Simultaneous determination of 6 kinds of N-nitrosamines genotoxic impurities in losartan potassium raw material and its formulations by GC-MS/MS / 中国药房

OBJECTIVE To establish a method for simultaneous determination of the contents of 6 kinds of N-nitrosamines genotoxic impurities in losartan potassium raw material and its formulations. METHODS GC-MS/MS was adopted to determine 6 kinds of N-nitrosamines genotoxic impurities in losartan potassium raw material， Losartan potassium tablet， Losartan potassium capsule and Losartan potassium hydrochlorothiazide tablets， such as N-nitrosodimethylamine （NDMA）， N-nitrosodiethylamine （NDEA）， N-ethyl-N-nitroso-2-propanamine （NEiPA）， N-nitrosodiisopropylamine （NDiPA）， N-nitrosodipropylamine （NDPA） and N-nitrosodibutylamine （NDBA）. The separation was performed on SHIMADZU SH-L-17Sil MS capillary column by temperature- programmed GC， with injector temperature of 250 ℃ ， sample size of 1 μL， carrier gas of helium， and carrier flow rate of 1 mL/min. Electron ionization and multiple reaction monitoring （MRM） data acquisition mode were used， with an ion source temperature of 250 ℃ and solvent delay time of 3.1 min. RESULTS The separation among NDMA， NDEA， NEiPA， NDiPA， NDPA， NDBA and adjacent chromatographic peaks was good， and the separation rate was higher than 3.8； the linear ranges of them were 4.9-486.0， 4.9-488.5， 4.5-451.5， 6.8-683.5， 5.2-525.0 and 5.2-520.0 ng/mL（all r≥0.999 8）. The limits of quantitation were 4.86， 4.88， 4.52， 6.84， 5.25 and 5.20 ng/mL； the limits of detection were 0.97， 0.98， 0.90， 1.37， 1.05 and 1.04 ng/mL. RSDs of repeatability tests were 2.2%-5.6%（n＝6）， those of precision tests were 0.5%-1.4%（n＝6）， and those of stability tests were 1.5%-3.4%（n＝5）， respectively. Average recoveries of low-， medium- and high-concentration solution were 83.4%-103.0% （RSDs were 1.2%-6.3%， n＝3）， respectively. No one among the 6 kinds of N-nitrosamines genotoxic impurities was detected in both losartan potassium raw material and formulations. CONCLUSIONS The method is good in separation effect， highly accurate， sensitive and simple. It can be used in the determination of the 6 kinds of N-nitrosamines genotoxic impurities.

Effect of Wine Processing on Odour Formation of Polygonatum cyrtonema Rhizoma by GC-MS / 中国实验方剂学杂志

ObjectiveBy exploring the volatile components， polysaccharide composition and changes in the contents of five carbohydrate components of Polygonatum cyrtonema rhizoma before and after processing， and then the effect of yellow rice wine on the odour formation of P. cyrtonema rhizoma was investigated. MethodThe volatile components of P. cyrtonema rhizoma before and after processing were detected by headspace gas chromatography-mass spectrometry（HS-GC-MS）， and sample data were subjected to principal component analysis（PCA） and orthogonal partial least squares-discriminant analysis（OPLS-DA） using SIMCA 14.1， then the differences between these components of P. cyrtonema rhizoma before and after processing were screened according to the principle of variable importance in the projection（VIP） value>1. Crude carbohydrate components in raw and wine-processed P. cyrtonema rhizoma were subjected to oxime and silylation， the carbohydrate components were analyzed by gas chromatography-mass spectrometry（GC-MS/MS）， and the relative contents of various components were calculated by peak area normalization， then quantitative analysis of four carbohydrate components was also carried out. ResultA total of 23 volatile components were identified from the raw products and the wine-processed products， including 15 components in raw products and 20 components in wine-processed products. Among them， 2-methylbutyraldehyde and isovaleraldehyde had a sweet odor and their contents increased after processing， but the contents of hexanal and caproic acid decreased， new components such as 2-acetylfuran and 5-methylfuranal were produced after processing. PCA and OPLS-DA results showed that there were significant differences between raw products and the wine-processed products， a total of 13 differential compounds were screened out， of which 7 showed an upward trend in relative content and 6 showed a downward trend. A total of 7 carbohydrate components， including 5 monosaccharides and 2 disaccharides， were identified in raw products and the wine-processed products. The results of determination showed that the contents of fructose， glucose， mannose and sucrose in P. cyrtonema rhizoma increased after wine-processing， and their increases were 4.54， 1.51， 2.93， 3.66 times， respectively. ConclusionAfter processing， the increase of aromatic flavor of P. cyrtonema rhizoma may be related to the increase of the contents of aldehydes such as 2-methylbutyraldehyde and isovaleraldehyde， while the decrease of raw flavor may be related to the decrease of the contents of volatile components such as hexanal and hexanoic acid， the increase of sweet flavor may be related to the increase of the contents of monosaccharides and oligosaccharides such as fructose and sucrose.

Determination of 53 pesticide residues in different category of Fritillaria by QuEChERS and GC-MS/MS / 中草药

Objective: To establish a method for simultaneous determination of 53 kinds of pesticides residual in different category of Fritillaria by using QuEChERS and gas chromatography tandem mass spectrometry, and applying to 193 batches sample screening. Methods: The forbidden, restricted and commonly used pesticides were selected as detecting indexes according to the result of this investigation. The samples were prepared by QuEChERS, and quantitative analysis was carried out by GC-MS/MS multiple-reaction monitoring (MRM) model. There were three supplemental levels for determining recoveries and RSD. Results: The results showed that all the 53 pesticides had good linearity in certain ranges with the correlation coefficients (R) higher than 0.997 8. The recoveries of more than 86.8% pesticides were ranged from 60% to 140% at three supplemental levels (1×LOD, 2×LOD, and 10×LOD), with the RSDs less than 15%. The LOD ranged of all pesticides were below 0.01 mg/kg. The result of 193 batches sample screening showed that 91 batches sample were detected 14 pesticides, and the detection rate was 47.2%. Conclusion: The detecting indexes is meaningful and the developed method is simple, rapid, sensitive, and reliable for screening multiple pesticide residues in different category of Fritillaria. The result has certain reference value for the cultivation and circulation supervision of different category of Fritillaria.

Analysis of pesticide residues in commercially available chenpi using a modified QuEChERS method and GC-MS/MS determination / 药物分析学报

To ensure the safety of the commercially available chenpi, a convenient and fast analytical method was developed for the determination of 133 pesticide residues in chenpi using gas chromatography-tandem mass spectrometry (GC-MS/MS). In this study, different extraction solvents, redissolution solvents and adsorbents were tested according to the recovery and purification effect to obtain a modified QuEChERS method. The samples were extracted with acetonitrile. During the clean-up step, octadecyl-modified silica (C18) and graphitized carbon black (GCB) were selected, and aminopropyl (NH2) was used instead of primary secondary amine (PSA) because of its weaker ion exchange capacity which had little effect on the recovery of ditalimfos. Samples were quantified by matrix-matched calibration with internal stan-dards. All pesticides showed good linearity in the respective range, both with values of r2 >0.99. The average recoveries of the pesticides spiked samples ranged from 70.0％ to 112.2％ with the RSDs of 0.2％–14.4％. The modified QuEChERS method was validated and applied to twenty real samples. Five pesticides were found in eight batches, but no pesticide exceeded the maximum residue limits (MRL, MRL reference to European commission).

QuEchERS pretreatment coupled to gas chromatography and tandem mass spectrometry to fast determination of 34 pesticide residues in Glycyrrhizae Radix et Rhizoma / 中国中药杂志

This study proposed a quantitative method for 34 pesticides including organochlorine,organophosphorus and pyrethroids in Glycyrrhizae Radix et Rhizoma herbs and medicinal slices,and analyzed the pesticide residues of collected Glycyrrhizae Radix et Rhizoma samples from different regions. With acetonitrile extraction and optimized Qu Ech ERS purification,the 32 batches of Glycyrrhizae Radix et Rhizoma herbs and medicinal slices were analyzed by matrix matching standard curve quantitative analysis under GC-MS/MS multi-response monitoring( MRM) mode. This study investigated the pretreatment of Glycyrrhizae Radix et Rhizoma samples based on the Qu Ech ERS method of Chinese Pharmacopoeia( 2015 edition,4),and the result showed that the recoveries of some pesticide was low and pigment has a strong interference in analysis,which result in worse purification effect. Therefore,this paper further optimized the Qu Ech ERS method and corrected the matrix matching standard curve method,and compensated the qualitative and quantitative effects of matrix effects on the detected target compounds in Glycyrrhizae Radix et Rhizoma. The results showed that 34 kinds of pesticide had good linear( R~2 of 0. 996 4 or higher) within a covering 0. 01-0. 2 mg·kg~(-1) concentration range. The limits of quantitation are less than 0. 01 mg·kg~(-1). This method was further applied to the simultaneous determination of 34 pesticide residues of typical organochlorine,organophosphorus and pyrethroids in 32 batches of Glycyrrhizae Radix et Rhizoma herbs and medicinal slices. Six batches containing beta-endosulfan,thiosulphate,o,p'-DDD and thrta-cypermethrin were detected,but none of them exceeded the limit of pesticide residues stipulated in the Chinese Pharmacopoeia and the EU Pharmacopoeia. This study indicates that the established method is rapid,convenient,accurate,and sensitive,which provides a rapid and efficient method for the simultaneous determination of typical organochlorine,organophosphorus and pyrethroids in Glycyrrhizae Radix et Rhizoma.

Determination of 69 Kinds of Pesticide Residues in Paeonia tactilora ，Astragalus membranaceus ，Ranunculus ternatus and Cornus officinalis by GC-MS/MS / 中国药房

OBJECTIVE： To establish the method for simultaneous determination of 69 kinds of pesticide residues in Paeonia tactilora， Astragalus membranaceus， Ranunculus ternatus and Cornus officinalis. METHODS： GC-MS/MS method was adopted. The determination was performed on HP-5MS fused silica capillary column with splitless injecting samples. The injector temperature was set at 240 ℃， and sample size was 1 μL. The carrier gas was high-purity helium， the inlet mode was constant pressure， the pre-column pressure was 146 kPa， and the temperature was programmed. Triple four-pole tandem mass spectrometry was used for the detection， and electron impact ion source was used as ion source. The temperature of the ion source was 230 ℃， ionization energy was 70 eV， and the collision gas was nitrogen. The inlet temperature was 280 ℃ and four-pole temperature was 150 ℃， mass spectrometry monitoring mode was multi-reaction monitoring （MRM）， and solvent delay time was 5 min. RESULTS： The linear range of 69 kinds of pesticide residue was 4.82-399.6 ng/mL （all r＞0.990）. LODs were all in the range of 0.001 7-0.013 3 mg/kg， and LOQs were all in the range of 0.000 5-0.004 mg/kg. RSDs of precision and stability tests were less than 10％ （n＝6）. RSD of reproducibility test was lower than 5％ （n＝6， only pesticide amidine and permethrin were detected）. The recoveries were in the range of 62.9％-123.5％ （all RSD＜10％， n＝6）. Among 12 batches of samples， dichlorvos and diphenylamine were detected in C. officinalis； chlordimeform and permethrin were detected in  A. membranaceus； diphenylamine and chlordimeform were detected in P. tactilora； diphenylamine and vinclozolin were detected in R. ternatus. CONCLUSIONS： The method is simple in operation and reproducible for simultaneous determination of 69 kinds of pesticide residue in   P. tactilora， A. membranaceus， R. ternatus and C. officinalis.

Determination of Paclobutrazol Residue in Ophiopogon japonicus from Sichuan by the QuEChERS Combined with GC-MS/ MS-internal Standard Detection / 中国药房

OBJECTIVE： To establish a method for measuring the paclobutrazol residue in Ophiopogon japonicus from Sichuan and detect the quality of O. japonicus from Sichuan from different sources. METHODS： Totally 50 batches of samples were collected from different origin places， commercial markets and manufacturers. The sample pretreatment method was QuEChERS method， .ie the sample was extracted by aqueous acetonitrile， salted out by QuEChERS extract package （containing anhydrous magnesium sulfate and anhydrous sodium acetate）， the extract solution was purified by QuEChERS purification package （containing anhydrous magnesium sulfate， N-propyl ethylenediamine， octadecylsilane chemically bonded silica， silica gel， graphitized carbon black） and then added into internal standard triphenyl phosphate. The paclobutrazol residue in O. japonicus from Sichuan was determined by GC-MS/MS. The determination was performed on DB-5MS column. The temperature programming was adopted， and the detector was triple quadrupole MS detector. The initial flow rate of carrier gas was 1.3 mL/min； acquisition mode was MRM. Injection method was splitless injection. RESULTS： The linear range of paclobutrazol was 1.01-505 ng/mL （r＝    0.999 7）. RSDs of precision， stability （24 h） and repeatability tests were 3.94％， 13.62％， 7.54％ （n＝6）， respectively. Average method recovery was 111.26％ （RSD＝5.43％， n＝9）. The paclobutrazol residue in 50 batches of sample were 0.02-2.72 mg/kg. CONCLUSIONS： Established method is simple， accurate， sensitive and reproducible. It also can be used for the determination of paclobutrazol residue in O. japonicus from Sichuan. The contents of paclobutrazol residue in O. japonicus from Sichuan from different sources are different greatly.

Method Establishment and Samples Screening for the Determination of Forbidden Pesticide Residues in Panax ginseng C.A.Mey / 中国药学杂志

OBJECTIVE： To establish a method for the determination of 33 kinds of pesticide residues in Panax ginseng C.A.Mey by GC-MS/MS and LC-MS/MS. METHODS： The 53 chemical monomers of 33 pesticide residues clearly prohibited by the Chinese ministry of agriculture were selected as the detection indicators. The samples were extracted with acetonitrile by high speed homogenizer. An LC-MS/MS analysis was performed on a CORTECSTM UPLC C18(2.1 mm×150 mm, 1.6 μm) column with isocratic elution of 0.1% formic acid (containing 5 mmol•L-1 ammonium formate) is mobile phase A, 95% acetonitrile(containing 5 mmol•L-1 ammonium formate and 0.1% formic acid)is mobile phase B.Electrospray ionization(ESI)source was applied by positive ionization in multiple reaction monitoring(MRM)modes. GC-MS/MS analysis was performed on a DM17ms(30 m×0.25 mm, 0.25 μm)capillary column with electron impact(EI)source, electron impact (EI) source was applied by positive ionization in multiple reaction monitoring modes (MRM). RESULTS: The correlation coefficient r of 33 pesticide residues showed good linearity in the linear range of 2 to 20 ng•mL-1 was greater than 0.990 0. The average recoveries at spiked levels of low level and high level (0.01 and 0.04 mg•kg-1), repeat 5 times per level. The average recovery was 87.57%-120.98%, and the RSD was between 1.45%-14.03%. CONCLUSION： The method can quickly and effectively detect pesticide residues in ginseng.

Avaliação da presença do 3-monocloro-1, 2-propanediol e glicidol em óleos vegetais comestíveis utilizando GC/MS/MS e seu risco toxicológico / Evaluation of the presence of 3-monochloro-1, 2-propanediol and glycidol in edible vegetable oils using GC/MS/MS and its toxicological risk

Cloropropanóis são um grupo conhecido de contaminantes relacionados ao processamento de alimentos. Eles são formados na reação entre lipídeos e cloretos quando submetidos ao tratamento térmico, e podem ser encontrados na forma livre ou ligada. O 3-monocloro-1,2-propanediol (3-MCPD), é classificado pela IARC como possível carcinógeno humano (grupo 2B). O glicidol (e seus ésteres), é classificado também pela IARC como uma substância provavelmente carcinogênica para seres humanos (grupo 2A), e, recentemente, vem sendo encontrado em alimentos. O objetivo deste trabalho foi avaliar a presença do 3-MCPD e do glicidol em óleos vegetais comestíveis utilizando a cromatografia gasosa com detector de massa triplo quadrupolo MS/MS. A técnica utilizada foi a preconizada pela AOCS Cd 29c-13, sendo uma análise indireta, e foi possível adaptá-la visando as determinações do 3-MCPD e glicidol através da construção de curvas de calibração e análises de amostras de referência. O método foi validado e os resultados indicaram o limite de detecção do composto 3-MCPD, de 42,4 µg/kg e o limite de quantificação de 50 µg/kg, e para o Glicidol indicaram o limite de detecção de 43,5 µg/kg e limite de quantificação de 50 µg/kg. Os resultados para 3-MCPD obtidos nos ensaios da curva de calibração e linearidade demonstraram que o método foi capaz de expressar resultados com boa linearidade (0 - 10 mg/kg , r2, = 0.9991). Os resultados obtidos nos ensaios de exatidão obedeceram aos critérios de 70 a 120% de recuperação, e ±20% de variação entre os resultados de acordo com SANTE (2017). O método em questão demonstrou ser seletivo, uma vez que não foram observados picos interferentes nos tempos de retenção dos compostos estudados. Os ensaios de precisão nos níveis baixos, médio e alto e robustez demonstraram que o método é robusto e preciso, portanto a validação foi considerada adequada ao uso pretendido. Foram analisadas 368 amostras de óleos vegetais (76 amostras de óleo de canola, 48 amostras de óleo de milho, 69 amostras de óleo de algodão, 33 amostras de óleo de palma, 10 amostras de óleo de palmiste, 50 amostras de oleína de palma, 30 amostras de óleo de soja e 51 amostras de óleo de girassol). As concentrações das amostras analisadas apresentaram resultados para 3-MCPD com valores médios entre 203 a 1205 µg/kg. Para o Glicidol os valores foram de 2 a 1198 µg/kg, com elevado o desvio padrão entre os resultados analíticos, onde o óleo de palma apresentou a maior variação de 1600 a 5260 µg/kg. Através da avaliação do risco realizada para o composto 3-MCPD foi possível detectar, utilizando o critério do pior cenário de exposição e resultados analíticos, os valores diários de consumo de óleo de algodão de 0,044 µg/kg p.c., de óleo de girassol 0,045 µg/kg p.c., óleo de canola 0,18 µg/kg p.c., óleo de palma de 0,28 µg/p.c, óleo de milho de 0,0462 µg/kg p.c., e o óleo de soja, de maior consumo no Brasil (72%) apresentou o valor de 0,27 µg/kg p.c. O consumo de todos estes óleos, pela a população brasileira, pode ser considerado seguro ao comparar com o valor de TDI Ingestão Diária Tolerável - de 2µg/kg p.c.. Através da avaliação do risco realizada também utilizando o critério de pior cenário de exposição e e resultados analíticos para o composto glicidol foi possível verificar que os valores diários de consumo de óleo de algodão de 0,061 µg/kg p.c., de óleo de girassol 0,03 µg/kg p.c., óleo de canola 0,13 µg/kg p.c. e de óleo de palma de 0,57 µg/p.c, de óleo de milho de 0,11 µg/kg p.c, e o óleo de soja de maior consumo no Brasil (72%) não ultrapassam o valor de 0,288 µg/kg p.c indicando consumo seguro destes óleos para a população brasileira baseado na TDI de 1000µg/kg p.c

Chloropropanols are a known group of contaminants related to food processing. They are formed during the reaction process between lipids and chlorides when submitted to heat treatment and can be found in free or bound form. The 3-monochloro-1,2-propanediol (3-MCPD), is classified by IARC as a possible human carcinogen (group 2B). Glycidol (and its esters), also classified by IARC as a substance likely to be carcinogenic to humans (group 2A), has recently been found in food. The present study aims to evaluate the presence of 3-MCPD and glycidol in edible vegetable oils using gas chromatography with triple quadrupole MS/MS mass detector. The technique applied is recommended by AOCS, guide Cd 29c-13, an indirect analysis, and allows quantification of 3-MCPD and glycidol by building the calibration curves and analysis of reference samples. The method was validated and the detection limit of the contaminant 3-MCPD of 42,4 µg/kg and the quantification limit of 50 µg/kg was established. For Glycidol the detection limit of was 43,5 µg/kg and quantification limit was 50 µg/kg. The results obtained in the calibration and linearity curves demonstrated that the method could express results with good linearity (0 10 mg/kg, r2, = 0.9991). The results obtained in the trueness trials agreed to the criteria of 70 to 120% of recovery, and ± 20% of variation between the results according to what is preconized by SANTE (2017). The method showed to be selective, since no interfering peaks were observed in the retention times of the studied compounds. The tests performed on low, medium and high values demonstrated the robustness and precision of the method, so the validation was considered completed and suitable for the purpose. A total of 368 vegetable oil samples were analyzed (76 samples of canola oil, 48 samples of corn oil, 69 samples of cottonseed oil, 33 samples of palm oil, 10 samples of kern palm oil, 50 samples of palm olein, 30 samples of soybean oil and 51 samples of sunflower oil). The results found in samples for 3-MCPD were within mean values between 203 and 1205 µg/kg. The results found in samples for glycidol were within mean values between 2 to 1198 µg/kg where palm oil presented the highest variation for glycidol from 1600 to 5260 µg/kg. Through the risk assessment for the contaminant 3-MCPD it was possible to detect the values based on exposed worst case scenario and analytical results. The results for cottom oil were 0,044 µg/kg bw, sunflower 0,045 µg/kg bw, canola 0,18 µg/kg bw and palm oil 0,28 µg/kg bw, corn oil 0,0462 µg/kg bw, and for soybean, which is the most consumed oil in Brazil (72%) the value of 0,27 µg/kg bw. These results indicates safe consumption for these oils based in the Theoretical Daily Ingestion - TDI of 2µg/kg bw. The risk assessment for the glycidol based on exposure worst case scenario and analytical results presented for cottom oil the value of 0,061 µg/kg bw, sunflower 0,03 µg/kg bw, canola oil 0,13 µg/kg bw , palm oil 0,57 µg/kg bw, corn oil 0,11 µg/kg bw and for soybean, which is the most consumed in Brazil - 72% the value of 0,27 µg/kg bw. These results indicates safe consumption for these oils based in the TDI of 1000µg/kg bw

Applications of GC-MS/MS automated mass spectral deconvolution and multi reaction monitor qualitative and quantitative analysis of volatile components of Chenxiang Huaqi Tablets / 中草药

Objective To analytically screen the volatile components from Chenxiang Huaqi Tablets (CHT) using gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS) combined with automated mass spectral deconvolution, and establish the methods of multiple components contents (camphor, bornyl acetate, and patchouli alcohol) from CHT using multi reaction monitor (MRM). Methods The chromatographic column was HP-5MS (30 m × 0.32 mm × 0.25 μm). Temperature program: the initial temperature was 100 ℃, at 15 ℃/min up to 300 ℃ for 2 min. Injection port temperature was 280 ℃; Ionization methods: EI ion source with ion source temperature of 230 ℃; Quadrupole temperature was 150 ℃; Interface temperature was 280 ℃; Inject volume was 1 μl. Results A total of thirteen components were screened by automated mass spectral deconvolution soft. Under the conditions of MRM collection, camphor, bornyl acetate, and patchouli alcohol were in the range of 4.5-90 mg/mL (r = 0.999 8), 3.3-66 mg/mL (r = 0.999 8), and 2.6-51.5 mg/mL (r = 0.999 9), respectively, the ratio of each component concentration to its peak area was linear, and the average recovery (n = 6) was 101.15%, 102.64%, and 100.10% respectively; The mass fraction of 10 batches of samples were in the ranges of 0.278-0.311, 0.381-0.438, and 0.229-0.381. Conclusion The method is accurate, simple, and good repeatability. It can be used for the simultaneous determination of camphor, bornyl acetate, and patchouli alcohol in CHT, which provides a reference for the improvement of the quality of this variety.

Investigation and Analysis of Pesticide Residues in Fructus Trichosanthis / 中国药学杂志

OBJECTIVE: To investigate the status of pesticide residues in Fructus Trichosanthis. METHODS: Seventy kinds of pesticide residues were detected by GC-MS-MS and 150 kinds of pesticide residues were detected by HPLC-MS-MS in 84 samples of Fructus Trichosanthis from leading producers of 11 provinces. RESULTS: The detection rate of pesticide residues in 84 Fructus Trichosanthis samples was 95.2%, with only 4 batch of samples without pesticide residues detection. Endosulfan sulfate, diphenlamine, fenvalerate, chlorantraniliprole, carbendazim, cyhalothrin, and bifenthrin had the highest detection rates, all above 10%. CONCLUSION: The detection rate of pesticide residues in Fructus Trichosanthis is high, but most of the detected pesticides have low contents, with few samples exceeding the limits.

Multi-Residue Analysis of Pesticides in Radix Ophiopogonis by GC-MS/MS / 中国药学杂志

OBJECTIVE: To establish a method for simultaneous determination of 56 kinds of pesticide residues in Radix Ophiopogonis by using gas chromatography tandem mass spectrometry (GC-MS /MS), and apply it to screening of 137 batches of samples. METHODS: The forbidden, restricted and frequently-used pesticides were selected as the detecting indexes. The samples were prepared by QuEChERS, and quantitative analysis was carried out by GC-MS /MS in multiple-reaction monitoring (MRM) mode. There were three supplemental levels for detection recoveries and RSD. RESULTS: All the 56 pesticides had good linearity in certain ranges with correlation coefficients(r) higher than 0.997 8. The recoveries of 96.4% pesticides ranged from 60% to 130% at three supplemental levels (1, 2 and 10 LODs), with the RSDs of 92.9% pesticides less than 15%. The LODs for most of the selected pesticides were below 0.01 mg•kg-1. Twelve pesticides were detected in 137 batches of samples. CONCLUSION: The detecting indexes are meaningful and the developed method is simple, rapid, sensitive and reliable for screening multiple pesticide residues in Radix Ophiopogonis. The test result has certain reference value for the cultivation and distribution supervision of Radix Ophiopogonis.

Study on the simultaneous measurement of residual level of three pesticides in nelumbinis semen using GC-MS/MS / 国际中医中药杂志

Objective To establish a quantitative method for the simultaneous measurement of the residual level of three pesticides in Nelumbinis semen by GC-MS/MS. Methods The samples were extracted by acetonitrile and purify by Cleanert TPH column. The samples were then tested by GC-MS/MS. Information on relative retention time and mass charge ratio was used for qualitative analysis. The peak area obtained by secondary ion MS of bifenthrin (181.1/166.1)was used as the reference peak to calculate the relative correction factor for the peak area of fenpropathrin (265.1/210.1) and deltamethrin (252.9/93.0), to establish a method using bifenthrin as the reference substance to determinate there sidual quantity of three pesticides in Nelumbinis semen by GC-MS/MS. Results When the injection quantity of the sample containing bifenthrin,fenpropathrin and deltamethrin in the range of 0.01-0.1 ng , there was a good linear relationship between the injection quantity and peak are a Limitation of quantification (LOQ) of bifenthrin , fenpropathrin and deltamethrin were 4.321×10-4 ng, 3.435×10-4 ng, 8.913×10-3 ng, respectively. The average recovery rates of bifenthrin, fenpropathrin and deltamethrin were 93.5％, 93.5％ and 93.8％, respectively. Conclusions The method of quantitative analysis of multi-components with a single-marker is simple, quick and accurate. It suitable for the detection of residual quantity of bifenthrin, fenpropathrin and deltamethrin in Nelumbinis semen.

The postmortem distribution of bromadiolone and its metabolite-benzylideneacetone in poisoned dogs / 中国法医学杂志

Objective To study the postmortem distribution of Bromadiolone and its metabolite-Benzylideneacetone in dogs and provide an experimental evidence for the sampling of Bromadiolone poisoning cases. Methods The dogs were given 2LD50 and 4LD50 Bromadiolone by intragastric administration. Anatomy was conducted immediately after death and samples of body fluids and viscera (heart blood; peripheral blood, bile, urine, heart, liver, spleen, lung, kidney, brain, urinary bladder, left leg muscle, stomach, stomach contents, pancreas) were collected and detected after the dogs poisoning death. The Bromadiolon and its metabolite-Benzylideneacetone contents in samples were analyzed by GC/MS. Results Hemorrhagic symptoms came out at 3d after Bromadiolone delivery and deaths occurred at (178.40±20.94)h after intoxication. The postmortem distribution of Bromadiolon and its metabolite-Benzylideneacetone in dogs was as following: 2LD50 Bromadiolon: bile>urine, liver, heart, kidney>heart blood, peripheral blood, spleen, lung and so on. Benzylideneacetone: the content in bile, urine, heart blood, peripheral blood, lung, stomach contents are higher. 4LD50 Bromadiolon: bile, urine>liver, peripheral blood>heart blood, stomach contents and others. Benzylideneacetone:contents in bile, urine and lung are higher. Conclusion The postmortem distribution of Bromadiolon and its metabolite-Benzylideneacetone in dogs is uneven, contents in bile, urine, liver, heart blood and peripheral blood are higher, whichare suggested for forensic toxicological analysis in Bromadiolon poisonig case.

Simultaneous determination of somedon and its metabolites by GC–MS/MS / 中国法医学杂志

Objective To develop a method of support liquid-liquid extraction (SLE) and simultaneous determination of 4 components in somedon and its 8 metabolites by GC–MS/MS. Methods Somedon and its metabolites were extracted by SLE and determined by GC-MS/MS in MRM mode. The qualitative analysis was based on retention time and ratio of ions. The quantitative analysis was based on internal standard method and calibration curve. Results After SLE and determination of 4 components in somedon and its 8 metabolites, the extraction rate were 37.57%~95.87%, the linear range were 0.12μg/mL~16.00μg/mL, the correlation coefficient(r)were 0.989 6~0.999 7, LOD were 0.08ng/mL~14.48ng/mL, the accuracy were 79.63%~122.90%, the interday and intraday precision were 0.99%~7.43% and 2.19%~10.60% respectively. Conclusion Simultaneous determination of somedon and its metabolites by GC–MS/MS in biological samples, which was rapid, simple, accurate and was high precision and recovery, can be used for qualitative and quantitative analysis in forensic cases.

Study on the stability of carbofuran and its metabolites in blood preserved at different conditions / 中国法医学杂志

Objective Study on the stability of carbofuran and its metabolite carbofuran phenol in blood preserved at different conditions,in order to provide a scientific evidence for forensic identification of carbofuran poisoning death. Methods The dogs were given intragastric administration with 4LD50(13.5mg/kg) of carbofuran, the blood were collected and divided into five equally groups preserved at 20℃(NC2.5mg/mL), 20℃(1%NaF), 20℃, 4℃ and -20℃, respectively. The concentrations of carbofuran and carbofuran phenol in above samples were detected by GC-MS/MS with MRM at 0d、5d、7d、15d、40d、83d and 150d. Results The concentration of carbofuran in preserved blood were found to be significant decrease at 7d(P < 0.05), then a steady decline. In each condition, the concentration of carbofuran phenol in preserved blood showed an increasing trend firstly, then a declined tendency. The concentration of carbofuran and carbofuran phenol descending fast in blood at 20 ℃ (NC) and 20 ℃ (1%NaF).Conclusion Carbofuran and carbofuran phenol in preserved specimens are found to be decomposed. The decomposition is quick at 20℃ and slow at -20℃. Citrate sodium and sodium fluoride are not suit for anticoagulation and antiputrefactiva. Biological specimens used for forensic identification of the carbofuran poisoning should be stored at refriferated or freezed, and be analyzed as soon as possible.

Simultaneous determination of 238 pesticide residues in Astrgalus membranaceus by GC-MS/MS / 中国药学杂志

OBJECTIVE: To study the multi-residues detection methods for Astrgalus membranaceus by GC-MS/MS. METHODS: The extraction was performed by modified QuEChERS method, and then cleaned by PSA solid phase extraction (SPE) cartridge. The residue detection was carried out by GC-MS/MS, which could identify and quantify pesticide simultaneously. RESULTS: The analytical performance was validated by recovery experiments that were fortified at three levels for each pesticide. In general, the recoveries ranged from 70% to 120% and the relative standard deviations (RSDs) were all less than 15%. The limits of detection (LODs) for most of the selected pesticides were below 0.01 mg · kg-1. CONCLUSION: The method shows high sensitivity, good repeatability and satisfactory cleaning-up excellence, which could be applied to the pesticide residue detection for Astrgalus Membranaceus. Copyright 2012 by the Chinese Pharmaceutical Association.

Analysis of plasticizer in compound aluminum hydroxide tablets with GC-MS/MS / 中国药学杂志

OBJECTIVE: To develop GC/MS method in detect plasticizers in compound aluminum hydroxide tablets adsorbed from pharmaceutical packaging. METHODS: The column: HP-5MS silica capillary column (30 m × 0.25 μm, 0.25 mm) was used; Ion source temperature was 230°C; Quadrupole temperature was 150°C; The total ion scanning rang: m/z 50~500. RESULTS: The diethylhexyl phthafate linearity was in the range of 0.5 -20.0 μg · mL-1 with a regression coefficient of 0.9990. The average recovery of this method was 98.8%, and RSD was 1.4%. The RSD of intra-day and inter-day was 2.8% and 3.1% respectively. CONCLUSION: This method is specificity, sensitive, and can be applied to detect and research DEHP which may be adsorbed or penetrated into drugs. Copyright 2012 by the Chinese Pharmaceutical Association.