生物样品的色谱-质谱定性确认指标CSCD

由于复杂基质的存在,生物样品中毒物的色谱-质谱定性确认指标与非生物样品有所不同。即使同为生物样品,定性确认指标也会因应用领域的不同而不尽相同。本文综述了法医毒物分析及其他应用领域生物样品中待测物的色谱-质谱定性确认指标的异同,这些确认指标主要包括保留时间、相对保留时间、信噪比、特征离子、特征离子的相对丰度、母离子-子离子对和离子对丰度比等。     

生物样品的色谱-质谱定性确认指标

由于复杂基质的存在,生物样品中毒物的色谱-质谱定性确认指标与非生物样品有所不同。即使同为生物样品,定性确认指标也会因应用领域的不同而不尽相同。本文综述了法医毒物分析及其他应用领域生物样品中待测物的色谱-质谱定性确认指标的异同,这些确认指标主要包括保留时间、相对保留时间、信噪比、特征离子、特征离子的相对丰度、母离子-子离子对和离子对丰度比等。     

优化AMDIS软件建库自动筛选常见有机毒物

目的优化AMDIS软件,建立常见有机毒物的GC/MS自动筛选方法。方法建立信息型中文常见毒物的质谱库,优化分离条件并测定多种毒物的保留时间,优化检索条件并测定多种毒物的检测限。结果建立含2344种常见药毒物的中文质谱库;测定了162种药毒物的保留时间及检测限。结论优化的AMDIS自动筛选常见药毒物,快速、灵敏、可靠,完全满足可疑含毒检材中毒物排查的要求。     

气质联用仪自动筛选常见毒物的应用研究

目的建立快速、灵敏的常见毒物的质谱自动筛选检测方法。方法建立常见毒物的质谱用户库，优化分离条件，优化质谱数据的自动分析参数，进行标样和样品分析。结果建立了含1306种常见毒物的质谱用户库；建立了自动筛选方法；得到了150种常见毒物的保留时间和检测限。结论建立的方法具有快速、灵敏、准确的优点，完全可替代繁杂的质谱检索手工操作。     

气相色谱与计算机结合在毒物分析中的应用──35种常见毒物的GC-PC系统分析检索

气相色谱法是毒物分析最常用的方法之一，通常是将本知物的保留时间与几种标准品的保留时间逐个对比，进行定性分析。而本方法是无需标准品，只要将测得未知物的三个保留时间值输入到计算机里，计算机可进行自动检索识别。本方法优点是在无标准样品的情况下，也可进行定性分析，把毒物的人工识别，变为计算机识别，既快速又准确。材料与方法一、仪器GC－7A型气相色谱仪，C－R1B型色谱数据处理机，FID检测器。TW386型计算机。二、样品35种常见毒物来源于沈阳、鞍山、及苏家屯等地区的药厂、农药厂以及公安部二所等。三、试剂所用试剂均…     

毛发中的毒物分析

在毒物分析中，尤其是法医学领域，毛发以其化学性质稳定，容易获得及贮存，不易受外界杂质于扰等优点而颇具研究价值．1954年,Goldblum等首次报道了利用紫外分光光度法检测豚鼠毛发中的巴比妥类含量[1]．近五十年来，毛发中毒物分析越来越受到重视，特别是七十年代末至今，毛发分析技术已基本趋于成熟．本文拟就毛发毒物分析中的毛发处理、检测方法等一些主要问题作一综述．1毒物与毛发的结合机制毛发根部的毛腺体（Follicle）与血液循环沟通，血液中的药（毒）物经血液循环输送到毛腺体，随着时间的推移，毛发成长为毛髓质（medull），外…     

离子色谱法检测土制硝铵氯化炸药爆炸残留物中的氯酸根

本文建立了离子色谱-抑制电导检测测定含有高浓度硝酸根的爆炸尘土中残留氯酸根的方法。使用高容量阴离子分析柱IonPac AS19，以KOH为流动相，梯度淋洗，氯酸根在8min左右出峰，15min之内完成常规离子的分析，方法的检测限为2．67ng／ml（S／N=3）。方法的线性范围为0．01～1000μg／ml，线性相关系数为0．9998。模拟样品中1μg／mlClO3^-的峰面积相对标准偏差为0．98％，峰高的相对标准偏差为0．66％。将此法应用于两起爆炸案的爆炸尘土样品测定，加标回收率在99％以上。对主要干扰物离子硝酸根的研究发现，即使3000μg／ml的硝酸根对低浓度氯酸根（几个ppm级）的测定也不存在干扰，确保了测定结果的准确性。     

高效液相色谱法测定盐酸曲马多血药浓度

目的 建立测定人血浆中盐酸曲马多浓度的HPLC-UV法。方法 血浆样品经碱化后,用二氯甲烷提取。采用依利特C18色谱柱(5μm),流动相为乙腈-磷酸盐缓冲液(74:26,pH6.5),检测波长为220um。结果 盐酸曲马多浓度在10～800ng/ml范围内与曲马多/内标物峰高比呈良好线性关系,r=0.9984,平均回收率为93.48％,最低定量检测浓度为10ng/ml;日内及日间RSD分别为3.81％～5.44％和3.95％～4.41％。结论HPLC-UV法用于血浆中盐酸曲马多浓度的检测,符合司法毒物分析及临床药血浓度测定的要求。     

HPLC／MS检测生物样品中的丁丙诺啡

目的建立了生物样品中丁丙诺啡的高效液相色谱-电喷雾串联质谱检测方法。方法样品经固相萃取提取净化、反相液相色谱分离后进行质谱检测，根据保留时间及特征离子进行定性分析，以母离子m／z468进行定量分析。结果在10-500ng／ml（ng／g）范围内峰面积与质量浓度的线性关系良好（r^2〉0．993）。在50、100、500ng／ml（ng／g）3个添加水平，尿、血、肝中丁丙诺啡的平均回收率为74％～94％，日内测定结果的相对标准偏差小于8％，日间测定结果的相对标准偏差小于10％。结论该方法简单、灵敏，特异性强，适用于生物样品中丁丙诺啡的分析检验。     

蓝色圆珠笔字迹色痕FT-IR光谱经时变化的研究

笔者曾用FT-IR光谱法对108种不同蓝色圆珠笔油墨进行了系统分析,确定了油墨组成成份,实现了种类认定.在此基础上,选取了二种不同种类的蓝色圆珠笔油墨字迹色痕,在紫外光下定时照射,根据各自光谱特征峰校正峰高的计算,确定相关峰的相对峰高比.根据相对峰高比值随时间变化的规律,进行了曲线拟合和计算机编程.同时,探讨了油墨组份之间随光照时间的变化,其目的是为了推断字迹色痕的“年龄”.     

SPE-HPLC分析全血中37种药（毒）物

目的建立全血中37种常见药(毒)物的固相萃取-高效液相色谱(SPE-HPLC)分析方法。方法以多沙普仑为内标,0.5mL全血经Oasis小柱固相萃取后,用HPLC进行分析,内源性物质不干扰测定。色谱柱采用LiChrospher!100RP-C18柱(250mm×4.0mm×5μm);二极管阵列检测器,检测波长为230nm和250nm,同时进行紫外扫描;柱温50℃。结果37种药(毒)物的绝对回收率除吗啡外均大于61.68%;日内及日间精密度均小于10%;检测限1～30ng/mL;线性相关系数在0.99798以上。结论本法快速、灵敏、重现性好,可用于实际案例中多种药(毒)物的分析。     

多虑平SPE-HPLC分析方法的建立及其应用

目的　建立尿样和全血中多虑平的固相萃取 高效液相色谱 (SPE HPLC)分析方法。方法　以多沙普仑为内标 ,1ml尿样或 0 5ml全血用Oasis小柱固相萃取后进Lichrospher 10 0RP 18e ( 2 5 0mm× 4mm ,5 μm)分析柱进行分析 ,2 3 0、 2 5 0nm同时进行检测。结果　尿样和全血中的检测限均 2ng/ml,线性相关系数r≥ 0 9992 ,天内和天间精密度均小于 6 75 % ,绝对回收率大于 85 % ,内源性物质不干扰测定。结论　本法快速、简便、准确 ,可用于实际案例的检测。     

A new marker for estimation of bloodstain age by high performance liquid chromatography.

The applicability of a new marker for estimation of bloodstain age by reverse-phase high performance liquid chromatography (HPLC) is described. Using a microBondasphere C18 column with a two step linear gradient of 10.5-46.25% acetonitrile in 0.1% trifluoroacetic acid, an intriguing peak (unidentified) at a retention time of about 5 min was observed on chromatograms from human adult bloodstains and designated as 'X'. The area of this peak, which could be detected in extracts of bloodstains, but not in their fresh whole blood, increased with time. The ratios of the X area to heme area in bloodstains stored at room temperature and 4 degrees C for up to 52 weeks old linearly correlated with stain age by plotting on a double logarithmic scale. In bloodstains exposed to fluorescent light at room temperature, the regression equation calculated from the ratios (Rx) and the ages of stains in weeks (W) is ln(1000.Rx) = 1.1084 + 0.3937.ln(7.W), and the coefficient of correlation (r) is 0.9776 (n = 144, P < 0.001). When stains were stored at 37 degrees C, the ratio transformed into logarithms correlated linearly with stain age. The regression equation describing the relationship in bloodstains exposed to fluorescent light at 37 degrees C is ln(1000.Rx) = 2.4477 + 0.0866.W (r = 0.9826, n = 144, P < 0.001). The results of the present study suggest that the HPLC method may be applicable to the estimation of bloodstain age.     

A rapid screening procedure for drugs and poisons in gastric contents by direct injection-HPLC analysis

A high performance liquid chromatographic method for toxicological drug screening of gastric content has been developed. The samples were diluted (1:3-1:30) in 0.01 N hydrochloric acid and injected into a reverse phase column for separation by gradient elution. Mobile phase consisted of solvent A (acetonitrile/water 90:10, 0.01 M sodium dodecylsulphate, 0.5% v/v glacial acetic acid) and solvent B (water/acetonitrile 90:10, 0.01 M sodium dodecylsulphate, 0.5% v/v glacial acetic acid); the gradient was programmed from 20 to 80% A in 30 min. The flow was kept constant at 1.5 ml/min. Two home-made internal standards, butyrylsalicylic acid and diacetyltubocurarine with retention times of 5.6 and 21.4 min, respectively, were used. Drugs are identified by matching their relative retention times and UV spectra (200-400 nm) with those contained in a home made library of more than 340 reference compounds (9 analgesics, 22 antidepressants, 30 antihistamines, 14 antihypertensives, 21 antirheumatics, 15 beta-blockers, 9 bronchodilators, 10 Ca antagonists, 14 diuretics, 26 neuroleptics, 25 tranquilizers, and other significant xenobiotic compounds). The fluorometric (FLD) emission spectrum (280-700 nm; excitation wavelength, 230 nm) was used as a further identification. At 50mg/l analyte concentrations, the injection of gastric content after dilution (1:3) produced S/N ratios in the range 8-140. The method is simple, rapid, rather inexpensive and proved to be a useful means of investigation if used in combination with GC-MS screening in blood. On the other hand, the system suffers from a relatively limited sensitivity for compounds with a low UV absorption and from interferences due to the presence in the matrix of some highly UV- and FL-responsive compounds (e.g. tryptophan).     

Comparative analysis of gamma-hydroxybutyrate and gamma-hydroxyvalerate using GC/MS and HPLC

This paper describes two analytical techniques used to separate and quantify gamma-hydroxybutyrate (GHB) and gamma-hydroxyvalerate (GHV). The first technique was a N,O-bis(trimethylsilyl)triflouro-acetimide-trimethylchlorosilane derivatization, followed by gas chromatography/mass spectrometry analysis using an HP-5 capillary column at a rate of 1.0 mL/min with a run time of 9.25 min. This technique was found to be sensitive (LOD 1 pg on column) and gave a low average error (5%) in a beverage study. When supplemented by a surrogate spike, the method yielded 97% analyte recovery from beverages. The second technique was high-performance liquid chromatography/UV (HPLC/UV) using a C-18 column with a (20:80% v/v) methanol:dibasic phosphoric buffer (10 mM, pH 3) at a rate of 1.00 mL/min with a run time of 7.5 min. UV detection occurred at 254 nm. This method was found to be less sensitive (LOD 0.05 microg on column) for direct analysis of aqueous samples. To remove interferences seen in the beverage study, a liquid-liquid extraction before HPLC analysis was tested. However, a decreased sensitivity (LOD 100 microg on column) and irreproducible peak profiles resulted.     

高效液相色谱法测定卡西酮

目的建立卡西酮的高效液相色谱检测方法。方法采用UPLC-DAD分析方法。分析柱:Agilent ZorbaxSB-Phenyl柱(250mm×4.6mm,5μm),流动相为三氟乙酸(pH 3.5)∶乙腈为85∶15,流速0.2mL/min,检测波长254nm。结果卡西酮在0.5～1 000μg/mL浓度范围内线性关系良好R2=0.999 4,日内与日间保留时间和峰面积的标准偏差(RSD)均<1.06%,检出限为0.068μg/mL,平均回收率95.9%。结论本方法峰形好,分离度好,线性范围良好,回收率高,适用于刑事案件中卡西酮的定性定量分析。     

Analysis of a simulated heroin distribution chain by HPLC

A heroin distribution chain was simulated by taking three different seizures and preparing four additional samples from each seizure by adding a paracetamol-caffeine mixture in varying amounts, resulting in three different batches each composed of five samples. All of the samples from the three batches were analyzed using HPLC with a UV-PDA detector at a wavelength of 230 nm. The area ratio of various opium alkaloids, acetylation products and components were compared. From the results of the UV area ratios, the fifteen samples could readily be separated into three batches of five samples, with each batch of five samples having a common origin.     

两个体混合样本比例的PCR-STR检测研究

目的探讨PCR-STR检测两个体混合样本比例的灵敏度。方法按不同比例将两个体全血、单个核细胞及纯DNA 3种不同的样本进行混合,应用AB I公司生产的profile p lus商品化试剂盒多重PCR扩增后,用AB I3100基因分析仪进行毛细管电泳,检测基因座及其峰面积,并就混合样本中两单个核细胞样本DNA含量百分比与扩增前混合样本比例的关系进行相关分析。结果当样本混合比例为4%+96%时,可明确区分混合样本中两个体的基因型,且扩增前混合细胞百分率与扩增后两者峰面积比值呈直线相关。结论PCR-STR检测两个体混合样本比例的灵敏度有一定范围,并可进行半定量。     

PowerPlex~ 21试剂盒扩增后的分型图谱中Y片段丢失的识别

目的依据分型图谱,直观、简便识别是否存在Amelogenin基因Y片段丢失的可能。方法采用计算分型图谱中等位基因峰高之和比值的方法,统计1 968份人员样本经Power Plex~ 21试剂盒扩增后Amelogenin与D3S1358基因座之间的均衡性、Amelogenin X等位基因与Amelogenin Y等位基因的均衡性以及D3S1358基因座不同等位基因的均衡性情况。结果 90.8%的女性样本Amelogenin X等位基因峰高不低于D3S1358基因座等位基因峰高和的60%,94.9%的男性样本Amelogenin X等位基因的峰高不超过D3S1358基因座等位基因峰高和的70%。结论 Power Plex~ 21试剂盒扩增后的分型结果中,当Amelogenin基因只检测到Amelogenin X等位基因,且Amelogenin X等位基因的峰高不及D3S1358基因座等位基因峰高之和的70%时,应考虑存在Y片段丢失的可能性。