GC/MS和GC法定性定量分析可卡因

目的建立用于可卡因案件检验鉴定的GC和GC/MS定性、定量分析方法。方法通过选择和优化,建立GC、GC/MS法检验可卡因的最佳分析条件;用分别含0.6mg/ml地西泮为内标的0.10、0.20、0.40、0.60、0.80、1.00、1.20mg/ml可卡因标准品乙醇液,考察线性范围和方法检测限。结果分析方法线性方程:GC/FID,Y=1.055X-0.0021,R2=0.9999,GC/NPD,Y=0.556X-0.0016,R2=0.9996;可卡因检测限:GC/FID法10ng,GC/NPD法2ng;分别以所建GC/FID、GC/NPD分析方法和内标法对案件中缴获的可卡因毒品进行定量分析,结果为72%±2.3%,且两方法定量重现性良好。结论本文所建方法可以用于可卡因涉毒案件的检验鉴定。     

HS-GC／FID分析血中的乙醚

目的建立顶空GC/FID分析血中乙醚的方法。方法用顶空GC/FID分析血中乙醚,并对萃取条件和色谱条件进行优化。结果方法的检出限为0.3ug/ml,回收率为81%,相对标准偏差为4.4%。结论该法简便、快速、灵敏,适合毒物分析检验的要求。     

Creatinine analysis in single collection urine specimens.

Controlled and uncontrolled fluid intake studies were conducted on series of volunteers over the 6 or 12 h of the study periods. Urine specimens were obtained from each subject randomly or at specified times relative to fluid ingestion. Creatinine analysis performed by a modification of the Abbott TDx procedure demonstrates that the values obtained from single collection specimens fall almost in the same range as the values from 24 h pooled collection specimens. The creatinine concentration can be used to indicate possible adulteration of urine specimens by dilution as a means of avoiding detection of use of drugs of abuse. Between 4 and 7 h are required for a decrease in creatinine concentration to about 100 mg/dL from an initial mean of about 170 mg/dL. A minimum of 6 h is needed for any creatinine value to fall to 50 mg/dL or less. Thus, it appears that creatinine output is sensitive to the amount of fluid ingested, but the relationship is neither linear nor immediate. The absence of a significant creatinine concentration in a specimen can be used as an indication of direct or indirect adulteration of the urine specimen by dilution or replacement with water. At NDSL-Great Lakes, a decline of the creatinine concentration to 30 mg/dL is used as a cutoff for differentiating between urine specimens that might have been tampered with to avoid detection of drug use and those specimens that are dilute for other reasons. Values at 10 mg/dL or less are suggestive of replacement by water. The information is provided to local commands for investigation prior to initiation of punitive action by the command.     

固相萃取一气相色谱法分析全血中的唑吡坦

目的建立全血中唑吡坦的固相萃取一气相色谱检测方法。方法采用OasisHLB固相萃取柱提取，GC／NPD定量检验，GC／MS定性检验。结果血样中唑吡坦平均提取回收率达88．6％，最低检出限达2×10-2μg／ml，线性相关系数为0．9976。结论该方法操作简便快速，提取回收率高，重现性好，可用于实际案例中唑吡坦的分析。     

Development of Rapid and Economical Colorimetric Screening Method for p‐Phenylenediamine in Variety of Biological Matrices and its Application to Eleven Fatal Cases of p‐Phenylenediamine Poisoning

A rapid colorimetric method for detection of p‐phenylenediamine (PPD) in various biological samples is developed. The o‐cresol test for acetaminophen detection has been modified to detect PPD in blood, urine, gastric contents, and liver. After precipitating protein with trichloroacetic acid solution (2 mL, 10% w/v), biological specimens were required to convert PPD metabolites to PPD by acid hydrolysis. Finally, o‐cresol solution (1 mL, 1% w/v), hydrogen peroxide (200 μL, 3%v/v), and concentrated ammonium hydroxide (0.5 mL) were added in the biological samples. The presence of PPD was indicated by formation of violet color which was turned to bluish green color within 10–15 min. The limit of detection was found to be 2 mg/L in blood, urine, and gastric contents and 2 mg/Kg in liver. This method is also free from any potential interference by p‐aminophenol, acetaminophen, and other amine drugs under test conditions. This method was successfully employed to thirteen fatal cases of PPD poisoning.     

人血、尿中富马酸喹硫平的气相色谱分析

目的建立人血、尿中富马酸喹硫平的气相色谱分析方法。方法用乙醚提取血、尿中的富马酸喹硫平，直接对其进行定性、定量分析。以正常人血、尿为空白样本，分别添加标准富马酸喹硫平，确定检材的前处理方法、色谱分析条件、工作曲线、线性范围、方法的精密度、回收率等，并对1例大剂量服用富马酸喹硫平中毒死者的体液浓度进行测定。结果该方法分析血、尿中富马酸喹硫平的线性范围分别为8．0～800．0μg／ml和20．0—800．0μg/ml；最低检测限分别为0．04μg／ml和0．10μg／ml（S／N≥3），日内、日间精密度均小于4％，回收率在97．08％-101．42％之间。结论该分析方法操作便捷、实用、准确度高，适用于富马酸喹硫平的临床血药浓度快速监测和法医毒物鉴定。     

GC/MS法检测全血中的奥氮平

目的采用乙睛-甲醇混合溶剂提取、气质联用分析法检测全血中奥氮平。方法针对奥氮平特性,在加入稳定剂硫代硫酸钠条件下采用乙睛-甲醇混合溶剂提取法,采用GC/MS分析法,对全血中的奥氮平进行定性、定量分析。并对提取介质、酸碱度、稳定剂种类及用量进行了考察。结果采用本文方法在奥氮平为1～400μg/mL浓度范围内呈良好的线性关系(r2=0.999 8,n=5),检出限为1.0ng,方法平均回收率可达66.5%(RSD=2.5%)。日内RSD为2.1%～3.9%,日间RSD为2.9%～4.5%。选择乙腈∶甲醇(V∶V=8∶2)混合溶剂进行液-液提取,稳定剂为300mg硫代硫酸钠。结论本文方法可用于全血中奥氮平检测,在相关案件检验中选择使用。     

毛细管气相色谱法测定酱油中4-甲基咪唑的含量

目的建立毛细管气相色谱法定量分析酱油中有毒成分4-甲基咪唑的方法。方法酱油样品在层析柱中用二氯甲烷洗脱,洗脱液浓缩后加入N,N-二甲基苯胺作为内标,采用DB-FFAP毛细管柱分离样品,氮磷检测器测定4-甲基咪唑含量。结果方法线性范围为4.9~1.5×102μg/L;检测限为0.16μg/L;标准加入0.0102mg和0.0602mg 4-甲基咪唑的平均回收率为97.25%和99.44%。结论本文方法具有操作简便、快速、准确等优点,可用于检验酱油中的4-甲基咪唑。     

The comparison of toluene determination between headspace-solid phase microextraction and headspace methods in glue-sniffer's blood and urine samples

An accurate and simple method was developed to determine the level of toluene in urine and blood quantitatively by using the gas chromatography/mass spectrometry (GC/MS) with headspace--solid phase microextraction (HS-SPME) technique. An assembly of SPME with a replaceable extraction fiber, coated with 100 microm polydimethylsiloxane, was used. The detection limit of toluene in blood and urine with HS-SPME technique was 10 times higher than that with headspace (HS) technique. To compare the HS-SPME with HS technique for the determination of toluene in biological fluids, blood and urine samples from glue sniffers were analyzed by both methods. The level of toluene by the two techniques was highly correlated: the correlation coefficient (r2) between the two sets of values were 0.98 and 0.96 in urine and blood, respectively.     

The detection of psilocin in human urine

Pharmacokinetic studies of psilocybin in humans have shown the rapid dephosphorylation of psilocybin to psilocin with further conversion to 4-hydroxy-tryptophole (4HT) and 4-hydroxyindole-3-acetic acid (4HIAA) in plasma. Our study shows that psilocin also undergoes conjugation and can be found in the urine as the psilocin-glucuronide conjugate. Recoveries after enzymatic hydrolysis of the urine with beta-glucuronidase (Helix Pomatia or E. Coli) when compared to non-hydrolyzed urine confirmed the presence of the glucuronide. Detection of psilocin from hydrolyzed and extracted samples was optimized for GC/MS by derivatization with MSTFA. The method developed allows for the detection of psilocin in urine with a limit of quantitation of 10 ng/mL, based on 5 mL of spiked urine. Using this method, our laboratory has confirmed the presence of psilocin in 6 out of 8 urine samples, with concentrations ranging from 10 ng/mL to greater than 200 ng/mL. Before implementation of the hydrolysis and derivatization steps, our limit of detection was 200 ng/mL, based on spiked urine standards. No case samples were positive without hydrolysis and derivatization.     

快速溶剂萃取法提取血中的有机磷类农药

目的建立生物检材血液中有机磷类农药的快速溶剂萃取方法。方法通过优化快速溶剂萃取各参数，提取血中的有机磷类农药，同时达到在线净化的效果，然后进行GC／FPD分析检测。结果血中5种常见有机磷类农药的平均回收率均在70％以上，在0．05μg／mL-5μg／mL浓度范围内线性关系良好，检测限（S／N=10）均低于20ng／mL。结论该方法优于其它传统提取方法，快速、简便、高效且操作自动化，可广泛应用于生物检材血液中有机磷类农药的检验鉴定。     

Validity testing of the TDx Cocaine Metabolite Assay with human specimens obtained after intravenous cocaine administration

Clinical specimens obtained from human subjects after intravenous cocaine administration were analyzed by the TDx Cocaine Metabolite Assay (TDx) and by GC/MS for benzoylecgonine. The TDx results were significantly correlated with results by GC/MS assay with no evidence of bias in the TDx assay. All cocaine metabolite positive specimens (greater than or equal to 300 ng/ml) were confirmed by GC/MS. Detection times to the last positive specimen by TDx assay and GC/MS assay of four subjects after a 20-mg intravenous dose of cocaine ranged from 29.3 to 39.1 h and 27.9 and 36.6 h, respectively. Overall, the TDx assay was found to be highly specific and accurate for the detection and measurement of benzoylecgonine in urine.     

GC/MS法测定人体血液和肾、肝组织中的丙泊酚

目的 采用气相色谱/质谱法检测人体血液和肾、肝组织中的丙泊酚.方法 心血和肾、肝组织中的丙泊酚经环己烷提取,采用气相色谱/质谱法,丙泊酚选择m/z 163、178,内标百里香酚选择m/z 150、135进行测定;并考察方法专属性、线性范围、定量线与检出限、回收率与精密度.结果 丙泊酚的保留时间为8.17min,与内标百里香酚分离良好;其在心血和肾、肝组织中的检测浓度线性关系良好,r值均大于0.992,最低检测质量浓度分别为0.05 μg/mL、0.10μg/g及0.05 μg/g,方法回收率90％ ～ 110％,日内、日间RSD均小于7％.结论 本文方法简便、灵敏、快速,其准确度、精密度和回收率均可满足生物检材中丙泊酚浓度的测定,可在相关研究及实践中选用.     

尿中氯胺酮及其代谢物检测的研究

目的建立氯胺酮滥用者尿中氯胺酮及其代谢物检测方法。方法尿液用有机溶剂液-液萃取,气相色谱/氮磷检测器、电子捕获检测器、氢火焰检测器和气-质联用仪测定。结果确认了尿液中氯胺酮的主要代谢物,尿液中氯胺酮及去甲氯胺酮的最小检测限均为2ng/mL,脱氢去甲氯胺酮的最小检测限为5ng/mL。结论所建方法快速、灵敏、准确,能够满足氯胺酮滥用者尿液检测的需要。     

Screening postmortem blood and tissues for nine classes [correction of cases] of drugs of abuse using automated microplate immunoassay

A commercially available enzyme-linked immunosorbant assay (ELISA) was evaluated as a screening procedure for the detection of nine classes of abused drugs in postmortem blood and tissue specimens. Specifically, postmortem blood, fluid and/or tissue homogenates were screened for amphetamine (AMP), methamphetamine (MET), barbiturates (BARB), benzodiazepines (BZD), cannabinoids (CNB), cocaine (benzoylecgonine; BE), morphine-specific (MOR), opiates (class; OPI), phencyclidine (PCP) and lysergic acid diethylamide (LSD) by ELISA and by coated tube radioimmunoassay (CTR) (BARB, BE, OPI, PCP, LSD) or double-antibody radioimmunoassay (DAR) (AMP/METH, BZD, CNB). Specimens that screened 'positive' by any method were confirmed and quantitated by gas chromatography/mass spectrometry (GC/MS). The only assay that appeared to perform less optimally than RIA was the MOR assay (five false negatives). However, this assay is very specific for free morphine while the GC/MS confirmation method provided a total morphine value. The OPI assay was more sensitive, producing fewer false negatives, and is recommended for broad class opiate screening. EIA is an adequate alternative to RIA for screening postmortem specimens, including blood and tissue, for nine major classes of drugs.     

Peak blood-ethanol concentration and the time of its occurrence after rapid drinking on an empty stomach

Healthy men, 20 to 60 years old, drank a moderate dose of ethanol in the morning after an overnight fast. They consumed either neat whisky in amounts corresponding to 0.34, 0.51, 0.68, 0.85, or 1.02 g of ethanol per kilogram of body weight or 0.80 g/kg ethanol solvent diluted with orange juice. The peak blood-ethanol concentration (BEC) increased with the dose administered, but the time required to reach the peak was not markedly influenced over the range of doses studied. At a dose of 0.68 g/kg, the peak BEC ranged from 52 to 136 mg/dL (N = 83), and slow absorption (a late-occurring peak) produced a lower peak BEC. The peak BEC was reached between 0 and 45 min for 77% of the subjects (N = 152) and between 0 and 75 min for 97% of them. The time of peaking in venous blood occurred, on average, 10 min later than in capillary (fingertip) blood although the peak BEC was not appreciably different; the mean venous BEC was 97.0 mg/dL (range, 76 to 112 mg/dL), and the mean capillary BEC was 99.6 mg/dL (range, 75 to 123 mg/dL). When subjects drank 0.80 g/kg ethanol diluted with orange juice over 30 min, the average BEC increment between the end of drinking and the peak was 33 mg/dL (range, 0 to 58 mg/dL). The rate of absorption of ethanol was 1.78 mg/dL/min (range, 0.52 to 4.8 mg/dL/min), and the peak BEC occurred within 60 min after the end of drinking in 92% of the trials. The largest BEC increment (mean, 21 mg/dL; range, 0 to 44 mg/dL) was seen during the first 15 min after the drinking period.     

GC法检测血液和尿液中甲基苯丙胺和咖啡因

目的建立同时测定血、尿中甲基苯丙胺和咖啡因含量的方法。方法应用GC／NPD技术,以4-苯基丁胺为内标,直接碱化,用氯仿提取,三氟乙酸酐衍生化,8CB熔融石英毛细管柱（30m×0．25mm×0．25μm）分析。结果生物样品中甲基苯丙胺与咖啡因在0．012—7．5μg/mL浓度范围内线性关系良好,检测限（S／N=3）依次为1．2ng／mL,0．6ng／mL（血）;1．6ng／mL,0．8ng／mL（尿）。苯丙胺在0．017—10．0μg／mL浓度范围内线性关系良好,检测限为1．6mg／mL（血）,3．2ng／mL（尿）。所有样本回收率均大于85％。结论本方法准确、灵敏,适用于血、尿中甲基苯丙胺及其代谢物苯丙胺的三氟乙酸酐衍生化物和咖啡因的同时检测,为判定滥用毒品种类、追查毒品来源以及研究生物体内甲基苯丙胺和咖啡因的交互影响提供了检测手段。     

Poppy seed consumption and toxicological analysis of blood and urine samples

Poppy seeds contain morphine in different amounts. Reported concentrations are up to 294 mg morphine/kg poppy seeds. Since penalties based on Street Traffic Law (parapgraph 24a StVG) in Germany (administrative offence) require definitive proof of morphine in blood samples, and the "Grenzwertkommission" in consultation with the Ministry of Transportation recommended a threshold of free morphine of 10 ng/mL, the question arose whether the consumption of poppy seeds can lead to a blood concentrations equal or higher than 10 ng/mL of free morphine. Therefore, five volunteers ate poppy seed products (50 mg morphine/kg poppy seeds). In urine, all on-site tests were enzyme immunologically positive for opiates and were positive to morphine by GC/MS. All the blood samples were negative to morphine by EIA and to free morphine by GC/MS. However, after hydrolysis, morphine was detected by GC/MS in all cases. Accordingly, in Germany, penalties based on parapgraph 24a StVG are not likely to cause road users any concerns should they have consumed poppy seeds. Driver Licensing Authorities, however, should be advised of this problem to avoid unjustified legal measures.     

分子印迹固相萃取法在血中苯丙胺类毒品分析中的应用

目的建立分子印迹固相萃取（MISPE）、GC/MS分析方法,用于血液中苯丙胺类毒品检测。方法 10mmol/L醋酸铵缓冲液（pH8.0）4倍稀释空白添加血液,1mL甲醇,1mL10mmol/L醋酸铵缓冲液（pH8.0）活化苯丙胺类分子印迹固相萃取柱;2×1mL去离子水、1mL60%的乙腈去离子水、1mL1%醋酸乙腈洗涤杂质;2×1mL1%甲酸/甲醇洗脱,洗脱液挥干定容,经GC/NPD、GC/MS分析检测。结果各种苯丙胺类毒品回收率均在90%以上,在20～5 000ng/mL浓度范围内线性关系良好,r2为0.995 7～0.998 9,LOQ在16～30ng/mL之间,LOD在8～15ng/mL之间。结论本方法回收率高,净化效果显著,稳定性好,杂质干扰少,可用于血液中低浓度苯丙胺类毒品的分析检测。     

Analysis of pain management drugs, specifically fentanyl, in hair: application to forensic specimens

This article discusses the immunoassay screening of pain management drugs, and the mass spectrometric confirmation of fentanyl in human hair. Hair specimens were screened for fentanyl, opiates (including oxycodone), tramadol, propoxyphene, carisoprodol, methadone, and benzodiazepines and any positive results were confirmed using gas chromatography or liquid chromatography with mass spectral detection. The specific focus of the work was the determination of fentanyl in hair, since autopsy specimens were also available for comparison with hair concentrations. Using two-dimensional gas chromatography with electron impact mass spectrometric detection, fentanyl was confirmed in four of nine hair specimens collected at autopsy. The accuracy of the assay at 10 pg/mg was 95.17% and the inter-day and intra-day precision was 5.04 and 13.24%, respectively (n=5). The assay was linear over the range 5-200 pg/mg with a correlation of r(2)>0.99. The equation of the calibration curve forced through the origin was y=0.0053x and the limit of quantitation of the assay was 5 pg/mg. The fentanyl concentrations detected were 12, 17, 490, and 1930 pg/mg and the results were compared with toxicology from routine post-mortem analysis. The screening of pain management drugs in hair is useful in cases where other matrices may not be available, and in routine testing of hair for abused drugs.