基质固相分散-反相高效液相色谱法测定水果中的氨基甲酸酯农药残留

应用基质固相分散-反相高效液相色谱法提取和测定了水果中三种氨基甲酸酯农药残留。通过实验确定了最佳前处理条件:弗罗里硅土作为萃取吸附剂,样品与吸附剂质量比为1∶4,洗脱剂为丙酮∶二氯甲烷=3∶7(V/V)的混合液,洗脱剂的体积为10 m L。在优化的实验条件下,三种氨基甲酸酯农药的检出限在0.02~0.62μg/g之间,测定的线性范围为0.20~40μg/g,相关系数在0.9957~0.9990之间。方法应用于检测水果样品时,平均加标回收率为80.4%~116.5%,相对标准偏差为0.7%~8.0%。     

凝胶渗透色谱净化-气相色谱/串联质谱分析蘑菇中的36种农药残留

建立了用凝胶渗透色谱净化-气相色谱/串联质谱分析蘑菇中36种农药残留的方法。蘑菇中的待测农药组分在30 ℃条件下用乙酸乙酯提取,高速匀浆后通过凝胶渗透色谱净化;选用填料为中性多孔的聚苯乙烯二乙烯基苯微球体的S-X3玻璃柱(22 g,19 cm×2 cm)作为凝胶渗透色谱净化柱,流动相为乙酸乙酯-环己烷(体积比为1∶1)溶液,流速5 mL/min;收集第7~15 min流出的液体用气相色谱-三重四极杆串联质谱仪测定。在0.01~1.0 mg/L的质量浓度范围内,各种农药标准溶液的线性相关系数均大于0.99。在样品中添加36种农药(添加水平为0.01,0.05,0.10 mg/kg)的混合标准溶液,平均回收率为72.6%~117.1%,相对标准偏差为2.0%~10.8%(n=5),最低检出限为 0.1~0.7 μg/kg,最低定量限为 0.2~2 μg/kg。     

高聚物型色谱柱分离乙酰半胱氨酸及其有关物质

考察高聚物型色谱柱(聚苯乙烯-二乙烯基苯(PS-DVB)麦科菲反相高效液相色谱柱,MKF-RP-MH)分离乙酰半胱氨酸以及有关物质的适用性。采用MKF-RP-MH色谱柱(4.6×250 mm,5μm),V(0.02 mol/L的磷酸盐缓冲液(pH 3.0))∶V(乙腈)=9∶1为流动相,流速为1 mL/min,检测波长210 nm,柱温为25℃。乙酰半胱氨酸峰与有关物质峰的分离度均大于1.5;乙酰半胱氨酸质量浓度在11~111 mg/L的范围内,具有良好的线性关系,回归方程为A=18.195ρ+0.5229,r=0.9995(n=8);乙酰半胱氨酸的定量限为11 mg/L;最低检测限为0.035μg;进样精密度RSD=0.24%(n=6)。     

气相色谱-三重四级杆质谱法同时测定水果配制酒中30种农药残留

建立气相色谱-三重四级杆质谱结合分散固相萃取样品处理同时测定水果酒中30种农药残留量的分析方法。样品经乙腈-乙酸乙酯（体积比为1∶1）提取,经1 200 mg无水硫酸镁、150 mg乙二胺-N-丙基硅烷（PSA）、15 mg石墨化炭黑（GCB）净化,采用HP-5色谱柱分离,多反应监测模式定量分析。30种农药在质量浓度5～200μg/L范围内,线性判别系数均大于0.998,方法检出限为0.03～0.40μg/kg,定量限为0.10～1.25μg/kg,样品加标试验平均回收率为84.2%～110.7%,相对标准偏差为0.8%～6.3%(n=6)。该方法操作简便、结果准确、重复性好,适用于水果酒中30种农药残留量的同时定量分析。     

凝胶渗透色谱-高效液相色谱-串联质谱法同时测定烟草中3种抑芽剂残留

建立了用凝胶渗透色谱净化-液相色谱-串联质谱分析烟草中3种抑芽剂残留的方法。卷烟中的待测抑芽剂组分用V(乙酸乙酯)∶V(环己烷)=1∶1超声提取后通过凝胶渗透色谱净化;凝胶色谱柱为Biobeads S-X3玻璃柱(50 g,400 mm×25 mm),流动相为V(乙酸乙酯)∶V(环己烷)=1∶1溶液,流速5 mL/min;收集第10~25 min流出的液体用液相色谱色谱-三重四极杆串联质谱仪测定。在0.5~100 ng/mL的质量浓度范围内,各种抑芽剂标准溶液的线性相关系数均大于0.99。在样品中添加3种抑芽剂(添加水平为5,20,100μg/kg)的混合标准溶液,平均回收率在86.2%~108.4%之间,3种抑芽剂的RSD在1.1%~7.5%之间;方法的检测限在0.01~0.06μg/kg之间。     

环境水样中9种三唑类农药的固相萃取-气相色谱-质谱分析

应用C18柱萃取/富集,NH2柱净化,气相色谱-质谱联用技术检测,建立了环境水样中9种三唑类农药同时分析的方法。9种目标农药在0.025～0.500 mg/L质量浓度范围内线性关系良好,方法的检出限为0.002～0.009 μg/L。以实际水样为基底,加标质量浓度为0.025 μg/L和0.100 μg/L时,9种目标农药的基底加标回收率和相对标准偏差(n=3)分别为68.4%～113.9%,1.6%～6.9%(河水)和70.3%～115.2%,0.8%～8.2%(海水)。该方法操作简单、灵敏度高、选择性好,符合多种农药残留分析的要求,并成功地应用于福建九龙江河口区表层水样中三唑类农药的残留状况调查。     

搅拌棒吸附子萃取与GC-MS法测定水中20种有机氯农药

建立了搅拌棒吸附子萃取/气相色谱-质谱法(SBSE/GC-MS)同时检测水中α-六六六、γ-六六六、β-六六六、七氯、δ-六六六、艾氏剂、环氧七氯、γ-氯丹、顺-氯丹、硫丹Ⅰ、p,p-滴滴伊、狄氏剂、异狄氏剂、p,p-滴滴滴、硫丹Ⅱ、p,p-滴滴涕、异狄氏剂醛、硫丹硫酸盐、甲氧滴滴涕、异狄氏剂酮20种有机氯农药含量的方法.样品在室温下经拌棒吸附子搅拌吸附,甲醇解吸附后,以J&W DB-35 MS(30 m×0.25 mm×0.25 μm)石英毛细管色谱柱为分析柱,气相色谱-质谱选择离子流模式检测.考察了萃取时间、氯化钠及甲醇加入量等对萃取的影响.实验结果表明:在2.5 ～20.0 μg/L 范围内,20种有机氯农药呈良好的线性关系,检出限(S/N=3)为0.008 ～0.118 μg/L,水样中分别添加2.5、20 μg/L的20种有机氯农药,回收率为 52% ～117%,相对标准偏差小于13%(n= 6).该方法操作简便、快速、灵敏度高,应用于实际样品检测,结果满意.     

高效液相色谱-串联质谱法检测中药材中有机磷农药残留量

研究了中药材中有机磷农药残留量的高效液相色谱-串联质谱同步检测方法.采用CAPCELL PAK MC C18反相柱,以乙腈为提取溶液,以Carb/PSA柱为净化柱,液相色谱-串联质谱仪测定.方法线性范围为10～500 μg/L,11种有机磷农药在此范围内线性良好,相关系数为0.9961～0.9999.在10～100 μg/kg浓度范围内,加标回收率在70%～110%之间,相对标准偏差为1.4%～11%,最低检出限为2～20μg/kg,符合残留检测分析要求.     

高效液相色谱化学发光检测人体血清及尿样中的盐酸肾上腺素

研究发现,盐酸肾上腺素在碱性条件下能显著增强铁氰化钾-鲁米诺化学发光强度。基于此建立了新的测定肾上腺素的方法。本方法以C18反相键合相为色谱柱,用0.01 mol/L邻苯二甲酸氢钾-甲醇(92∶8,V/V)为流动相,实现了对人体血清及尿样中盐酸肾上腺素的分离与测定。在最适宜条件下,方法的线性范围为10~5000μg/L;检出限为4.0×10-6g/L;相对标准偏差为3.0%(n=11)。     

梯度淋洗-电导抑制离子色谱法同时测定果汁中26种有机酸和阴离子

通过对色谱柱类型、流速、柱温、pH值、淋洗液浓度等影响因素的研究,建立了多级梯度淋洗-电导抑制离子色谱同时测定果汁中26种有机酸和阴离子的分析方法。结果表明,当流速为1.00 mL/min、柱温为30℃、pH值为5.5~6.8时,26种组分的测定结果更准确。26种组分在0.02~10.0 mg/L范围内具有良好的线性关系（r均大于0.995）,检出限（S/N=3）为0.17~52.0 μg/L;在0.20~2.00 mg/L添加水平下的回收率为85.58%~108.86%,相对标准偏差为0.15%~7.65%（n=6）。该方法简便快速、灵敏度好、准确度高,适于果汁中26种组分的痕量分析。     

Toxicokinetics of strychnine and brucine after the oral administration of Biqi capsule to rats by RRLC–MS/MS

Biqi capsule is a well‐known traditional Chinese medicine formula that has been widely applied for the clinical treatment of such diseases as rheumatoid arthritis, scapulohumeral periarthritis and cervical spondylopathy. However, there is concern regarding the toxicity of Biqi capsule owing to its active ingredients, strychnine and brucine. To investigate the toxicokinetics of strychnine and brucine after oral administration of Biqi capsule to rats, a sensitive and simple rapid‐resolution liquid chromatography/tandem mass spectrometry method was developed to determine the levels of strychnine and brucine in rat plasma. Chromatographic separation was performed on a Capcell Pak C₁₈ MG II (3.0 μm, 2.0 × 35 mm) column by gradient elution with acetonitrile and 0.2% formic acid as the mobile phase. The method was validated over the range of 0.25–250 ng/mL for strychnine and 0.025–25 ng/mL for brucine. The intra‐ and inter‐day accuracies of strychnine and brucine in rat plasma were 100.3–106.6 and 90.75–106.1% respectively, and the precisions were within 14.2%. The established method was successfully applied to the toxicokinetic study of strychnine and brucine after single and multiple oral administration of Biqi capsule to male and female rats at 0.4, 0.8 and 1.6 g/kg doses. The results showed different toxicokinetic characteristics in the different groups.     

Ultra‐performance liquid chromatography–tandem mass spectrometric assay for the simultaneous determination of brucine,strychnine and brucine N‐oxide in rat plasma: application to a pharmacokinetic study

A rapid, simple and sensitive UHPLC‐MS/MS method was developed and validated for the simultaneous determination of brucine, strychnine and brucine N‐oxide in rat plasma using huperzine A as an internal standard (IS) after protein precipitation with methanol. The analytes were separated on a Purospher® STAR RP₁₈ UHPLC column (2 µm, 2.1 × 100 mm) by gradient elution using a mobile phase composed of methanol and water (containing 0.1% formic acid) at a flow rate of 0.3 mL/min. Brucine, strychnine, brucine N‐oxide and IS were detected in positive ion multiple reaction monitoring mode by means of an electrospray ionization interface (m/z 395.2 → 324.1, m/z 335.2 → 184.1, m/z 411.2 → 394.2, m/z 243.1 → 226.1). The calibration curve was linear over the range of 1–500 ng/mL for brucine and strychnine and 0.2?50 ng/mL for brucine N‐oxide. The intra‐ and inter‐day precisions of these analytes were all within 15% and the accuracy ranged from 85 to 115%. The stability experiment indicated that the plasma samples at three concentration levels were stable under different conditions. The developed method was successfully applied for the first time to pharmacokinetic studies of brucine, strychnine and brucine N‐oxide following a single oral and intravenous administration of modified total alkaloid fraction in rats. Copyright © 2016 John Wiley & Sons, Ltd.     

Combination of hollow fiber-based liquid-phase microextraction with sweeping techniques in micellar electrokinetic chromatography for the determination of Strychnos alkaloids in human urine

A new method for the enrichment of Strychnos alkaloids in biological samples via liquid-phase microextraction (LPME) based on porous polypropylene hollow fibers in combination with on-line sweeping in micellar electrokinetic chromatography was developed. The calibration curve was linear over the range of 20-200 ng mL-1 for both strychnine and brucine in human urine sample. The detection limits (S/N=3:1) for strychnine and brucine were 1 ng mL-1 and 2 ng mL-1, respectively. The LPME-sweeping method has been successfully applied to the analysis of strychnine and brucine in real urine samples.     

Development and validation of a TLC-densitometric method for the simultaneous quantitation of strychnine and brucine from Strychnos spp. and its formulations

A simple, sensitive, and specific thin-layer chromatography densitometric method has been developed for the simultaneous quantitation of strychnine and brucine. These two marker compounds are quantitated in the seeds of Strychnos nux-vomica, Strychnos ignatii, and its formulations. The method involves densitometric evaluation of strychnine and brucine after resolving it by high-performance TLC on silica gel plate with toluene-ethyl acetate-diethyl amine-methanol (7:2:1:0.3 v/v) as the mobile phase. The method is validated for precision (interday and intraday), repeatability, and accuracy. The relationship between the concentration of standard solutions and the peak response is linear within the concentration range of 160 to 480 ng/spot for strychnine and 80 to 480 ng/spot for brucine. Instrumental precision is found to be 0.54 and 0.78 (% CV), and repeatability of the method is 1.01 and 1.06 (% CV) for strychnine and brucine, respectively. Accuracy of the method is checked by recovery study conducted at three different levels and the average percentage recovery is found to be 99.13% for strychnine and 100.16% for brucine. The proposed HPTLC method for the simultaneous quantitation of strychnine and brucine is found to be simple, precise, specific, sensitive, and accurate, and it can be used for routine quality control of raw material of Strychnos spp. It also can be applied in quantitating any of these marker compounds in other formulations.     

Rapid separation of strychnine and brucine on a dynamically modified poly(dimethylsiloxane) microchip followed by electrochemical detection

A method has been developed for rapidly separating and detecting strychnine and brucine using a poly(dimethysiloxane) (PDMS) microchip and electrochemical (EC) detection. PDMS microchannels dynamically modified by Brij35 are shown to be more efficient than native ones. The two analytes are well separated within 90 s in 70 mmol/L acetate buffer (pH 5.5) containing 0.01% (v/v) Brij35. Detection limits were found to be 1.0 μmol/L for strychnine and 0.2 μmol/L for brucine at S/N=3. The method was used to determine trace strychnine and brucine in rat serum, and the results obtained correlate well with those obtained via high-performance liquid chromatography (HPLC).      

Rapid and sensitive determination of strychnine and brucine in human urine by capillary electrophoresis with field‐amplified sample stacking

A simple, rapid, sensitive and low‐cost method using capillary electrophoresis (CE) coupled with field‐amplified sample stacking (FASS) has been developed and validated for the simultaneous determination of strychnine and brucine residues in human urine. Before sample loading, a water plug (3.5 kPa, 3 s) was injected to contain sample cations and to permit FASS. Electrokinetic injection at a voltage (20 kV, 25 s) was then used to introduce cations. Separation was performed using 20 mM acetate buffer (pH 3.8) with an applied voltage of 20 kV. The calibration curves were linear over a range of 8.00–2.56 ∞ 10² ng/mL (r = 0.9995) for strychnine and 10.0–3.20 × 10² ng/mL (r = 0.9999) for brucine. Extraction recoveries in urine were greater than 79.6 and 82.8% for strychnine and brucine, respectively, with an RSD of less than 4.9%. The detection limits (signal‐to‐noise ratio 3) for strychnine and brucine were 2.00 and 2.50 ng/mL, respectively. A urine sample from one healthy female volunteer (26 years old, 50 kg) was pretreated and analyzed. Strychnine and brucine levels in urine could be detected 24 h after administration. On these grounds, this method was feasible for application to preliminary screening of trace levels of abused drugs for both doping control and forensic analysis. Copyright © 2009 John Wiley & Sons, Ltd.     

Hollow fiber-based liquid-phase microextraction combined with on-line sweeping for trace analysis of Strychnos alkaloids in urine by micellar electrokinetic chromatography

A new method for the enrichment of Strychnos alkaloids in biological samples via liquid-phase microextraction (LPME) based on porous polypropylene hollow fibers combined with on-line sweeping in micellar electrokinetic chromatography (MEKC) was developed. Strychnos alkaloids were first extracted from urine sample which was adjusted to alkaline conditions (0.5 mol l(-1) NaOH). The unionized analytes were subsequently extracted into 1-octanol impregnated in the pores of hollow fibers, and then into an acidic acceptor solution (100 mmol l(-1) H3PO4) inside the hollow fiber. The extract was analyzed directly by on-line sweeping in MEKC. In the method, the compound berberine was used as the internal standard (I.S.) for the improvement of the experimental reproducibility. The calibration curve was linear over a range of 20-200 ng ml(-1) for both strychnine and brucine in human urine sample, with a correlation coefficient of 0.996 and 0.997, respectively. The detection limits (S/N=3:1) for strychnine and brucine were 1 and 2 ng ml(-1), respectively. The LPME-sweeping method has been successfully applied to the analysis of strychnine and brucine in real urine sample, indicating that LPME-sweeping-MEKC is a promising combination for analysis of basic drugs present at low levels in some biological matrices.     

超高效液相色谱法测定虾青素

建立超高效液相色谱法快速检测虾青素的方法。采用UPLC BEH C_8色谱柱(50 mm×2.1 mm,1.7μm),考察了流动相、流量及柱温对虾青素样品分离的影响,确定了最佳色谱条件:等度洗脱,流动相为甲醇–水(体积比为75∶25),流量为0.5 mL/min,柱温为40℃,检测波长为475 nm。虾青素的质量浓度在0.2~10.0μg/mL范围内与其色谱峰面积呈良好的线性关系,线性相关系数r=0.998 8,检出限(S/N=3)为0.1μg/mL,定量限(S/N=10)为0.2μg/mL。测定结果的相对标准偏差为0.41%(n=6),加标回收率为105.8%~110.3%。该方法快速、简单、可靠、灵敏、重复性好,可用于虾青素有关样品的快速检测。     

高效液相色谱法测定皮炎宁酊中间苯二酚和水杨酸的含量

采用高效液相色谱法测定了皮炎宁酊中间苯二酚和水杨酸的含量。色谱柱为ＨｙｐｅｒｓｉｌＯＤＳ柱,流动相为Ｖ（甲醇）∶Ｖ（水）∶Ｖ（乙酸）＝５０∶５０∶０．９。检测波长为２８５ｎｍ。在此条件下,间苯二酚和水杨酸可与其降解产物及杂质完全分开。     

全二维气相色谱-电子捕获检测器法分析土壤中毒杀芬同类物的残留

建立了全二维气相色谱-电子捕获检测器(GC× GC-μECD)检测土壤中毒杀芬同类物的分析方法.以非极性的DB- XLB(20 m×0.25 mm×0.25 μm)为第一色谱柱,中等极性的BPX-50(2 m×0.1 mm×0.1 μm)为第二色谱柱,对土壤中23种高关注毒杀芬同类物进行了分离鉴定,并采用基质曲线外标法进行定量分析.本方法在1～200,μg/L浓度范围内,毒杀芬同类物的线性相关系数(r2)均大于0.99,方法检出限(S/N=3)为0.039～0.482 μg/L,基质加标毒杀芬同类物的回收率为55％～115％,相对标准偏差(RSD)均小于30％(n=5).利用本方法对毒杀芬污染的土壤样品进行了测定,获得了较好的分离效果.