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Objective To establish a quality control method for monitoring the blood concentrations of cyclosporin A and tacrolimus by HPLC-MS/MS,and to evaluate the quality control samples using the Westgard multi-rule theory.Methods HPLC-MS/MS was used to determine the concentration of cyclosporin A and tacrolimus in human whole blood.The quality control samples of low,medium and high concentration levels in the therapeutic drug monitoring process were statistically analyzed,Levery-Jennings and Z-score quality control charts were drawn,and the Westgard multi-rule theory was applied for in-house quality control evaluation.Results The established method was fully validated with linear ranges of 10.40-1 040.00 ng·mL-1 and 0.50-49.50 ng·mL-1,the quantification limits were 10.40 and 0.50 ng·mL-1,respectively.The extraction recoveries were 108.61％-113.24％and 101.99％-109.37％,respectively.The matrix factors normalized by internal standard were 106.68％-111.27％and 95.70％-97.81％for cyclosporin A and tacrolimus,respectively.The intra-day and inter-day accuracy and precision were less than 15.0％.Other parameters were also validated and met the acceptance criteria.Levery-Jennings and Z-score quality control charts showed that there were 4 warnings(violation of the 12s rule)in the results of the 26 groups of quality control samples in the third quarter of 2022,and no phenomenon was observed to be out of control.Conclusion The established in-house quality control system for therapeutic drug monitoring of cyclosporin A and tacrolimus can effectively ensure the accuracy of blood drug concentration detection.
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AIM To analyze the component composition of Xeriga-4 Powder,and to determine the contents of phellodendrine,chlorogenic acid,gardenoside,berberine,rutin and curcumin.METHODS The high performance liquid chromatography-Q-exactive orbitrap mass spectrometry(HPLC-Q-Exactive-MS)qualitative analysis was performed on a 35℃thermostatic Agilent ZORBAX SB-Aq column(4.6 mm×150 mm,5 μm),with the mobile phase comprising of methanol-0.1%formic acid flowing at 0.35 mL/min in a gradient elution manner,and electron spray ionization source was adopted in positive and negative ion scanning.High performance liquid chromatography tandem mass spectrometry(HPLC-MS/MS)quantitative analysis was performed on a 35℃thermostatic Shim-pack GIST-HP C18 column(2.1 mm×100 mm,3 μm),with the mobile phase comprising of methanol-0.1%formic acid flowing at 0.25 mL/min in a gradient elution manner,and electron spray ionization source was adopted in positive and negative ion scanning with multiple reaction monitoring mode.RESULTS Total 65 constituents were identified,containing 19 alkaloids,13 organic acids,13 flavonoids,7 curcumins,6 iridoids,4 fatty acids,2 aldehydes,and 1 amino acid.Six constituents showed good linear relationships within their own ranges(r≥0.999 1),whose average recoveries were 96.44%-102.37%with the RSDs of 2.05%-3.74%.CONCLUSION This study can provide a reference for the quality control for Xieriga-4 Powder.
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Objective:To establish a determination method of high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS)for serum hydrogen sulfide(H2S),so as to determine serum H2S.Methods:This study collected serum samples of 30 patients who admitted to Beijing Jishuitan Hospital affiliated to Capital Medical University from April 2023 to May 2023,and they were divided into osteoporosis group and control group according to whether existed osteoporosis,with 15 cases in each group.HPLC-MS/MS and enzyme-linked immunosorbent assay were used respectively to determine serum H2S.And then,the precision,accuracy and correlation between the two methods were evaluated.Results:HPLC-MS/MS can fast detect the content of serum H2S through detecting methylene blue in the serum,which analysis time was only 1.5 minutes,and its specificity was higher.The relative standard deviation(RSD)value of quality control plasma was 8.77%,and that of quality control plasma with the standard and pure water with standard were respectively 4.58% and 8.23%.The precisions of them met the requirement of detection(less than 20%).The recovery was 103.5% through used the above data,and the accuracy accorded with the requirements of quantitative detection(recovery was 103.5%).Conclusion:HPLC-MS/MS method is rapid and accurate in detecting H2S,which can accurately detect the content of serum H2S.This method has a series of advantages include fast,high throughput,high sensitivity and favorable stability,which contributes to conduct basic research of the content of serum H2S in the cellular pathways of human.
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Objective@#To establish a non-derivatization-PriME-ultra-high performance liquid chromatography-tandem mass spectrometry method for simultaneou determination of 9 kinds of biogenic amines in yellow rice wine.@*Methods@#Yellow rice wine samples were purified by PriME HLB solid phase extraction column purification, separated using Waters XSelect HSS T3 column (150 mm×2.1 mm, 3 μm), and qualified using multiple reaction monitoring mode, electrospray ion source positive ion and external standard method.@*Results@#There was a good linear relationship for the 9 kinds of biogenic amines at 2.0 to 500.0 μg/L (r≥0.996). The limit of detection was 0.1 to 0.2 mg/L, and the limit of quantitation was 0.3 to 0.6 mg/L. The spike recovery rate of 9 kinds of biogenic amines ranged from 83.5% to 108.6% at 0.1 and 1.0 mg/L, with relative standard deviations of 2.8% to 8.7%.@*Conclusion@#Non-derivation-prime ultra-high performance liquid chromatography-tandem mass spectrometry can be used for the rapid quantitative detection of biogenic amines in yellow rice wine.
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OBJECTIVE To establish a method for simultaneous determination of 15 bile acids in Tongren niuhuang qingxin pills， and to determine the contents of 15 batches of samples. METHODS Using dehydrocholic acid as internal standard， the determination was performed by ultra-high performance liquid chromatography-tandem mass spectrometry （UPLC-MS/MS） method. The determination was performed on Hypersil GOLD C18 column with methanol-0.1% formic acid solution as the mobile phase by gradient elution at the flow rate of 0.2 mL/min. The column temperature was 40 ℃ ， and the sample size was 2 µL. Using heated electrospray ion source， parallel reaction monitoring mode scanning was performed in negative ion mode. SPSS 24.0 software was used for chemical pattern recognition analysis of content determination results. RESULTS The 15 bile acid components had a good linear relationship with peak area （all R2≥0.998 9）； their precision， repeatability and stability were all good （all RSD≤5.49%）； the average recoveries were 93.8%-105.7% （RSD was 0.5%-5.8%）. The average contents of taurocholic acid， 7-oxodeoxycholic acid， 12-dehydrocholic acid， glycocholic acid， 3-oxo-7α， 12α-hydroxy-5β-cholanoic acid， taurochenodeoxycholic acid， 3α-hydroxy- 7-oxo-5β -cholanic acid， hyocholic acid， taurodeoxycholic acid sodium salt hydrate， hyodeoxycholic acid， cholic acid， glycochenodeoxycholic acid， glycodeoxycholic acid， chenodeoxycholic acid and deoxycholic acid were 670.56， 25.97， 10.54， 280.12， 4.04， 29.81， 182.98， 813.55， 120.95， 220.31， 797.37， 18.37， 68.59， 30.13， 59.82 μg/g， respectively. Both cluster analysis and principal component analysis divided 15 batches of Tongren niuhuang qingxin pills into 2 categories， S1-S12 as one category and S13-S15 as the other category. CONCLUSIONS The established method is accurate， sensitive and specific， and can determine many types of bile acids. It also can quickly achieve the quantitative analysis of 15 bile acids in Tongren niuhuang qingxin pills， which is suitable for the quality control of this drug.
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ObjectiveA method was developed for the rapid determination of 18 common disinfection by-products including halogenated oxides and haloacetic acid （HAAs） in drinking water by high performance liquid chromatography tandem mass spectrometry （HPLC-MS/MS）. MethodThe water sample was filtered by 0.22 μm hydrophilic membrane then the analytes were separated on a PFP （2.1 mm× 100 mm， 2.7 μm） pentafluorophenyl column with 0.1% acetic acid and acetonitrile as mobile phase gradient elution. Ionization in anionic electrospray mode was detected by multi-reaction monitoring （MRM） mode. The external standard method was used for quantitation. ResultsThe correlation coefficients of 18 disinfection by-products were above 0.999 in the corresponding linear range. The average spiked recoveries of 1， 10 and20 times of LOQ of each analyte were 91.6%‒101.8%， and the relative standard deviation （RSD） was 1.2%‒6.4%. The LOD and LOQ were 0.020‒2 μg·L-1 and 0.050‒5 μg·L-1， respectively. ConclusionThis method is simple， sensitive and accurate， and could be used for the routine analysis of 18 common disinfection by-products in drinking water.
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Objective:High performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was used to quantify the levels of vitamins A, D and E in pregnant women during the second trimester, and to investigate the change trends of serum vitamins A, D and E levels during pregnancy.Method:A total of 720 pregnant women with an average age of (29.7±4.4) years and 12-22 weeks of gestation were included from October 1, 2021 to October 30, 2022 in the obstetrics department of the People′s Hospital of Wuhan University. The concentrations of vitamins A, D and E were determined by HPLC-MS/MS. The concentration levels of each group were statistically analyzed and the deficiency rate were calculated.Results:The distribution range of vitamin A, D and E (95% CI) was 0.74-2.74 μmol/L, 2.88-25.37 ng/ml and 6.18-35.08 μmol/L, with the deficiency rates were 9.30%, 93.76% and 35.83%, respectively. Vitamin A, D and E levels in the twin group were (1.67±0.51) μmol/L, (13.18±7.44) ng/ml and 11.97 (8.85, 14.60) μmol/L, respectively. They were significantly higher than those in the singlet group (1.45±0.36) μmol/L, (10.87±5.26) ng/ml and 10.46 (6.99, 14.11) μmol/L, with statistical significance by independent sample t-test ( P<0.001). The concentration of vitamin D in the lower BMI group (<22 kg/m 2) was (12.54±5.74) ng/ml, significantly higher than that in the fat group (≥22 kg/m 2) (10.46±4.90) ng/ml, and the rank-sum test was statistically significant ( P<0.001). Conclusion:In this study, the levels of three vitamins were monitored in mid-pregnancy using HPLC-MS/MS, and the changes of serum vitamin A, D, and E levels during pregnancy were analyzed.
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OBJECTIVES@#To establish a rapid method for the analysis of bucinnazine in blood by UPLC-MS/MS and to apply the method to the practical case.@*METHODS@#After the internal standard was added to blood, the protein was precipitated with 900 μL mixed solution (Vacetonitrile∶Vwater=8∶2). After vortex and centrifugation, the protein was measured through 0.22 μm filter membrane. The separation was performed on C18 chromatography column, with acetonitrile and 5 mmol/L ammonium acetate containing 0.1% formic acid aqueous as mobile phase gradient elution at the flow rate of 0.4 mL/min. Multiple reaction monitoring scan was performed in electrospray positive ion mode, quantitative measurement was performed by internal standard method, and methodological verification was carried out.@*RESULTS@#The linear relationship of bucinnazine in blood was good in the range of 0.5-200 μg/L, the correlation coefficient (r) was 0.999 7, the limit of detection was 0.1 μg/L, the limit of quantitation was 0.5 μg/L, and the recovery was 78.3%-83.8% at 1, 10 and 100 μg/L mass concentration levels. The matrix effect was 69.4%-73.8%, the intra-day precision was 1.9%-2.8%, and the inter-day precision was 2.8%-3.2%, the accuracy was 3.1%-3.5%. The stability test results of 1 and 100 μg/L mass concentrations at -25 ℃ showed that the accuracy (bias) of 10 d was less than 4.5%.@*CONCLUSIONS@#This method has the advantages of simple pre-treatment process, fast sample processing speed, high sensitivity of instrument analysis, good stability of content determination and reliable identification results, and can meet the needs of case identification.
Subject(s)
Tandem Mass Spectrometry/methods , Chromatography, Liquid , Chromatography, High Pressure Liquid/methods , AcetonitrilesABSTRACT
OBJECTIVES@#To establish a method for the simultaneous quantitative analysis of etomidate and its metabolite etomidate acid in blood, and to discuss its application value in actual cases.@*METHODS@#Acetonitrile precipitate protein method was used, and C18 column was selected. Gradient elution was performed with acetonitrile and 5 mmol/L ammonium acetate within 6 min. Electrospray ionization source in positive ion mode was used. The internal standard etomidate acid-d5 was obtained by etomidate-d5 alkaline hydrolysis reaction. Ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was used for quantitative analysis. The methodological verification was conducted.@*RESULTS@#Etomidate and etomidate acid in blood showed good linear relationship in the quantitative linear range (r>0.999), with the lower limit of quantification was 2.5 ng/mL and 7.5 ng/mL, respectively. The accuracy, precision, recovery rate, and matrix effect of the method met the professional verification standards. The practical application results showed that etomidate and etomidate acid could be detected in the blood of the abusers, and their mass concentrations ranged from 17.24 to 379.93 ng/mL.@*CONCLUSIONS@#The method established in this study can simultaneously quantify etomidate and etomidate acid in blood, which is simple and convenient to operate with accuracy. It can meet the detection needs of actual cases and provide technical support for law enforcement to crack down on etomidate abuse.
Subject(s)
Chromatography, High Pressure Liquid/methods , Chromatography, Liquid , Etomidate , Tandem Mass Spectrometry/methods , Liquid Chromatography-Mass Spectrometry , AcetonitrilesABSTRACT
Objective To establish a high-performance liquid chromatography-tandem mass spectrometry(LC-MS/MS)method for the simultaneous determination of seven vitamin Bs(VBs)in rat plasma.Methods The plasma samples were pretreated using the protein precipitation method.The chromatographic separation was achieved using an Agilent ZORBAX SB-Aq column(2.1 mm×150 mm,3.5 μm),with a mobile phase composed of 0.01%formic acid(A)and methanol(B)in a gradient elution mode.The flow rate was set at 0.3 mL·min-1 and the column temperature was maintained at 30℃.Mass spectrometric detection was performed using positive ion mode in multiple reaction monitoring.2,4,5,6-Deuteronicotinamide was used as the internal standard.Results Methodological validation results showed that the lowest limits of quantitation(LOQs)for the seven VBs ranged from 7.5 to 300 ng/mL,while the highest LOQs ranged from 1 000 to 20 000 ng·mL-1.Within a certain concentration range,all compounds showed a good linearity(r2>0.992 2).The accuracies ranged from 86.0%to 117.6%,and both intra-and inter-batch precision were less than 20%.Additionally,all analytes demonstrated extraction recoveries greater than 86.1%.No significant matrix effects were observed,and the stability was good.The established validation method was successfully applied to the pharmacokinetics study of single intragastric administration of VB solution in SD rats.Conclusion The analytical method established in this study is simple,rapid,sensitive,and exclusive for the simultaneous determination of VB in real plasma samples.This LC-MS/MS method provides a new analytical tool for further exploring the physiological and pathological effects of VB.
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Background Dicamba is widely used in agricultural production in China, but it is extremely soluble in water and can be harmful to human health when it enters the body via water drinking. It is necessary to establish an accurate, sensitive, and rapid detection method to determine the residues of dicamba in domestic drinking water. Objective To establish two methods for the determination of dicamba residues in drinking water by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) and gas chromatography-tandem mass spectrometry (GC-MS/MS) respectively. Methods The conditions of the proposed method using HPLC-MS/MS included CAPCELL PAK ST chromatographic column, ammonium formate water solution and methanol as the mobile phase, and isocratic elution. The system was operated under multiple reaction monitoring mode and electrospray negative ionization mode. Trimethylsilylated diazomethane was used as a derivatizing agent for GC-MS/MS, and an external standard curve was used to evaluate the system. The residues of dicamba in seven water samples of tap water or secondary water supply from six regions in Chengdu were detected by the established systems to evaluate their applicability and to understand the status quo of dicamba residues in drinking water. Results For the HPLC-MS/MS, the linear range of dicamba was 1.00-100 μg·L−1, the regression equation was \begin{document}$\hat Y $\end{document}=1250.9X+2681.5, the correlation coefficient was 0.9988, the relative standard deviations were 1.23%-26.3%, the limit of detection was 0.95 μg·L−1, and the spiked recoveries were 91.8%-111%. For the GC-MS/MS, the linear range of dicamba was 0.200-10.0 μg·L−1, the regression equation was \begin{document}$\hat Y $\end{document}=190597X+40911, the correlation coefficient was 0.9993, the relative standard deviations were 0.64%-3.90%, the limit of detection was 0.18 μg·L−1, and the spiked recoveries were 97.3%-105%. No dicamba residue was identified in the seven water samples of tap water or secondary water supply from six regions in Chengdu by the proposed methods. Conclusion The two detection methods established in this study are sensitive and rapid, meet the requirements from the detection of dicamba residues in drinking water, and provide an experimental basis for subsequent research on the detection of dicamba residues. In the future, it is necessary to continue to pay attention to the pollution of dicamba in drinking water in Chengdu.
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Objective@#To establish a ultra-high performance liquid chromatography-tandem triple quadrupole mass spectrometry method for rapid simultaneous determination of quinclorac, acetochlor, butachlor and metolachlor in urine.@*Methods@#Urine samples were diluted 10 times, prepared into the mixed standard solution, and subjected to gradient elution on the ACQUITY UPLC BEH C18 column (100 mm×2.1 mm, 1.7 μm) with 0.1% formic acid and acetonitrile as the mobile phase. The quinclorac, acetochlor, metolachlor and butachlor levels were determined using electrospray ionization-positive ultra-high performance liquid chromatography-tandem triple quadrupole mass spectrometry with the multiple reaction monitoring mode.@*Results@#Four herbicides were effectively separated on the ACQUITY UPLC BEH C18 column (100 mm× 2.1 mm, 1.7 μm), and good linear relationships were observed for quinclorac, acetochlor and butachlor at 1 to 25 μg/L and for metolachlor at 0.2 to 25 μg/L, with all linear correlation coefficients of >0.999. The detection limts of quinclorac, acetochlor, butachlor and metolachlor were 0.10, 0.10, 0.20 and 0.01 μg/L, respectively. The recovery rates of quinclorac, acetochlor and butachlor were 107.42%, 93.94% and 90.27% from urine samples at a spiked level of 5 µg/L, with relative standard deviations of 4.82%, 3.84% and 6.76%, and the recovery rate of metolachlor was 89.51% at a spiked level of 0.5 µg/L, with a relative standard deviation of 8.98%.@*Conclusion@#The chromatography and mass spectrometry conditions are optimized in this ultra-high performance liquid chromatography-tandem mass spectrometry, which is effective for rapid simultaneous determination of quinclorac, acetochlor, metolachlor and butachlor in urine samples.
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@#An innovative approach to quantitatively analyze the histamine and its precursor histidine simultaneously in biological matrices was established for the first time based on double adsorption combined with high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS).The internal standard was 2-dihydroxybenzoic acid (DHB).The plasma and brain tissue homogenate was protein precipitated with 3-fold acetonitrile, and the supernatant was then sampled for injection analysis.The chromatographic separation of the target components was achieved on an amino chromatography column (ODS-SPXBridge? Amide).Gradient elution was carried out with the mobile phase consisting of solvent A (0.1% formic acid and 1mmol/L ammonium formate in water) and solvent B (acetonitrile).Mass spectrometry was employed for quantitative analysis with ESI ion source in multiple reaction monitoring (MRM) mode.In order to improve the specificity and accuracy, activated carbon and calcite were used for the double adsorption of biological matrices for the first time.The adsorbed matrix was then used for methodology validation.The results showed that histamine and histidine were linear in the quantitative range (correlation coefficient r ≥ 0.999).Accuracy, precision, extraction recovery, matrix effect and stability all met the requirements of biological sample analysis.All results suggested that the present method could not only be efficiently and reliably used for simultaneous quantitative analysis of histamine and histidine in biological samples, but also provide reference for the detection of other endogenous substances.
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Endogenous ribonucleotides(RNs)and deoxyribonucleotides(dRNs)are important metabolites related to the pathogenesis of many diseases.In light of their physiological and pathological significances,a novel and sensitive pre-column derivatization method with N-(t-butyldimethylsilyl)-N-methyltri-fluoroacetamide(MTBSTFA)was developed to determine RNs and dRNs in human cells using high-performance liquid chromatography tandem mass spectrometry(HPLC-MS/MS).A one-step extraction of cells with 85％methanol followed by a simple derivatization reaction within 5 min at room temper-ature contributed to shortened analysis time.The derivatives of 22 nucleoside mono-,di-and tri-phosphates were retained on the typical Cig column and eluted by ammonium acetate and acetonitrile in 9 min.Under these optimal conditions,good linearity was achieved in the tested calibration ranges.The lower limit of quantitation(LLOQ)was determined to be 0.1-0.4 μM for the tested RNs and 0.001-0.1 μM for dRNs.In addition,the precision(CV)was＜15％and the RSD of stability was lower than 10.4％.Furthermore,this method was applied to quantify the endogenous nucleotides in human colorectal carcinoma cell lines HCT116 exposed to 10-hydroxycamptothecin.In conclusion,our method has proven to be simple,rapid,sensitive,and reliable.It may be used for specific expanded studies on intracellular pharmacology in vitro.
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Objective: To establish a method for rapid determination of bongkrekic acid (BA) in plasma by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Methods: In November 2020, plasma samples were extracted by methanol and acetonitrile (1∶1) and purified directly. The samples were separated by C18 column. Gradient elution was carried out with 5 mmol/L ammonium acetate water acetonitrile solution as mobile phase. Under the optimized instrument conditions, the electrospray ionization multiple reaction monitoring (MRM) mode was used, and the external standard method was used for quantitative analysis. Results: The linear relationship of BA in plasma was good in the concentration range of 2-100 μg/L, the correlation coefficient was 0.9998, the average recovery was 83.7%-112.0%, the relative standard deviation within and between batches was less than 10%, the detection limit of the method was 0.7 μg/L and the lower limit of quantification was 2.0 μg/L. Conclusion: The method is simple, rapid, accurate and sensitive, and can meet the requirements for the determination of BA in blood samples of poisoning patients.
Subject(s)
Humans , Bongkrekic Acid , Chromatography, High Pressure Liquid , Solid Phase Extraction , Tandem Mass SpectrometryABSTRACT
OBJECTIVES@#To analyze the characteristics of diphenidol poisoning cases and to provide clues and technical means for the identification of such cases.@*METHODS@#Biological samples of 9 deaths caused by diphenidol poisoning were detected by ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), and the characteristics of these cases were analyzed retrospectively.@*RESULTS@#Most of the deaths caused by diphenidol poisoning were young females. The dosage was between 60 and 300 tablets, and the mass concentration of diphenidol in the postmortem blood ranged from 0.87 to 99.00 μg/mL. There was no correlation between the dosage and the concentration of diphenidol in the blood.@*CONCLUSIONS@#Diphenidol poisoning has the characteristics of high concealment and lethality. More attention should be paid to suicide cases, and diphenidol should be recommended as a routine detection item to avoid missing detection.
Subject(s)
Female , Humans , Chromatography, Liquid/methods , Tandem Mass Spectrometry/methods , Retrospective Studies , Administration, OralABSTRACT
OBJECTIVES@#To establish a combined high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) and gas chromatography-mass spectrometry (GC-MS) method to detect the synthetic cannabinoid CUMYL-PEGACLONE in e-cigarette oil and hair.@*METHODS@#HPLC-MS/MS and GC-MS were used to establish the detection method of CUMYL-PEGACLONE, and the hair of drug-involved persons and the seized e-cigarette oil were detected.@*RESULTS@#The main mass spectrometry characteristic ions m/z of CUMYL-PEGACLONE measured by GC-MS were 91, 179, 197, 254 and 372. CUMYL-PEGACLONE had a good linear relationship in the mass concentration range of 2-50 ng/mL, and the linear correlation coefficient (r) was greater than 0.99. The limit of detection (LOD) of CUMYL-PEGACLONE in hair was 0.01 ng/mg, and the limit of quantitation (LOQ) was 0.02 ng/mg. The LOD of CUMYL-PEGACLONE in e-cigarette oil was 1 ng/mg, and the LOQ was 2 ng/mg. The average recoveries of CUMYL-PEGACLONE under the attempt at high, intermediate and low levels in blank human hair and e-cigarette oil matrix were 98.2%-132.4% and 93.5%-110.6%, and the intraday and intraday precision were 1.2%-12.9% and 0.7%-2.9%. CUMYL-PEGACLONE was detected in the hair of 15 drug-involved persons. Except for 1 person who was lower than LOQ, the concentration of CUMYL-PEGACLONE in the hair of other 14 persons was 0.035-0.563 ng/mg. The mass fraction of CUMYL-PEGACLONE in 2 e-cigarette oil were 0.17% and 0.21%, respectively.@*CONCLUSIONS@#The established HPLC-MS/MS and GC-MS methods are applied to the detection of HPLC-MS/MS in drug-related cases, which provides strong evidence support for the handling authority to quickly investigate these cases, and also provides a reference for the identification of such substances in future.
Subject(s)
Humans , Illicit Drugs/analysis , Tandem Mass Spectrometry , Electronic Nicotine Delivery Systems , Cannabinoids , Hair/chemistry , Limit of Detection , Substance Abuse Detection/methodsABSTRACT
Objective To establish a method combining QuEChERS and ultra-high liquid chromatography-tandem mass spectrometry （UPLC-MS/MS） for rapid screening and testing of three types of new psychoactive tryptamines in human blood： 5-MeO-DALT, 5-MeO-MiPT and 5-MeO-DiPT. Methods The effects of the type of extractant, the type and dosage of salting-out agent, and the dosage of adsorbent on the test results of the three tryptamines were investigated. Blood samples were processed by QuEChERS method and then determined by UPLC-MS/MS. Results The linear relationships of 5-MeO-DALT, 5-MeO-MiPT and 5-MeO-DiPT in human blood were good in the range of 0.5-100, 0.5-100 and 0.2-100 ng/mL, respectively, with their coefficients higher than 0.99. The limits of detection （LODs） were 0.1-0.2 ng/mg. The recoveries ranged from 84.86% to 94.57%. Intra-day and inter-day precisions were good. Conclusion The method is simple, rapid, easy to operate and has a high recovery. It is suitable for the qualitative and quantitative study of tryptamines in blood and can provide the reference for public security organs to deal with related cases.
Subject(s)
Humans , Chromatography, High Pressure Liquid , Chromatography, Liquid , Limit of Detection , Tandem Mass Spectrometry , TryptaminesABSTRACT
Objective To establish a detection system of ultra high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) for everolimus concentration in whole blood of liver transplant recipients. Methods The proteins of samples were precipitated with methanol and zinc sulfate, and everolimus-D4 was used as the internal standard. Phenomenex Kinetex PFP column was used. The mobile phase A was water (containing 2 mmol/Lammonium formate and 0.1% formic acid), and the mobile phase B was methanol (containing 2 mmol/L ammonium formate and 0.1% formic acid). The gradient elution was performed with the flow rate of 1 mL/min, the column temperature of 50 ℃ and the injection volume of 1 μL. The multi-reaction monitoring mode was used to quantitatively analyze with electrospray positive ionization. The UPLC-MS/MS detection system required only 100 μL of whole blood, and could achieve a sufficient lower limit of quantification without complicated sample preparation. The total running time was within 4.5 min. Linear regression (1/x2) analysis was performed using peak area of everolimus / peak area of everolimus-D4 (y) and concentration of everolimus/concentration of everolimus-D4 (x) to calculate the calibration function and analyze its accuracy and linear relationship. UPLC-MS/MS was used to detect the trough blood concentration of everolimus in blood samples of 5 recipients after liver transplantation. Results The accuracy of quality control was within 15%, and the linear relationship of everolimus was good in the blood concentration range of 1-100 ng /mL(R2 > 0.990). Trough blood concentration of everolimus measured in blood samples of 5 liver transplant recipients ranged from 3.77 to 9.27 ng/mL. Conclusions The detection system of UPLC-MS/MS in this study is suitable for monitoring the concentration of everolimus in whole blood of liver transplant recipients because of its high accuracy, simple sample processing method and short detection time.
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Objective::To investigate the effect of polyethylene glycol 400 (PEG400) on rat bile excretion of baicalin and its main metabolite [baicalein 6-O-β-D-glucuronide (B6G)], and to analyze its mechanism of action. Method::Rats were randomly divided into baicalin+ water group and baicalin+ PEG400 group, the anesthesia was induced by intraperitoneal injection of 10% chloral hydrate (dose of 4 mL·kg-1) to prepare a rat bile duct intubation model. After the rats were fully awake, rats were given baicalin aqueous solution and baicalin PEG400 solution with dose of 168 mg·kg-1 for baicalin, respectively. And bile was collected from 0 h to 12 h after administration. UPLC-MS/MS was used to determine the concentration of drug excreted through bile at different time periods. Thermo Hypersil GOLD C18 column was used with acetonitrile (A)-0.1% formic acid solution (B) as the mobile phase for gradient elution (0-9 min, 90%-27%B; 9-10 min, 27%-90%B; 10-12 min, 90%B), the flow rate was 0.3 mL·min-1, the column temperature was 30 ℃, the injection volume was 5 μL. The mass spectra were obtained in positive ion mode with electrospray ionization (ESI). The effects of PEG400 on the activities and expressions in rat liver of uridine diphosphate glucuronyltransferase (UGT) 1A8 and UGT1A9 were studied in vitro incubation assay and enzyme linked immunosorbent assay (ELISA). Result::Compared with the baicalin+ water group, in the baicalin+ PEG400 group, the bile cumulative excretions of baicalin and B6G increased by 1.8 times and 2.1 times within 12 h, respectively. PEG400 increased the enzyme activities of UGT1A8 and UGT1A9 by 2.0 times and 1.5 times, and their concentrations in liver were increased by 2.2 times and 1.3 times, respectively. Conclusion::PEG400 can significantly increase the bile excretion of baicalin and its main metabolite B6G by enhancing the activities and expressions of UGT1A8 and UGT1A9, and its promoting effect on bile excretion of B6G is greater than that of baicalin, which provides a basis for the rational clinical application of PEG400 and the design of new dosage forms of flavonoids such as baicalin.