Preparation of Antihypertensive Drugs in Biological Matrix with Solvent Front Position Extraction for LC–MS/MS Analysis

Solvent front position extraction procedure was used to prepare biological samples containing selected antihypertensive drugs (ramipril, lercanidipine, indapamide, valsartan, hydrochlorothiazide, perindopril, and nebivolol). Substances separated from the biological matrix components (bovine serum albumin) were quantified by means of liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Sample preparation process was performed with the use of a prototype horizontal chamber with a moving pipette driven by a 3D printer mechanism enabling a controlled eluent flow velocity. Application of this device was advantageous for simultaneous preparation of several samples for further quantitative analysis, with a synchronized reduction of manual operations and solvent consumption. Quantitative results obtained for the majority of the investigated antihypertensive drugs in a complex biological matrix were satisfactory. The values of the %RSD were around 5% for six of the seven substances (with the exception of indapamide). The method exhibits a suitable accuracy (the relative error percentage was below 10% for most drugs). The values of LOD and LOQ were in the range of 1.19 µg/L–8.53 µg/L and 3.61 µg/L–25.8 µg/L, respectively.     

Response Surface Optimization of Dispersive Solid-Phase Extraction Combined with HPLC for the Rapid Analysis of Multiple Coccidiostats in Feed

Since antimicrobials were banned as feed additives, coccidiostats with favorable anticoccidial action and growth promotion have been widely used in the breeding industry. The monitoring of coccidiostats in feed is necessary, while the current methods based on mass-spectrometer analysis have limited applicability and matrix effects could interfere with the results. Accordingly, in the present paper, a rapid analytical strategy for the simultaneous determination of six synthetic coccidiostats in feed using high-performance liquid chromatography coupled with diode-array detection was developed. Coccidiostats in chicken feeds were extracted with the trichloroacetic acid–acetonitrile solution. The cleanup was performed by dispersive solid-phase extraction after the optimization of the response surface methodology. The method exhibited good linearity for target coccidiostats within the range of 0.05~20 µg/mL. Recoveries for six compounds in fortified feed samples were from 67.2% to 107.2% with relative standard deviations less than 9.6%. The limit of detection was 0.2~0.3 mg/kg. The successful application of the method in commercial feed verified that it is effective and sensitive for the rapid determination of multiple coccidiostats in chicken feeds.     

多次溶剂萃取-气相色谱/串联质谱法测定热熔胶中的多环芳烃

建立了热熔胶中16种多环芳烃( PAHs)的多次溶剂萃取-气相色谱/串联质谱测定方法。详细研究了样品的萃取条件、净化条件和气相色谱/串联质谱测定条件,并与气相色谱-质谱法进行了对比。样品以10 mL正己烷为萃取溶剂,于60℃超声萃取20 min,萃取液依次经冷冻后离心、二甲基亚砜萃取2次、正己烷反萃取2次进行净化,得到的净化液以气相色谱/串联质谱法多反应监测( MRM)模式进行检测。本方法的线性相关系数( R2)均大于0.9969,检出限为1.0~10μg/kg,精密度小于6.3%,16种PAHs的加标回收率为80.4%~117.6%。考察了串联质谱检测的基质效应,发现基质效应不明显。本方法检出限优于气相色谱-质谱法(23~94μg/kg),并能增加定性和定量分析的准确性。本方法灵敏、准确可靠,满足热熔胶中PAHs测试要求。     

化学衍生与萃取联用技术在生物样品预处理中的应用

近年来各种萃取技术与化学衍生联用的模式作为一种新型样品处理技术广泛应用于生物样品预处理.这种联用技术不仅能有效去除样品基质,还能有效改善极性大、挥发性强、热稳定性差的目标分析物的回收率,提高方法的选择性和灵敏度.研究者根据待分析物及衍生试剂性质选取不同的联用模式.本文评述了萃取技术与化学衍生联用模式以及其在生物样品预处理中的应用.     

微波能用于酵母中海藻糖高效液相色谱分析样品制备的研究

利用微波能提取酵线中的海藻糖，建立了一种海藻糖分析样品的快速制备方法。高效液相色分析结果表明，无论是提取选择性、还是提取时间消耗，用微波法提取均具有常规提取法所无法比拟的优越性。经２０ｓ微波处理后，海藻糖酶已失活，故有效防止了提取过程中海藻糖的降解。微波提取不失为一种良好的样品的制备方法，尤其适用于对酵母低谢的研究。     

Optimization of the Sample Preparation Procedure for the Determination of Trace Elements in Auricularia auricula by Inductively Coupled Plasma-Optical Emission Spectrometry

This study aimed to develop a precise and accurate method of sample preparation of Auricularia auricula for inductively coupled plasma-optical emission spectrometry-based trace element determination and to compare concentrations of seven trace elements (Mg, Fe, Mn, Zn, Ni, Cr, Sr) in six A. auricula samples belonging to three varieties with two cultivation substrates. Five sample preparation procedures, microwave-assisted digestion, nitric acid digestion with hot plate heating, nitric acid and perchloric acid digestion with hot plate heating, nitric acid digestion with ash content, and aqua regia digestion with ash content, were compared. The performance of the procedures was determined based on the precision and accuracy of the results and the limits of detection of the elements. The best results, with limits of detection of 0.60–6.60?ng?·?mL^?1 and recoveries for spiked samples between 93.80 and 105.00%, were found using nitric acid digestion with ash content. Six A. auricula samples were analyzed using the proposed procedure. Among the tested elements, the concentration of Fe was highest in all six A. auricula samples up to a maximum concentration of 284.83?µg?·?g^?1. The concentrations of Mn, Cu, and Ni increased in mixed stands (basswood, birch, and mongolica) compared with pine sawdust cultivation.     

Lipemia in the Plasma Sample Affects Fentanyl Measurements by Means of HPLC-MS2 after Liquid-Liquid Extraction

Examination of fentanyl levels is frequently performed in certain scientific evaluations and forensic toxicology. It often involves the collection of very variable blood samples, including lipemic plasma or serum. To date, many works have reported the methods for fentanyl detection, but none of them have provided information about the impact on the assay performance caused by an excessive amount of lipids. This aspect may be, however, very important for highly lipophilic drugs like fentanyl. To address this issue, we developed the liquid chromatography method with mass spectrometry detection and utilized it to investigate the impact of lipids presence in rabbit plasma on the analytical method performance and validation. The validation procedure, conducted for normal plasma and lipemic plasma separately, resulted in good selectivity, sensitivity and linearity. The limits of detection and quantification were comparable between the two matrices, being slightly lower in normal plasma (0.005 and 0.015 µg/L) than in lipemic plasma (0.008 and 0.020 µg/L). Liquid–liquid extraction provided a low matrix effect regardless of the lipid levels in the samples (<10%), but pronounced differences were found in the recovery and accuracy. In the normal plasma, this parameter was stable and high (around 100%), but in the lipemic matrix, much more variable and less efficient results were obtained. Nevertheless, this difference had no impact on repeatability and reproducibility. In the present work, we provided reliable, convenient and sensitive method for fentanyl detection in the normal and lipemic rabbit plasma. However, construction of two separate validation curves was necessary to provide adequate results since the liquid-liquid extraction was utilized. Therefore, special attention should be paid during fentanyl quantification that involves lipemic plasma samples purified by this technique.     

分子印迹整体柱在样品前处理及色谱分析中的应用

分子印迹整体柱(MIPMC)结合了分子印迹聚合物的立体选择性高和整体柱制备简单、柱压低以及传质速率快等优点,是一种极具应用潜力的样品前处理介质和色谱固定相.该文详细介绍了分子印迹整体柱的制备方法,综述了近年分子印迹整体柱在样品前处理及色谱分析中的应用进展,并对其发展趋势做了展望.     

加速溶剂萃取-液相色谱-质谱/质谱法分析动物组织中的壬基酚、辛基酚和双酚A

建立了测定内分泌干扰物质烷基酚、双酚A的液相色谱-电喷雾串联质谱(负离子模式)分析方法,优化了样品前处理方法。以二氯甲烷作提取溶剂,采用加速溶剂萃取法萃取动物组织样品,萃取液用500 mg OASIS氨基固相萃取柱进行浓缩净化。对流动相组分和流动相添加剂对质谱的离子化效率进行了考察,测得3种化合物在高、中、低3个添加水平的回收率为88%~101%,相对标准偏差小于15%;双酚A、壬基酚和辛基酚的方法检出限分别为0.3, 0.05和0.1 μg/kg。对从北京市场上采集的27份动物组织样品进行检测,结果表明壬基酚广泛存在于各种动物源性食品中,检出含量为0.49~55.98 μg/kg,其中鱼肉组织中都检出壬基酚,而且其含量也较高(9.13~55.98 μg/kg)。     

液相色谱-质谱法测定不粘锅特富龙涂层中全氟辛酸铵残留

报道了一种基于快速溶剂提取(ASE)-液相色谱-串联质谱(LC-MS/MS)法定量测定不粘锅特富龙涂层中全氟辛酸铵(APFO)残留分析方法。采用乙腈快速溶剂提取不粘锅涂层中的APFO残留,以乙腈和10mmol/L乙酸铵水溶液为流动相,经高效液相色谱分离,以多极反应监测(MRM)测定。本方法在0.5~100μg/L内线性良好(R2=0.9995);检出限1 ng/g;方法回收率在80.5%~124.6%之间,相对标准偏差为1.33%~9.30%。本方法准确、快速、简便,可用于不粘锅涂层中APFO残留的检测。     

胶束液相色谱法测定制剂和尿样中布洛芬

采用胶束液相色谱法分离和测定制剂和尿样中布洛芬,考察了表面活性剂的种类及浓度、柱温、流动相pH值,流速对布洛芬色谱保留行为的影响,探讨并提出了布洛芬在吐温-80为非离子表面活性剂的胶束液相色谱中的色谱保留模型。以ZORBAXExtend-C18色谱柱(4.6mm×250mm,5μm),20mmol.L-1吐温-80和25mmol.L-1磷酸氢二钾(pH7.8)混合溶液为流动相,在263nm处进行测定,布洛芬的保留时间为5.8min。布洛芬的质量浓度在0.2～1.0g.L-1范围内呈线性关系,检出限(3S/N)为1.1ng,平均回收率达98.3%～102.1%。     

加速溶剂萃取/超高效液相色谱-串联质谱法测定沉积物中三苯甲烷类杀菌剂

采用超高效液相色谱-三重四极杆质谱(UPLC-MS/MS),结合加速溶剂萃取(ASE)前处理技术,建立了同时测定沉积物中3种三苯甲烷类残留(孔雀石绿、结晶紫、亮绿)的方法。干燥研磨后的底泥样品用中性氧化铝混合分散,以乙腈-Mc Ilvaine缓冲溶液(体积比10∶2)为萃取液,经ASE萃取富集后进入液相色谱-串联质谱分析,内标法定量。结果表明:3种三苯甲烷类化合物的峰形对称并完全分离,在0.5~50.0μg/L范围内线性良好(r0.998);在1 500 psi压力及60℃萃取温度下,目标物的回收率为65.8%~112%,相对标准偏差(n=6)为5.1%~14.4%,方法检出限为0.006~0.007μg/kg,定量下限为0.024~0.028μg/kg。该方法已用于滆湖沉积物中3种目标化合物的检测,为我国环境监管提供了技术支撑和数据支持。     

Pharmacokinetic study of amoxicillin in human plasma by solid‐phase microextraction followed by high‐performance liquid chromatography–triple quadrupole mass spectrometry

Sensitive and selective analytical procedures based on high‐performance liquid chromatography with mass spectrometric detection were developed for the determination of amoxicillin in human plasma samples. Samples were prepared by applying in‐house manufactured molecularly imprinted solid‐phase microextraction probes. The detection of target compounds was performed in multiple reaction monitoring mode. The multiple reaction monitoring detection was operated in the positive electrospray ionization mode using the transitions of m/z 366 ([M + H]⁺) → 349 for amoxicillin and m/z 390 ([M + H]⁺) → 372 for gemifloxacin. The method was validated with precision within 15% relative standard deviation and accuracy within 15% relative error. The method was successfully applied to study of the pharmacokinetics of amoxicillin in human plasma after oral administration of amoxicillin. Copyright © 2013 John Wiley & Sons, Ltd.     

污泥和沉积物中微量大环内酯类、磺胺类抗生素、甲氧苄胺嘧啶和氯霉素的测定

利用超声波辅助萃取(USE)技术,联合固相萃取(SPE)净化浓缩以及液相色谱-电喷雾串联质谱(LC-ESI-MS/MS)技术,建立了城市污泥和河流底泥中微量-痕量大环内酯类、磺胺类抗生素、甲氧苄胺嘧啶和氯霉素的多目标定量分析方法.样品经USE提取,SPE净化后,用LC-ESI-MS/MS检测.选择C18为分析柱,甲醇、5 mmol/L醋酸铵和0.1%甲酸混合溶液为流动相,选择在ESI正电离源下多反应监测(MRM)模式检测.对比了USE和加速溶剂萃取(ASE)对抗生素的萃取效率,优化了萃取条件.结果表明: USE和ASE对所选抗生素的萃取效率相当; 而50%甲醇溶液在酸性条件下(pH 2)萃取效率最好.抗生素的方法检出限为2.2～66.9 ng/g(干重,下同); 回收率介于74.7%～111.8%之间; 相对标准偏差小于10.6%.应用此方法在广州某污水处理厂脱水污泥及某河涌底泥中检测到磺胺二甲基嘧啶、克拉霉素、脱水红霉素及罗红霉素等多种抗生素,含量为6.8～125.6 ng/g.     

正相硅胶/选择洗脱-气相色谱法、液相色谱-质谱法检测食品中甲胺磷残留及其作用机理研究

以正相硅胶/选择洗脱为核心,建立了一种适用于各种复杂基质食品中甲胺磷残留分析的前处理方法.样品用无水Na2SO4配合乙酸乙酯均质研磨,超声波辅助提取,提取液经PSA粉末分散固相萃取和LC-Si柱单一溶剂选择洗脱净化后,供气相色谱仪(GC)和超高效液相色谱-串联质谱仪(UPLC-MS/MS)分析.气相色谱采用火焰光度检测器(FPD),液相色谱-质谱联用采用电喷雾正离子方式(ESI+),T3键合技术(HSS T3)和亲水作用(HILIC)超高效液相色谱柱分离,外标法定量.方法简便、快速,通过优化前处理和上机条件,在最优条件下进行测试,气相色谱法、液相色谱-质谱联用法的定量下限(S/N≥10)为0.0007～0.006 mg/kg,回收率分别为73%～90%, 81%～96%,相对标准偏差分别为2.4%～6.1%, 5.2%～10.8%.并对选择洗脱净化过程中的作用机理进行了研究.     

快速溶剂萃取–气相色谱质谱法测定土壤中戊唑醇残留量

建立快速溶剂萃取–气相色谱质谱法测定土壤中戊唑醇残留量的分析方法。土壤样品经ASE–350快速溶剂萃取仪萃取,萃取液用硅酸镁(弗罗里硅土)柱净化浓缩,然后用选择离子监测/全扫描(SIM/SCAN)模式,气相色谱–质谱法测定土壤中的戊唑醇含量。该方法检出限为0.008 mg/kg,加标回收率为84.0%~97.5%,测定结果的相对标准偏差为2.2%~11.6%(n=6)。该方法具有分离效果好,灵敏度高,重现性好,前处理操作简便等优点,可用于测定土壤中戊唑醇的残留量。     

Applications of Deep Eutectic Solvents in Sample Preparation and Extraction of Organic Molecules

The use of deep eutectic solvents (DES) is on the rise worldwide because of the astounding properties they offer, such as simplicity of synthesis and utilization, low-cost, and environmental friendliness, which can, without a doubt, replace conventional solvents used in heaps. In this review, the focus will be on the usage of DES in extracting a substantial variety of organic compounds from different sample matrices, which not only exhibit great results but surpass the analytical performance of conventional solvents. Moreover, the properties of the most commonly used DES will be summarized.     

盘式固相萃取–超高效液相色谱–串联质谱法快速测定环境水样中3种微囊藻毒素

建立盘式固相萃取–超高效液相色谱–串联质谱(UPLC–MS–MS)快速测定环境水样中3种微囊藻毒素(MCs)的方法。环境水样经过盘式固相萃取柱净化,采用Waters BEH C_(18)色谱小柱,以乙腈–0.2%甲酸水溶液为流动相,梯度洗脱分离后,UPLC–MS–MS多级监测正离子模式下外标法进行定性定量分析。3种微囊藻毒素在0.05~10.0μg/L范围内呈现良好线性关系,相关系数均大于0.999 4,方法检出限为0.02 ng/L。对同一环境样品进行0.1,1.0,5.0μg/L 3种浓度的加标回收试验,平均回收率为82.8%~108.8%,测定结果的相对标准偏差为2.1%~10.1%(n=6)。该方法快速、灵敏、准确,可有效应用于环境水样中微囊藻毒素的监测。     

液液萃取/液相色谱-串联质谱法分析海水中的短裸甲藻毒素

建立了基于液液萃取/液相色谱-串联质谱法定量分析海水中3种短裸甲藻毒素(BTX-1、BTX-2、BTX-3)。利用液相色谱-串联质谱的高灵敏度,将海水的分析体积减至20 mL;通过响应面优化确定了海水中短裸甲藻毒素的最佳提取条件:加6 g氯化钠,旋涡时间60 s,用5 mL乙酸乙酯提取2次。3种短裸甲藻毒素的线性范围为1～200μg/L,其检出限均为0.02μg/L,定量下限均为0.05μg/L,平均回收率为95.4%～104%,日内相对标准偏差(RSD)为2.2%～5.3%,日间RSD为3.0%～4.5%。方法降低了样品的分析体积,提高了前处理效率,且时效性和适用性强,实现了污染海水中短裸甲藻毒素的高效率痕量分析。