离子交换色谱-氢化物发生双道原子荧光法同时测定砷和硒形态

建立了离子交换色谱-氢化物发生双道原子荧光联用同时测定4种As形态和3种Se形态的方法,并优化了各种实验参数。采用PRP-X100阴离子交换分析柱可以在10min内同时分离、检测As和Se形态。在8%HCl和1.5%(m/V)KBH4的氢化物反应条件下,进样量100μL,各形态的检出限为:As(Ⅲ)0.2μg/L、DMA0.3μg/L、MMA0.2μg/L、As(Ⅴ)0.3μg/L、SeCys0.6μg/L、Se(Ⅳ)0.5μg/L、SeMet3μg/L。当各As形态浓度为100μg/L、各Se形态浓度为200μg/L,各形态的精密度RSD(n=7)均小于5%。当各As形态浓度范围为5～100μg/L、SeCys和Se(Ⅳ)浓度范围为10～200μg/L、SeMet浓度范围为50～200μg/L时,各形态均可得到良好的线性关系,线性相关系数均大于0.9992。用建立的方法测定了富硒营养品中的As和Se形态,加标回收率在91%～115%之间。     

唾液中大麻毒品液相小体积提取HPLC检测

建立了小体积液相提取HPLC测定唾液中大麻类毒品含量的方法。在pH=4缓冲溶液中,加入1mL含大麻标准品的家兔唾液试样,用0.5mL氯仿超声振荡提取5min,4000r/min离心10min,取下层液体挥干,用1mL乙腈溶解后进行HPLC分析。唾液中四氢大麻酚(THC)、大麻二酚(CBD)、大麻酚(CBN)、四氢大麻酚酸的检出限(3S/N)分别为16ng、10ng、11ng、10 ng,标准曲线线性范围分别为0.32μg/μL～3.20μg/μL、0.10μg/μL～1.00μg/μL、0.11μg～1.10μg/μL、0.20μg/μL～2.00μg/μL。平均回收率均在95%～105%之间。相对标准偏差(n=6)均在3%以内。     

杨树嫩茎质外体微透析液中K+,Na+,Ca2+的分析

采用微透析法获取3种杨树嫩茎质外体汁液的灌流液,流速1μL/min,探针截留分子量为30 kDa,无须处理直接通过原子吸收光谱(石墨炉法)测定样品中Na+,K+,Ca2+浓度,通过建立实时、无损检测离子浓度变化的实验技术,进行杨树生理生化的研究。此方法加标回收率在95.8%~103.1%之间。研究表明,吴屯杨、小胡杨和小美旱的Na+含量分别为1034~1156μg/L,1493~1611μg/L和1586~1703μg/L;K+含量分别为1012~1237μg/L,941~964μg/L和1095~1201μg/L;Ca2+含量分别为4976~5237μg/L,4786~5042μg/L和5893~6142μg/L,本方法为在植物应激反应中通过离子浓度变化来适应外界环境的研究提供可靠数据。     

亲水作用色谱-串联质谱测定尿液中尼古丁和可替宁

建立了测定人尿液中尼古丁和可替宁含量的亲水作用色谱-串联质谱(HILIC-MS/MS)方法。尿样加入尼古丁-d4和可替宁-d3同位素内标后,用水稀释10倍,经过滤后的滤液由超高效液相色谱-串联质谱(UPLC-MS/MS)进行分离分析。采用ACQUITY UPLC~BEH HILIC色谱柱(50 mm×3.0 mm,1.7μm),以甲醇和体积分数为0.1%的氨水为流动相,流速为0.2 mL/min,在电喷雾电离源正离子模式下测定尿液中尼古丁和可替宁的含量,用标准曲线法定量。尼古丁和可替宁在1.0~1 000μg/L范围内线性关系良好,相关系数分别为0.994 9和0.995 8;检出限分别为0.082μg/L和0.077μg/L;定量限分别为0.27μg/L和0.26μg/L;加标回收率分别为90.4%~103.5%和93.0%~104.6%;相对标准偏差分别为4.80%~6.21%和4.22%~7.15%。应用所建立的方法测定了200份尿样,结果表明,吸烟人群尿中尼古丁含量为26.68~854.30μg/L,可替宁含量为36.66~1 191.18μg/L(n=86,M_(nicotine)=76.00μg/L,M_(nicotine)=83.52μg/L,M为中位数);非吸烟人群尿中尼古丁含量为5.08~69.66μg/L,可替宁含量为3.16~28.21μg/L(n=114,Mnicotine=7.53μg/L,M_(nicotine)=3.79μg/L)。该方法快速灵敏,操作简单,适用于尿样中尼古丁和可替宁的批量测定,能满足烟草暴露评价的需要。     

地下水检测典型挥发性有机物标准样品研究

依据我国地下水污染现状,研究制备了地下水中典型挥发性有机物(VOCs)质量控制模拟标准样品,包含4种卤代烃和6种苯系物,经过气相色谱/质谱分析检测,均匀性和稳定性良好。组织行业内9家实验室,探索开展水中挥发性有机物检测的协作定值研究。开展不确定度来源分析和量值评定,标准样品的标准值和扩展不确定度(k=2)为:三氯甲烷(60.6±5.4)μg/L、四氯化碳(60.2±7.4)μg/L、三氯乙烯(60.4±5.8)μg/L、四氯乙烯(60.6±7.6)μg/L、苯(60.9±4.2)μg/L、甲苯(60.4±4.8)μg/L、乙苯(60.7±5.0)μg/L、邻二甲苯(60.5±6.2)μg/L、间二甲苯(60.4±6.2)μg/L、对二甲苯(60.4±6.2)μg/L。本标准样品主要用于地下水、地表水和饮用水环境监测工作中质量控制、分析方法验证、仪器性能的核查以及技术人员能力考核等。     

利用乙酸对电感耦合等离子体质谱法的增敏效应测定砷与硒

建立了100 g/L乙酸基体改进电感耦合等离子体质谱法分析难电离元素砷和硒的方法。以100 g/L乙酸作为基体改进剂,可使砷和硒信号分别增加4~7倍。方法检出限分别为0.019μg/L和0.11μg/L,6次测定标准样品中10.0μg/L砷和硒的相对标准偏差(RSD)均小于3%。     

场放大进样-胶束电动色谱法测定胡黄连中的香草酸、肉桂酸和阿魏酸

利用胶束电动色谱测定胡黄连中的香草酸、肉桂酸和阿魏酸;在联用场放大进样后,富集倍数提高30倍以上,检出限降至3.6μg/L,线性范围向下延伸到14μg/L。胶束扫集电动色谱缓冲体系为100mmol/L十二烷基磺酸钠(SDS)+20mmol/L磷酸钠(pH=2.20)+15%甲醇,分离电压-20kV。进样电压-8kV,进样时间20s,进水时间160s(H=20.0cm),测量波长214nm。考察了SDS浓度、进样长度、进样电压等对分离效果的影响。在优化条件下,3种有机酸在10min内出峰,峰面积相对标准偏差(RSD)≤5.9%。方法检出限、线性范围、相关系数分别为:香草酸3.6μg/L、14～460μg/L、0.9996;肉桂酸9.8μg/L、20～310μg/L、0.9994;阿魏酸11μg/L、22～180μg/L、0.9996。回收率为95.4%～107%。     

石墨炉原子光谱法测定工业废渣中痕量元素砷、铅、铬、钡、银

建立了石墨炉原子吸收光谱法测定检测工业废渣中痕量元素砷、铅、铬、钡、银的方法。采用悬浮进样,硝酸-硫酸混合酸溶解样品。10g/L Mg(NO3)2作基体改进剂,提高了砷的灰化温度,加入10g/L CaCO3防止钡在石墨炉中形成不易挥发的碳化钡,增加了钡的灵敏度。回收率为98%～112%,测定结果的相对标准偏差为2.22%～4.46%。As的线性范围2～80μg/L,Pb的线性范围1～60μg/L,Cr的线性范围0.5～20μg/L,Ba的线性范围5～150μg/L,Ag的线性范围1～100μg/L。     

电化学氢化物发生原子荧光法同时测定砷和锑

采用电化学氢化物发生与原子荧光联用技术，同时测定了样品中的As和Sb含量。对各种实验参数和干扰情况进行了详细研究。As在0～500μg/L，sb在0～300μg/L之间均有良好的线性关系；相对标准偏差(RSD)(10μg/L，n=11)分别是3．7％和1．8％；检出限分别为0．14μg/L和0．20μg/L。     

螯合树脂在线富集火焰原子吸收法测定痕量铅和镉

在pH=4.88的乙酸-乙酸钠缓冲溶液中,用螯合离子交换树脂富集铅和镉,以1.50mol/L HNO3作洗脱液,火焰原子吸收法测定洗脱液中痕量铅和镉。该方法对铅和镉的线性范围分别是4.0～80.0μg/L和2.0～30.0μg/L,检出限分别为1.3μg/L和0.7μg/L。该方法用于地表水中痕量铅和镉的测定,分析结果满意。     

High-throughput simultaneous analysis of buprenorphine, methadone, cocaine, opiates, nicotine, and metabolites in oral fluid by liquid chromatography tandem mass spectrometry

A method for simultaneous determination of buprenorphine (BUP), norbuprenorphine (NBUP), methadone, 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP), cocaine, benzoylecgonine (BE), ecgonine methyl ester (EME), anhydroecgonine methyl ester (AEME), morphine, codeine, 6-acetylmorphine (6AM), heroin, 6-acetylcodeine (6AC), nicotine, cotinine, and trans-3′-hydroxycotinine (OH-cotinine) by liquid chromatography tandem mass spectrometry in oral fluid (OF) was developed and extensively validated. Acetonitrile (800 μL) and OF (250 μL) were added to a 96-well Isolute-PPT+protein precipitation plate. Reverse-phase separation was achieved in 16 min and quantification was performed by multiple reaction monitoring. The assay was linear from 0.5 or 1 to 500 μg/L. Intraday, interday, and total imprecision were less than 13% (n?=?20), analytical recovery was 92–114% (n?=?20), extraction efficiencies were more than 77% (n?=?5), and process efficiencies were more than 45% (n?=?5). Although ion suppression was detected for EME, cocaine, morphine, 6AC, and heroin (less than 56%) and enhancement was detected for BE and nicotine (less than 316%), deuterated internal standards compensated for these effects. The method was sensitive (limit of detection 0.2–0.8 μg/L) and specific (no interferences) except that 3-hydroxy-4-methoxyamphetamine interfered with AEME. No carryover was detected, and all analytes were stable for 24 h at 22 °C, for 72 h at 4 °C, and after three freeze–thaw cycles, except cocaine, 6AC, and heroin (22–97% loss). The method was applied to 41 OF specimens collected throughout pregnancy with a Salivette® OF collection device from an opioid-dependent BUP-maintained pregnant woman. BUP ranged from 0 to 7,400 μg/L, NBUP from 0 to 71 μg/L, methadone from 0 to 3 μg/L, nicotine from 32 to 5,020 μg/L, cotinine from 125 to 508 μg/L, OH-cotinine from 11 to 51 μg/L, cocaine from 0 to 419 μg/L, BE from 0 to 351 μg/L, EME from 0 to 286 μg/L, AEME from 0 to 7 μg/L, morphine from 0 to 22 μg/L, codeine from 0 to 1 μg/L, 6AM from 0 to 4 μg/L, and heroin from 0 to 2 μg/L. All specimens tested negative for EDDP and 6AC. This method permits a fast and simultaneous quantification of 16 drugs and metabolites in OF, with good selectivity and sensitivity.     

Determination of glyoxal,methylglyoxal, and diacetyl in red ginseng products using dispersive liquid–liquid microextraction coupled with GC–MS

A simple and rapid dispersive liquid–liquid microextraction method coupled with gas chromatography and mass spectrometry was applied for the determination of glyoxal as quinoxaline, methylglyoxal as 2‐methylquinoxaline, and diacetyl as 2,3‐dimethylquinoxaline in red ginseng products. The performance of the proposed method was evaluated under optimum extraction conditions (extraction solvent: chloroform 100 μL, disperser solvent: methanol 200 μL, derivatizing agent concentration: 5 g/L, reaction time: 1 h, and no addition of salt). The limit of detection and limit of quantitation were 1.30 and 4.33 μg/L for glyoxal, 1.86 and 6.20 μg/L for methylglyoxal, and 1.45 and 4.82 μg/L for diacetyl. The intra‐ and interday relative standard deviations were <4.95 and 5.80%, respectively. The relative recoveries were 92.4–103.9% in red ginseng concentrate and 99.4–110.7% in juice samples. Red ginseng concentrates were found to contain 191–4274 μg/kg of glyoxal, 1336–4798 μg/kg of methylglyoxal, and 0–830 μg/kg of diacetyl, whereas for red ginseng juices, the respective concentrations were 72–865, 69–3613, and 6–344 μg/L.     

固相萃取高效液相色谱法测定水中痕量-微囊藻毒素

微囊藻毒素是有害的蓝藻水华释放的有毒代谢物,对人类及环境具有很大危害性。建立了固相萃取－高效液相色谱测定水中痕量藻毒素的方法。该法对两种常见微囊藻毒素MC－LR、MC－RR的检测限为0．02－0．05μg/L,线性定量范围为0．1－50μg/L。应用该法分析了天然水样,表明方法具有实用性。     

酶联免疫吸附分析法测定水产品及水中孔雀石绿和无色孔雀石绿

本文报道一种同时测定水产品及水样中孔雀石绿(MG)和无色孔雀石绿(LMG)的间接竞争酶联免疫吸附分析法。对无色孔雀石绿分子进行修饰,使其与载体蛋白交联,得到免疫原和包被抗原,经过多次免疫动物制得抗无色孔雀石绿的多克隆抗体。在优化的实验条件下,IC50值(标准曲线中吸光度抑制至最大吸光度值的50%时所对应的待测物浓度)为0.9~2.6μg/L,检出限为0.02~0.10μg/L,无色孔雀石绿在水样及水产品中的回收率为76.2~95.0%,与孔雀石绿的交叉反应率为95.25%。真实样品测定中,两种食用鱼养殖水样及一个鱼样中未检出孔雀石绿和无色孔雀石绿,但在观赏鱼养殖水样及另一鱼样中检出孔雀石绿和无色孔雀石,浓度分别为1.84μg/L和1.38μg/L。     

Determination of Bromate in Bottled Drinking Water from Saudi Arabian Markets by HPLC/ICP-MS

The determination of bromate BrO₃ ^? in 50 different bottled drinking water samples collected from Saudi Arabian markets has been investigated using liquid chromatography inductively coupled plasma mass spectrometry (HPLC/ICP-MS). For analysis, samples were injected directly without any further pretreatment or dilution, using only a 50 μL injection volume. The method showed: detection limit of 0.5 μg/L, limit of quantification of 1.0 μg/L, 1.0 ? 200.0 μg/L linearity range (r² = 0.9998), relative standard deviation (%RSD) for reproducibility (inter-day precision) values of 14% and 4% for low and high concentration levels (10,100 μg/L), respectively. The results obtained for bromate showed that 30% of the samples are acceptable as US EPA standards (10 μg/L), 40% of the samples are acceptable as Gulf (Saudi Arabia) standards (25 μg/L), and almost 60% of the samples exceed the allowable limits for bromate in bottled drinking water.     

Trace analysis of anions in organic matrices by ion chromatography coupled with a novel reversed-phase column for on-line sample pretreatment

An ion chromatography(IC) system coupled with on-line column-switching technique was used to determine anions ofμg/g levels in organic chemicals of analytical reagent grade.A novel polystyrene-divinylbenzene-carbon nanotube(PS-DVB-CNT) stationary phase was utilized for matrix elimination.A calibration study was conducted by preparing and analyzing eight concentrations(between 10 and 5000μg/L) of eight standards in deionized water.The linearity was between 0.9978 and 1.And the detection limits ranged from 1.54μg/L to 10.02μg/L.A spiking study was performed on two representative organic chemicals.The recoveries were between 84.3%and 119.6%.     

毛细管区带电泳法测定冬虫夏草及鹿茸制品中核苷和碱基成分

应用毛细管区带电泳法测定分别以冬虫夏草菌丝体粉和鹿茸血为主要原料制品中的多种核苷和碱基成分。对实验条件进行了优化,结果表明,以20mmol/L硼砂-15mmol/Lβ-环糊精为缓冲溶液(pH=9.4),分离电压22kV,检测波长254nm,电动进样为10kV、5s时,在10min内同时分离测定了虫草素、腺嘌呤、鸟嘌呤、尿嘧啶、腺苷、次黄嘌呤、尿苷、鸟苷和肌苷。各组分在0.2～200μg/mL范围内呈线性关系,检出限的范围是0.07～1.67μg/mL。5个批次的冬虫夏草菌丝粉保健品中腺嘌呤、尿嘧啶、腺苷、鸟苷、尿苷5组分的定量结果分别在0.15～0.19mg/g、0.72～0.92mg/g、1.44～1.59mg/g、1.51～2.32mg/g和1.77～2.56mg/g范围内,加标回收率的范围是82.83%～109.21%;2个批次的鹿茸血保健品中次黄嘌呤、尿苷的定量结果在36.55～49.97μg/mL和86.08～108.97μg/mL范围内,加标回收率的范围分别是89.68%～96.79%和99.05%～102.81%。     

THE STUDY OF LUMINOL-H_2O_2-IO_4~--S~(2-)CHEMILUMINESCENCE SYSTEM AND ITS APPLICATION

This paper reports a new chemiluminescence system i.e.luminol-H_2O_2-IO_4~- catalyzed by sulphide ion(S~(2-)).Based on this catalysis,a newchemiluminescence(CL)method for the determination of trace S~(2-)is pro-posed.The detection limit is 0.2μg/LS~(2-),the linear dynamic range is 5μgto 100βμg/L S~(2-)and the variation coefficient at an sulphide concentrationof 100μg/L S~(2-)is 4.5%(n=10).The method has been satisfactory applied tothe determination of trace sulphide ion in water.