supported. The toxin orellanine as a diglucoside is very unstable in an aqueous acidic environment.[i1]?However, in the present study, it was possible to record an additional substance in animal stomach fluids using GC-MSafter ingestion ofC. rubellus. This substance, which has been namedrubelline, is part of a toxic mixture inC. orellanusandC. rubellusand is closely related to orellanine. The structure of rubelline is more suitable than orellanine for absorptionfromthe digestive tract and for transport in the blood. The presented hypothesis is that rubellineis absorbed in the digestive tract and transportedin the blood to the kidney, where it is biotransformed to orellanine and accumulatedto toxic levels. The process of biotransformationis in itself also damaging for the kidney and liver.[i2]?GC-MS instrumentation enables the separation of substances in biological samples and in the extract fromC. rubellus. The GC-MS with SMB technique was used to record the mass ion and to record a detailed fragmentation picture.