IF 0.7 4区化学 Q4 CHEMISTRY, ANALYTICAL

色谱

Pub Date : 2023-12-01 DOI: 10.3724/SP.J.1123.2023.06010

Zhenyong Zhang

Chiral compounds play an important role in the pharmaceutical industry owing to their unique biological activities. The enantiomers must be separated because they can exhibit different pharmacological activities. Thus, the development of chiral separation methods is essential to determine the purity of enantiomers. 4-Chloromethyl-2,2-dimethyl-1,3-dioxolane is an important chiral pharmaceutical intermediate. In this context, a method based on chiral capillary gas chromatography was established for the separation and determination of the enantiomers of 4-chloromethyl-2,2-dimethyl-1,3-dioxolane. The separation of (R)- and (S)-4-chloromethyl-2,2-dimethyl-1,3-dioxolane was initially investigated using two conventional stationary-phase capillary columns: SH-I-5Sil MS and SH-WAX. The stationary phase of SH-I-5Sil MS consisted of 5% phenyl and 95% polymethylsiloxane, whereas the stationary phase of SH-WAX consisted of 100% crosslinked polyethylene glycol. Neither of the columns exhibited chiral selectivity, so they both were unable to separate the enantiomers of 4-chloromethyl-2,2-dimethyl-1,3-dioxolane. Subsequently, the separation of (R)- and (S)-4-chloromethyl-2,2-dimethyl-1,3-dioxolane was investigated using four chiral columns: Rt-bDEXm, Rt-bDEXsm, Rt-bDEXse, and InertCap CHIRAMIX. Among the chiral columns, Rt-bDEXse, which used a stationary phase composed of 2,3-di-O-ethyl-6-O-tert-butyl dimethylsilyl β-cyclodextrin added to 14% cyanopropyl phenyl and 86% dimethyl polysiloxane, achieved the best separation of (R)- and (S)-4-chloromethyl-2,2-dimethyl-1,3-dioxolane. Thus, this column was selected as the analytical column for further method optimization. Detection was performed using a hydrogen flame ionization detector. The effects of various gas chromatographic parameters, such as linear velocity, initial column temperature, column heating rate, and solvent type, on the separation of (R)- and (S)-4-chloromethyl-2,2-dimethyl-1,3-dioxolane were investigated. The optimal chromatographic conditions included a linear velocity of 70 cm/s, an initial column temperature of 70 ℃, and a column heating rate of 2.0 ℃/min. The final column oven temperature was 150 ℃. Methanol, ethanol, ethyl acetate, n-hexane, dichloromethane, and dimethyl sulfoxide were selected as solvents. The results showed that dimethyl sulfoxide interfered with the peaks of the target compounds, whereas the other solvents had no significant effect on the peak shape and separation of (R)- and (S)-4-chloromethyl-2,2-dimethyl-1,3-dioxolane. Methanol was finally selected as the solvent in this study. Further experiments revealed that (R)- and (S)-4-chloromethyl-2,2-dimethyl-1,3-dioxolane could be rapidly separated within 10 min, with a resolution greater than 1.5. A good linear relationship was observed in the range of 0.5-50.0 mg/L, with a linear correlation coefficient

手性化合物因其独特的生物活性而在制药业中发挥着重要作用。由于对映体具有不同的药理活性，因此必须将其分离。因此，开发手性分离方法对于确定对映体的纯度至关重要。4-氯甲基-2,2-二甲基-1,3-二氧戊环是一种重要的手性医药中间体。为此，我们建立了一种基于手性毛细管气相色谱法的方法，用于分离和测定 4-氯甲基-2,2-二甲基-1,3-二氧戊环的对映体。首先使用两种传统的固定相毛细管色谱柱研究了(R)-和(S)-4-氯甲基-2,2-二甲基-1,3-二氧戊环的分离：SH-I-5Sil MS 和 SH-WAX。SH-I-5Sil MS 的固定相由 5% 的苯基和 95% 的聚甲基硅氧烷组成，而 SH-WAX 的固定相由 100% 的交联聚乙二醇组成。这两种色谱柱都不具有手性选择性，因此都无法分离 4-氯甲基-2,2-二甲基-1,3-二氧戊环的对映体。随后，研究人员使用四种手性色谱柱分离了(R)-和(S)-4-氯甲基-2,2-二甲基-1,3-二氧戊环：Rt-bDEXm、Rt-bDEXsm、Rt-bDEXse 和 InertCap CHIRAMIX。在这些手性色谱柱中，Rt-bDEXse 使用的固定相由 2,3-二-O-乙基-6-O-叔丁基二甲基硅基 β-环糊精添加到 14% 的氰丙基苯基和 86% 的二甲基聚硅氧烷组成，它实现了(R)-和(S)-4-氯甲基-2,2-二甲基-1,3-二氧戊环的最佳分离。因此，该分析柱被选为进一步优化方法的分析柱。检测采用氢火焰离子化检测器。研究了线性速度、色谱柱初始温度、色谱柱加热速率和溶剂类型等各种气相色谱参数对(R)-和(S)-4-氯甲基-2,2-二甲基-1,3-二氧戊环分离的影响。最佳色谱条件包括线速度为 70 cm/s，柱初始温度为 70 ℃，柱加热速率为 2.0 ℃/min。最终柱温为 150 ℃。溶剂选择甲醇、乙醇、乙酸乙酯、正己烷、二氯甲烷和二甲亚砜。结果表明，二甲亚砜会干扰目标化合物的峰形，而其他溶剂对(R)-和(S)-4-氯甲基-2,2-二甲基-1,3-二氧戊环的峰形和分离没有明显影响。本研究最终选择了甲醇作为溶剂。进一步的实验表明，(R)-和(S)-4-氯甲基-2,2-二甲基-1,3-二氧戊环可在 10 分钟内快速分离，分辨率大于 1.5。在 0.5-50.0 mg/L 范围内线性关系良好，线性相关系数大于 0.998。(R)-和(S)-4-氯甲基-2,2-二甲基-1,3-二氧戊环的检出限分别为 0.07 和 0.08 mg/L，相应的定量限分别为 0.22 和 0.25 mg/L。以甲醇为空白，在 0.5、2.0 和 10.0 mg/L 三个添加水平下进行了加标回收试验，以确定该方法的准确性。(R)-和(S)-4-氯甲基-2,2-二甲基-1,3-二氧戊环的回收率分别为94.0%-99.1%和96.0%-98.8%，相对标准偏差分别为1.26%-4.87%和1.51%-4.46%。该方法高效可靠，可作为分离 4-氯甲基-2,2-二甲基-1,3-二氧戊环对映体的参考。该方法还可用于评估制药行业中其他手性化合物的对映体纯度，以及生产手性药物和其他相关化合物。

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引用次数: 0

[Determination of 14 β-agonists in animal meat by ultra high performance liquid chromatography-tandem mass spectrometry]. [超高效液相色谱-串联质谱法测定动物肉中的 14 种 β-兴奋剂]。

IF 0.7 4区化学 Q4 CHEMISTRY, ANALYTICAL

色谱

Pub Date : 2023-12-01 DOI: 10.3724/SP.J.1123.2023.03008

Jieqiong Dong, Jin Xiao, Xin Zhou, Ning Li, Xuesong Wang, Junjie Kang

The addition of β-agonists to animal feed can significantly improve the lean-meat rate of pigs, cattle, sheep, and other animals. However, the food residues of β-agonists are harmful to human health. When meat with β-agonist residues is consumed, poisoning symptoms such as palpitation, dizziness, and muscle tremors may develop, and damage to the cardiovascular system, liver, and kidney may occur. In this study, a method based on ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was established for the rapid detection of 14 β-agonists (clenbuterol, salbutamol, ractopamine, clorprenaline, terbutaline, tulobuterol, bromobuterol, bambuterol, zilpaterol, mabuterol, fenoterol, arformoterol, cimaterol, and cimbuterol) in animal food sources. The sample pretreatment method and chromatographic conditions were optimized. The samples were hydrolyzed with β-glucuronidase hydrochloride/aryl sulfate esterase in ammonium acetate buffer (pH 5.2). Enzymatic hydrolysis was performed in a constant-temperature water bath ((36±2) ℃) oscillator for 16 h. The samples were cooled to room temperature and extracted with 0.5% formic acid acetonitrile. NaCl was added to separate the organic and aqueous phases, and 5 mL of the upper organic layer was purified using a one-step purification solid-phase extraction column. After drying with nitrogen at 50 ℃, the residue was dissolved in 0.4 mL of 0.2% formic acid aqueous solution. The samples were passed through a 0.22 μm filter and detected by UHPLC-MS/MS with gradient elution using acetonitrile and 0.1% formic acid aqueous solution as the mobile phases. The analytes were separated on a Phenomenex Kinetex F5 column and detected by positive-ion scanning in multiple-reaction monitoring (MRM) mode. Internal and external standard methods were used for quantitative analysis. The effects of the extract pH, solid-phase extraction column, purification method, and dissolved solution on the extraction efficiency were optimized during pretreatment. UHPLC-quadrupole time-of-flight MS was used to verify the purification effect of the one-step purification solid-phase extraction column, and the results indicated that this type of column could remove most of the phospholipids, sphingolipids, and glycerides in the sample extract. The factors influencing the different chromatographic columns and mobile phases were investigated. MS scanning was conducted in positive-ion mode with needle pump injection in mass-only mode, and the two daughter ions with the highest responses for each target were selected as the quantitative and qualitative ions. The declustering potential (DP) and collision energy (CE) of each ion were separately optimized in MRM mode. The switching mode of the mass spectrum and waste liquid was used, and the mobile phase was switched to waste liquid after all the target peaks were removed. These steps ensured that impurities in the sample flowed out of the

在动物饲料中添加β-兴奋剂可以显著提高猪、牛、羊等动物的瘦肉率。然而，β-兴奋剂的食物残留对人体健康有害。食用残留有β-兴奋剂的肉类，可能会出现心悸、头晕、肌肉震颤等中毒症状，并可能对心血管系统、肝脏和肾脏造成损害。本研究建立了一种基于超高效液相色谱-串联质谱（UHPLC-MS/MS）的方法，用于快速检测动物性食品中的14种β-兴奋剂（克伦特罗、沙丁胺醇、莱克多巴胺、氯丙那林、特布他林、图鲁布特罗、溴布特罗、班布特罗、齐帕特罗、马布特罗、非诺特罗、阿福莫特罗、西马特罗和辛布特罗）。对样品前处理方法和色谱条件进行了优化。样品在乙酸铵缓冲液（pH 5.2）中用盐酸β-葡糖醛酸酶/芳基硫酸酯酶水解。酶水解在恒温水浴（(36±2) ℃）振荡器中进行 16 小时。样品冷却至室温，用 0.5% 甲酸乙腈萃取。加入 NaCl 分离有机相和水相，用一步净化固相萃取柱净化上层有机层 5 mL。在 50 ℃ 下用氮气干燥后，将残留物溶解在 0.4 mL 的 0.2% 甲酸水溶液中。样品经 0.22 μm 过滤器过滤后，以乙腈和 0.1% 甲酸水溶液为流动相，采用 UHPLC-MS/MS 梯度洗脱检测。分析物在 Phenomenex Kinetex F5 色谱柱上分离，并在多反应监测（MRM）模式下通过正离子扫描进行检测。定量分析采用了内部和外部标准方法。在预处理过程中，对提取物的 pH 值、固相萃取柱、纯化方法和溶解液对提取效率的影响进行了优化。采用超高效液相色谱-四极杆飞行时间质谱验证了一步纯化固相萃取柱的纯化效果，结果表明该柱能去除样品提取物中的大部分磷脂、鞘脂和甘油酯。研究了不同色谱柱和流动相的影响因素。质谱扫描在正离子模式下进行，针泵进样在纯质量模式下进行，选择每个目标物响应最高的两个子离子作为定量和定性离子。在 MRM 模式下，分别优化了每个离子的解聚电位（DP）和碰撞能量（CE）。采用质谱和废液切换模式，在去除所有目标峰后将流动相切换为废液。这些步骤确保了样品中的杂质及时流出色谱柱，避免了过量杂质对质谱的影响。14 种 β-兴奋剂在 1.0-50 μg/L 范围内呈良好的线性关系，相关系数大于 0.99。检测限（LOD）和定量限（LOQ）分别为 0.1-0.2 和 0.3-0.6 μg/kg。在低、中、高添加水平下，14种β-兴奋剂的平均回收率为70.25%至117.48%，相对标准偏差（RSD）为0.63%至14.29%。采用所开发的方法对猪肉、牛肉和羊肉样品进行了分析。结果与国家标准方法接近，表明该方法准确可靠。该方法稳定性好、准确度高，适用于动物肉中β-兴奋剂的定性和定量检测。

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引用次数: 0

[Determination of nine organic amine compounds in CO₂ absorption liquid by hydrophilic interaction liquid chromatography-electrostatic field orbitrap high resolution mass spectrometry]. [亲水相互作用液相色谱-静电场orbittrap高分辨率质谱法测定CO2吸收液中的9种有机胺化合物]。

IF 0.7 4区化学 Q4 CHEMISTRY, ANALYTICAL

色谱

Pub Date : 2023-09-01 DOI: 10.3724/SP.J.1123.2022.12014

Ze-Kun Tang, Hui-Hui Wan, Hong Li, Shao-Yun Chen, Jin-Feng Zhao, Yu-Ming Sun, Rui Cai, Qiang Xu, Hua Zhang

Carbon dioxide (CO₂) absorption and capture is an effective measure to achieve the "dual carbon" goal of carbon peak and carbon neutrality in China. Organic amine compounds are widely used in the industrial separation and recovery of CO₂. Thus, the establishment of analytical methods for organic amine compounds is of great significance for the research and development of carbon capture and storage (CCS) technology and carbon capture, utilization and storage (CCUS) technology. In this study, a method was developed for the determination of nine organic amine compounds in CO₂ absorption liquid by hydrophilic interaction liquid chromatography (HILIC)-electrostatic field orbitrap high resolution mass spectrometry. The sample was diluted with water and filtered through a 0.22 μm nylon membrane before sampling and analysis. An Accucore HILIC column (100 mm×2.1 mm, 2.6 μm) was used for separation at 30 ℃. Gradient elution was conducted using 90% acetonitrile aqueous solution containing 5 mmol/L ammonium formate and 0.1% formic acid as mobile phase A and 10% acetonitrile aqueous solution containing 5 mmol/L ammonium formate and 0.1% formic acid as mobile phase B. Determination was performed using an electrospray ion source (ESI) in the positive ion mode. The quantitative analysis was carried out by standard addition method. The chromatographic retention performance of different chromatographic columns and the influence of different mobile phases on the separation of the organic amine compounds were compared, and the method was validated. The results showed that the linear ranges of the nine organic amine compounds were 0.04-25000 ng/mL with the linear correlation coefficients (R²) greater than 0.9910. The limits of detection (LODs) of the method were in the range of 0.0004-0.0080 ng/mL, and the limits of quantification (LOQs) of the method were in the range of 0.0035-0.0400 ng/mL. The average recoveries of the method ranged from 85.30% to 104.26% with relative standard deviations (RSDs) of 0.04%-7.95% at the spiked levels of 1, 1.5 and 3 times sample concentration. The established method was applied to detect the absorption waste liquid of a cement plant, and nine organic amine compounds could be effectively detected. The stability of the actual sample was tested, and the RSDs were 0.10%-6.35% in 48 h at 4 ℃. The method is sensitive, rapid and accurate for the determination of the nine organic amine compounds in industrial waste water. It can provide reference for the detection of organic amine compounds, and provide strong technical support for the research and industrial application of CO₂ capture technology.

二氧化碳（CO2）吸收和捕获是实现我国碳达峰和碳中和“双碳”目标的有效措施。有机胺化合物广泛用于CO2的工业分离和回收。因此，建立有机胺化合物的分析方法对碳捕获与储存（CCS）技术和碳捕获、利用与储存（CCUS）技术的研发具有重要意义。本研究建立了亲水相互作用液相色谱-静电场-轨道阱高分辨率质谱法测定CO2吸收液中9种有机胺化合物的方法。在取样和分析之前，用水稀释样品并通过0.22μm尼龙膜过滤。使用Accucore HILIC柱（100 mm×2.1 mm，2.6μm）在30℃下进行分离。使用含有5mmol/L甲酸铵和0.1%甲酸的90%乙腈水溶液作为流动相A，使用含有5mmol/L甲酸铵和1%甲酸的10%乙腈水溶液用作流动相B进行梯度洗脱。使用电喷雾离子源（ESI）在正离子模式下进行测定。采用标准加入法进行定量分析。比较了不同色谱柱的色谱保留性能以及不同流动相对有机胺化合物分离的影响，并对该方法进行了验证。结果表明，9种有机胺化合物的线性范围为0.04-25000ng/mL，线性相关系数（R2）大于0.9910。该方法的检测限（LOD）在0.0004-0.0080 ng/mL范围内，定量限（LOQ）在0.0035-0.0400 ng/mL范围。在1倍、1.5倍和3倍样品浓度的加标水平下，该方法的平均回收率在85.30%至104.26%之间，相对标准偏差（RSD）为0.04%-7.95%。将所建立的方法应用于某水泥厂吸收废液的检测，可以有效地检测出9种有机胺化合物。测试了实际样品的稳定性，在4℃下48小时内的RSD为0.10%-6.35%。该方法灵敏、快速、准确，适用于工业废水中9种有机胺类化合物的测定。可为有机胺化合物的检测提供参考，为CO2捕集技术的研究和工业应用提供强有力的技术支持。

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引用次数: 0

[Detection and analysis of moving reaction boundary-based electrophoresis distance using smartphone images]. [使用智能手机图像检测和分析基于移动反应边界的电泳距离]。

IF 0.7 4区化学 Q4 CHEMISTRY, ANALYTICAL

色谱

Pub Date : 2023-09-01 DOI: 10.3724/SP.J.1123.2023.06001

Xin-Qiao Song, Ze-Hua Guo, Wei-Wen Liu, Gen-Han Zha, Liu-Yin Fan, Cheng-Xi Cao, Qiang Zhang

Electrophoresis titration (ET) based on the moving reaction boundary (MRB) theory can detect the analyte contents in different samples by converting content signals into distance signals. However, this technique is only suitable for on-site qualitative testing, and accurate quantification relies on complex optical equipment and computers. Hence, applying this method to real-time point-of-care testing (POCT) is challenging. In this study, we developed a smartphone-based ET system based on a visual technique to achieve real-time quantitative detection. First, we developed a portable quantitative ET device that can connect to a smartphone; this device consisted of five components, namely, an ET chip, a power module, a microcontroller, a liquid crystal display screen, and a Bluetooth module. The device measured 10 cm×15 cm×2.5 cm, weighed 300 g, and was easy to hold. Thus, it is suitable for on-site testing with a run time of only 2-4 min. An assistant mobile software program was also developed to control the device and perform ET. The colored electrophoresis boundary can be captured using the smartphone camera, and quantitative detection results can be obtained in real time. Second, we proposed a quantitative algorithm based on ET channels. The software was used to recognize the boundary migration distance of three channels, a standard curve based on two given contents of the standards was established using the two-point method, and the content of the test sample was calculated. Human serum albumin (HSA) and uric acid (UA) were used as a model protein and biosample, respectively, to test the performance of the detection system. For HSA detection, different HSA solutions were mixed with a polyacrylamide gel (PAG) stock solution, phenolphthalein was added as an indicator, and sodium persulfate and tetramethyl ethylenediamine (TEMED) were used to promote polymerization to form a gel. For UA detection, agarose gel was filled into the ET channel, the UA sample, urate oxidase, and leucomalachite green were added into the anode cell and incubated for 20 min. ET was then performed. The fitting goodness (R2) values of HSA and UA were 0.9959 and 0.9935, respectively, with a linear range of 0.5-35.0 g/L and a log-linear range of 100-4000 μmol/L. The limits of detection for HSA and UA were 0.05 g/L and 50 μmol/L, respectively, and the corresponding relative standard deviations (RSDs) were not greater than 2.87% and 3.21%, respectively. These results demonstrate that the detection system has good accuracy and sensitivity. Clinical samples collected from healthy volunteers were used as target blood samples, and the developed system was used to measure serum total protein and UA levels. Serum samples from five volunteers were selected, standard curves of total serum protein and UA were established, and the test results were compared with hospital standard testing results. The relative errors for serum total protein and UA were less than 6.0

基于移动反应边界（MRB）理论的电泳滴定（ET）可以通过将含量信号转换为距离信号来检测不同样品中的分析物含量。然而，这项技术仅适用于现场定性测试，准确的定量依赖于复杂的光学设备和计算机。因此，将这种方法应用于实时护理点测试（POCT）具有挑战性。在本研究中，我们开发了一种基于视觉技术的智能手机ET系统，以实现实时定量检测。首先，我们开发了一种便携式定量ET设备，可以连接到智能手机；该装置由ET芯片、电源模块、微控制器、液晶显示屏和蓝牙模块五部分组成。该装置尺寸为10厘米×15厘米×2.5厘米，重量为300克，易于握持。因此，它适用于现场测试，运行时间仅为2-4分钟。还开发了一个辅助移动软件程序来控制设备并执行ET。使用智能手机摄像头可以捕捉彩色电泳边界，并实时获得定量检测结果。其次，我们提出了一种基于ET通道的定量算法。该软件用于识别三个通道的边界偏移距离，使用两点法建立了基于两个给定标准内容的标准曲线，并计算了试样的含量。使用人血清白蛋白（HSA）和尿酸（UA）分别作为模型蛋白和生物样品来测试检测系统的性能。对于HSA检测，将不同的HSA溶液与聚丙烯酰胺凝胶（PAG）储备溶液混合，加入酚酞作为指示剂，并使用过硫酸钠和四甲基乙二胺（TEMED）促进聚合以形成凝胶。对于UA检测，将琼脂糖凝胶填充到ET通道中，将UA样品、尿酸盐氧化酶和无色孔雀绿加入阳极细胞中并孵育20分钟。然后进行ET。HSA和UA的拟合优度（R2）分别为0.9959和0.9935，线性范围为0.5-35.0g/L，对数线性范围为100-4000μmol/L。HSA和UA的检测限分别为0.05 g/L和50μmol/L，相应的相对标准偏差（RSD）分别不大于2.87%和3.21%。这些结果表明，该检测系统具有良好的精度和灵敏度。从健康志愿者身上采集的临床样本被用作目标血液样本，所开发的系统被用于测量血清总蛋白和UA水平。选择5名志愿者的血清样本，建立血清总蛋白和UA的标准曲线，并将检测结果与医院标准检测结果进行比较。血清总蛋白和UA的相对误差分别小于6.03%和6.21%，相应的RSD分别小于3.72%和5.84%。这些发现验证了所提出的检测系统的准确性和可靠性。本文介绍的基于智能手机的ET检测系统具有几个优点。首先，它实现了血清总蛋白和UA的便携式实时检测。其次，与传统的基于彩色边界的ET策略相比，它不依赖光学检测设备或计算机来获得定量检测结果；因此，它可以降低操作的复杂性，并提供可移植性和实时度量。第三，在同一设备上实现了血清总蛋白和UA两种生物标志物的检测，从而提高了ET方法的多靶点检测潜力。这些优点使所开发的方法成为临床应用和实时POCT的一个有前途的检测平台。

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引用次数: 0

[Rapid extraction and detection of five alkaloids in dried khat by solvent extraction-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry]. [溶剂萃取-高效液相色谱-四极杆飞行时间质谱法快速提取和检测干卡塔叶中的五种生物碱]。

IF 1.2 4区化学 Q4 CHEMISTRY, ANALYTICAL

色谱

Pub Date : 2023-09-01 DOI: 10.3724/SP.J.1123.2023.03009

Hong-Fei Shi, Bo-Peng Xu, Cheng-Xin Xu, Xiu-Qi Zhou, Hong-Fu Xu

Khat is a common plant that grows primarily in Eastern Africa and the Arabian Peninsula. Cathinone, norpseudoephedrine, and norephedrine are the main psychoactive components of khat. Experimental studies have shown that red and green khat have similar cathinone contents, but green khat contains more norpseudoephedrine and norephedrine than red khat. Research indicates that Ethiopians believe that red khat has stronger psychoactive effects than green khat. Therefore, we speculated that other substances in red khat may enhance its psychoactive effects. Using the sampling method, we identified two other psychoactive components in khat: methcathinone and ethcathinone. At present, only a few studies on the extraction and detection of alkaloids from khat have been published in China, and no reports on the extraction and detection of methcathinone and ethcathinone from khat are available. In this study, we established an extraction and detection method for five alkaloids in dried khat using high performance liquid chromatography-quadrupole time-of-flight mass spectrometry (HPLC-Q-TOF MS). To establish the extraction method, we optimized the extraction solvent and process. The amounts of dichloromethane and sodium hydroxide added during the purification step were also optimized. To establish the detection method, we optimized the chromatographic and MS conditions. The final extraction and detection method was as follows: Dried khat powder (0.1 g) was loaded into a polypropylene centrifuge tube, added with 1 mL of 0.05 mol/L hydrochloride aqueous solution, and vortex-oscillated for 3 min for extraction. The sample was centrifuged at 10000 r/min for 3 min. Next, 600 μL of the supernatant was placed in a centrifuge tube, added with 1 mL of dichloromethane, shaken for 1 min, and centrifuged at 10000 r/min for 3 min. Subsequently, 300 μL of the supernatant was placed in a centrifuge tube, added with 80 μL of 1 mol/L sodium hydroxide aqueous solution, shaken for 1 min, and added with 1 mL of acetonitrile. Vortex oscillation was performed for 2 min to extract the sample, after which solid sodium chloride (0.4 g) was added to the mixture, followed by shaking for 1 min to separate the acetonitrile and aqueous phases. The mixture was then centrifuged at 10000 r/min for 3 min. Finally, the supernatant was collected and diluted for further testing. The five target analytes were separated on a ZORBAX Eclipse Plus Phenyl-Hexyl column (100 mm×3.0 mm, 1.8 μm) via gradient elution using 0.1% acetic acid aqueous solution and acetonitrile as mobile phases with a flow rate of 0.3 mL/min and column temperature of 30 ℃. The analytes were identified using the targeted MS/MS method under positive electrospray ionization mode and quantified using the external standard method. The five alkaloids showed good correlations (all correlation coefficients (r2)≥0.9976) with their respective linear ranges. The limits of detection were between 0.08 and 0.75 μg/L, a

哈特是一种常见的植物，主要生长在东非和阿拉伯半岛。儿茶酮、去甲伪麻黄碱和去甲麻黄碱是卡塔叶的主要精神活性成分。实验研究表明，红卡塔叶和绿卡塔叶具有相似的卡西酮含量，但绿卡塔叶比红卡塔叶含有更多的去甲伪麻黄碱和去甲麻黄碱。研究表明，埃塞俄比亚人认为红卡塔叶比绿卡塔叶具有更强的精神活性。因此，我们推测红卡塔叶中的其他物质可能会增强其精神活性。使用抽样方法，我们在卡塔叶中鉴定了另外两种精神活性成分：甲卡西酮和乙卡西酮。目前，国内对卡塔叶生物碱提取和检测的研究较少，对卡塔叶甲卡西酮和乙卡西酮的提取和检测尚无报道。本研究采用高效液相色谱-四极杆飞行时间质谱法（HPLC-Q-TOF-MS）建立了干卡塔叶中五种生物碱的提取和检测方法。为了确定提取方法，我们对提取溶剂和工艺进行了优化。在纯化步骤中加入的二氯甲烷和氢氧化钠的量也进行了优化。为了建立检测方法，我们对色谱和质谱条件进行了优化。最终提取和检测方法如下：将干卡塔叶粉末（0.1g）装入聚丙烯离心管中，加入1mL 0.05mol/L盐酸水溶液，涡旋振荡3min提取。样品以10000 r/min离心3分钟。接下来，将600μL上清液置于离心管中，加入1mL二氯甲烷，振荡1分钟，并以10000 r/min离心机离心3分钟，随后，将300μL上清液放入离心管，加入80μL 1mol/L氢氧化钠水溶液，振荡1分钟，并加入1mL乙腈。进行涡旋振荡2分钟以提取样品，之后向混合物中加入固体氯化钠（0.4g），然后振荡1分钟以分离乙腈和水相。然后将混合物以10000r/min离心3分钟。最后，收集上清液并稀释以进行进一步测试。5种目标分析物在ZORBAX Eclipse Plus Phenyl Hexyl柱（100 mm×3.0 mm，1.8μm）上以0.1%乙酸水溶液和乙腈为流动相，梯度洗脱，流速0.3 mL/min，柱温30℃。分析物在正电喷雾电离模式下使用靶向MS/MS方法进行鉴定，并使用外标法进行定量。5种生物碱与各自的线性范围具有良好的相关性（相关系数r2≥0.9976）。检测限在0.08至0.75μg/L之间，定量限在0.25至2.50μg/L之间。从两种生物碱含量不同的植物中提取的5种生物碱的平均回收率在90.7%至105.2%之间。样品内精密度在0.5%至2.3%之间，日间精密度在1.0%至2.5%之间，日间精度在1.3%至3.3%之间。该方法能够快速预处理样品，灵敏度高，稳定性好，准确度合适。基于以上结果，我们得出结论，所提出的方法符合卡塔叶的检测和鉴定要求。因此，它可以为卡塔叶的理化鉴定提供有价值的参考，并为进一步研究其精神活性成分提供支持。

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引用次数: 0

[New pretreatment method for detecting petroleum hydrocarbons in soil: silica-gel dehydration and cyclohexane extraction]. [检测土壤中石油烃的新预处理方法：硅胶脱水和环己烷萃取]。

IF 0.7 4区化学 Q4 CHEMISTRY, ANALYTICAL

色谱

Pub Date : 2023-09-01 DOI: 10.3724/SP.J.1123.2023.04019

Jian Qu, Yu-Wen Ni, Hao-Ran Yu, Hong-Xu Tian, Long-Xing Wang, Ji-Ping Chen

Oil is a primary source of energy worldwide. However, the use of oil produces large amounts of pollutants, which are detrimental to the environment. The presence of petroleum hydrocarbons in soil is a critical marker of environmental pollution and safety. Rapid on-site detection technology has been broadly used in emergency tracking, offering critical information support for effective reactions to environmental emergencies. Thus, it is expected to play an increasingly critical role in environmental remediation efforts. The current approach for petroleum hydrocarbon detection in soil mainly involves Soxhlet extraction with a combination of solvents, including acetone and n-hexane. The samples are then analyzed after rotary evaporation, dehydration with anhydrous sodium sulfate, and purification using a magnesium silica-type adsorbent. Unfortunately, this approach requires sample analysis to be performed in the laboratory, which is tedious and time consuming, and consumes large amounts of solvents. Moreover, the rotary evaporator is not portable. Therefore, this method is not appropriate for the rapid on-site detection of petroleum hydrocarbons. In this study, a rapid on-site detection method based on silica-gel dehydration and cyclohexane extraction was developed for the extraction and pretreatment of petroleum hydrocarbons (C10-C40) in soil. First, an appropriate amount of silica gel was added to the soil, and the mixture was completely ground to eliminate moisture. Next, petroleum hydrocarbons were extracted with 40 mL of cyclohexane, and the extract was cleaned by Florisil solid-phase extraction (SPE) column elution. Finally, the samples were analyzed by gas chromatography (GC) to evaluate the above method. The silica gel exhibited optimal adsorption properties compared with anhydrous sodium sulfate, calcium oxide, and molecular sieves, with recovery of 87.5%. The effects of different soil water content (5%, 10%, and 20%) and silica gel (1, 3, 5, and 10 times the moisture content) dosage on the extraction of petroleum hydrocarbons were investigated. The recoveries of petroleum hydrocarbons increased from 74.0% to 103.8% after 15 min of invasive extraction (relative standard deviation, RSD, <10.1%) when silica gel amounting to 10 times the moisture content was used. Five types of silica gels with different properties were purchased from four manufacturers, and the effects of these silica gels on the dehydration and extraction efficiency of petroleum hydrocarbons in soil were assessed. The results showed that amorphous silica gel led to low recoveries (<60%), spherical silica gel achieved extraction efficiencies of approximately 70%-90%, and alkaline silica gel produced recoveries with poor precision. Therefore, neutral spherical silica gel was used for further experiments. The fingerprints of petroleum hydrocarbons with different carbon numbers are an important reference for identifying pollution sources. Thus, ensuring good recover

石油是世界范围内的主要能源。然而，石油的使用会产生大量的污染物，对环境有害。土壤中石油碳氢化合物的存在是环境污染和安全的重要标志。快速现场检测技术已广泛应用于紧急情况跟踪，为有效应对环境紧急情况提供关键信息支持。因此，预计它将在环境修复工作中发挥越来越重要的作用。目前检测土壤中石油烃的方法主要包括用包括丙酮和正己烷在内的溶剂组合进行索氏提取。然后在旋转蒸发、用无水硫酸钠脱水和用镁-二氧化硅型吸附剂纯化后对样品进行分析。不幸的是，这种方法需要在实验室中进行样品分析，这是乏味和耗时的，并且消耗大量溶剂。此外，旋转蒸发器不是便携式的。因此，该方法不适用于石油碳氢化合物的现场快速检测。本研究开发了一种基于硅胶脱水和环己烷提取的快速现场检测方法，用于土壤中石油烃（C10-C40）的提取和预处理。首先，向土壤中加入适量的硅胶，并将混合物完全研磨以消除水分。接下来，用40mL环己烷提取石油烃，并通过Florisil固相萃取（SPE）柱洗脱清洗提取物。最后，用气相色谱法对样品进行分析，对上述方法进行评价。与无水硫酸钠、氧化钙和分子筛相比，硅胶具有最佳的吸附性能，回收率为87.5%。研究了不同土壤含水量（5%、10%和20%）和硅胶（含水量的1、3、5和10倍）用量对石油烃提取的影响。石油烃的回收率在侵入提取15分钟后从74.0%增加到103.8%（相对标准偏差、RSD、，

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引用次数: 0

[Simultaneous determination of six rare sugars in solid foods by high performance liquid chromatography-evaporative light-scattering detection]. 【高效液相色谱-蒸发光散射检测法同时测定固体食品中的六种罕见糖】。

IF 0.7 4区化学 Q4 CHEMISTRY, ANALYTICAL

色谱

Pub Date : 2023-09-01 DOI: 10.3724/SP.J.1123.2023.02014

Yu Liu, Jia-Li Xing, Jian Shen, Xiao-Li Bi, Ling-Yan Mao, Xiao-Rong Xu, Shu-Fen Zhang, Yong-Jiang Lou, Xi Wu, Ying-Hua Mu

Excessive sugar consumption is associated with metabolic health problems. Rare sugars are gradually being used as substitutes for sugar, and their consumption is increasing daily, raising food-safety issues such as false advertising, adulteration, and overdosing. The determination of rare-sugar compounds has attracted considerable attention in recent years. However, no standard method for the simultaneous determination of six rare sugars (allulose, tagatose, trehalose, isomaltulose, erythritol, and mannitol) in solid foods is available. Therefore, establishing a suitable analytical method for these sugars is necessary. In this study, high performance liquid chromatography coupled with evaporative light-scattering detection was used to determine rare sugars in solid foods. The optimum chromatographic and detector conditions were determined by evaluating the instrument parameters. Analysis was carried out on a Zorbax Original NH2 column (250 mm×4.6 mm, 5 μm) via flow-rate gradient elution (0-15 min, 1.0 mL/min; 15-18 min, 1.0-2.0 mL/min; 18-25 min, 2.0 mL/min) with acetonitrile-water (80∶20, v/v) as the mobile phase. Sharp and symmetric chromatographic peaks were obtained under these conditions. The resolutions for all the six rare sugars were greater than 1.5. Optimization of the evaporative light-scattering detector was extremely important to the responses of the rare-sugar compounds. The two most significant parameters were the nebulizer carrier gas flow rate and drift tube temperature. The detection system was operated under the following conditions: the drift tube temperature was set to 50 ℃, the nebulizer carrier gas was high-purity nitrogen, the carrier gas flow rate was 1.0 mL/min, the nitrogen pressure was regulated to 275.79 kPa, and the gain factor was set to 3. The sample was extracted with 25 mL of water, shaken and vortexed for 10 min, purified with 200 μL of zinc acetate solution and 200 μL of potassium ferricyanide solution, and centrifuged at 4500 r/min for 10 min. Next, 1 mL of the supernatant was passed through a 0.22 μm aqueous-phase filter membrane, and the filtrate obtained was analyzed using the evaporative light-scattering detector. The six rare sugars were quantitatively analyzed using the external standard method and showed good linearity with coefficients of determination (R2) greater than 0.9985. The limits of detection and quantification were 0.020-0.60 and 0.60-1.8 g/100 g, respectively. In addition, when blank solid food samples were spiked with the analytes at three levels, the average recoveries of the six rare sugars were 92.6%-103.2%, with relative standard deviations (RSDs) of 0.7%-4.4%. An RSD of <5% indicated that the method had good precision. Interference experiments were performed to determine whether the sugars and artificial sweeteners commonly found in solid foods affected the targets. The method established in this study was used to analyze the contents of the six rare

过量摄入糖与代谢健康问题有关。稀有糖正逐渐被用作糖的替代品，其消费量每天都在增加，这引发了虚假广告、掺假和过量使用等食品安全问题。近年来，稀有糖化合物的测定引起了人们的极大关注。然而，目前还没有同时测定固体食品中六种罕见糖（allulose、tagatose、海藻糖、异麦芽酮糖、赤藓糖醇和甘露醇）的标准方法。因此，有必要为这些糖建立一种合适的分析方法。本研究采用高效液相色谱-蒸发光散射检测相结合的方法测定固体食品中的稀有糖。通过对仪器参数的评估，确定了最佳色谱和检测器条件。在Zorbax Original NH2柱（250 mm×4.6 mm，5μm）上，以乙腈-水（80∶20，v/v）为流动相，以流速梯度洗脱（0-15 min，1.0 mL/min；15-18 min，1.0-2.0 mL/min；18-25 min，2.0 mL/min）。在这些条件下获得了尖锐且对称的色谱峰。所有六种稀有糖的分辨率都大于1.5。蒸发光散射检测器的优化对稀有糖化合物的响应非常重要。两个最重要的参数是喷雾器载气流速和漂移管温度。检测系统在以下条件下运行：漂移管温度设置为50℃，喷雾器载气为高纯度氮气，载气流速为1.0mL/min，氮气压力调节至275.79kPa，增益因子设置为3。样品用25mL水提取，振荡和涡旋10分钟，用200μL乙酸锌溶液和200μL铁氰化钾溶液纯化，并以4500r/min离心10分钟。接下来，将1mL上清液通过0.22μm水相滤膜，使用蒸发光散射检测器分析获得的滤液。使用外标法对六种稀有糖进行了定量分析，并显示出良好的线性，测定系数（R2）大于0.9985。检测限和定量限分别为0.020-0.60和0.60-1.8g/100g。此外，当空白固体食品样品中加入三种水平的分析物时，六种稀有糖的平均回收率为92.6%至103.2%，相对标准偏差为0.7%至4.4%

{"title":"[Simultaneous determination of six rare sugars in solid foods by high performance liquid chromatography-evaporative light-scattering detection].","authors":"Yu Liu, Jia-Li Xing, Jian Shen, Xiao-Li Bi, Ling-Yan Mao, Xiao-Rong Xu, Shu-Fen Zhang, Yong-Jiang Lou, Xi Wu, Ying-Hua Mu","doi":"10.3724/SP.J.1123.2023.02014","DOIUrl":"10.3724/SP.J.1123.2023.02014","url":null,"abstract":"Excessive sugar consumption is associated with metabolic health problems. Rare sugars are gradually being used as substitutes for sugar, and their consumption is increasing daily, raising food-safety issues such as false advertising, adulteration, and overdosing. The determination of rare-sugar compounds has attracted considerable attention in recent years. However, no standard method for the simultaneous determination of six rare sugars (allulose, tagatose, trehalose, isomaltulose, erythritol, and mannitol) in solid foods is available. Therefore, establishing a suitable analytical method for these sugars is necessary. In this study, high performance liquid chromatography coupled with evaporative light-scattering detection was used to determine rare sugars in solid foods. The optimum chromatographic and detector conditions were determined by evaluating the instrument parameters. Analysis was carried out on a Zorbax Original NH2 column (250 mm×4.6 mm, 5 μm) via flow-rate gradient elution (0-15 min, 1.0 mL/min; 15-18 min, 1.0-2.0 mL/min; 18-25 min, 2.0 mL/min) with acetonitrile-water (80∶20, v/v) as the mobile phase. Sharp and symmetric chromatographic peaks were obtained under these conditions. The resolutions for all the six rare sugars were greater than 1.5. Optimization of the evaporative light-scattering detector was extremely important to the responses of the rare-sugar compounds. The two most significant parameters were the nebulizer carrier gas flow rate and drift tube temperature. The detection system was operated under the following conditions: the drift tube temperature was set to 50 ℃, the nebulizer carrier gas was high-purity nitrogen, the carrier gas flow rate was 1.0 mL/min, the nitrogen pressure was regulated to 275.79 kPa, and the gain factor was set to 3. The sample was extracted with 25 mL of water, shaken and vortexed for 10 min, purified with 200 μL of zinc acetate solution and 200 μL of potassium ferricyanide solution, and centrifuged at 4500 r/min for 10 min. Next, 1 mL of the supernatant was passed through a 0.22 μm aqueous-phase filter membrane, and the filtrate obtained was analyzed using the evaporative light-scattering detector. The six rare sugars were quantitatively analyzed using the external standard method and showed good linearity with coefficients of determination (R2) greater than 0.9985. The limits of detection and quantification were 0.020-0.60 and 0.60-1.8 g/100 g, respectively. In addition, when blank solid food samples were spiked with the analytes at three levels, the average recoveries of the six rare sugars were 92.6%-103.2%, with relative standard deviations (RSDs) of 0.7%-4.4%. An RSD of <5% indicated that the method had good precision. Interference experiments were performed to determine whether the sugars and artificial sweeteners commonly found in solid foods affected the targets. The method established in this study was used to analyze the contents of the six rare ","PeriodicalId":9864,"journal":{"name":"色谱","volume":"41 9","pages":"781-788"},"PeriodicalIF":0.7,"publicationDate":"2023-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10507526/pdf/cjc-41-09-781.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"10287264","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

[One-step generation of droplet-filled hydrogel microfibers for 3D cell culture using an all-aqueous microfluidic system]. [使用全水性微流体系统一步生成用于3D细胞培养的液滴填充水凝胶微纤维]。

IF 1.2 4区化学 Q4 CHEMISTRY, ANALYTICAL

色谱

Pub Date : 2023-09-01 DOI: 10.3724/SP.J.1123.2023.06008

Meng-Qian Zhao, Hai-Tao Liu, Xu Zhang, Zhong-Qiao Gan, Jian-Hua Qin

Hydrogel microfibers, which are characterized by flexible mechanical properties, a uniform spatial distribution, large surface areas, and excellent biocompatibility, hold great potential for various biomedical applications. However, the fabrication of heterogeneous hydrogel microfibers with high cell-loading capacity and the ability to carry multiple components via an environmentally friendly method remains challenging. In this study, we developed a novel pneumatic pump-assisted all-aqueous microfluidic system that enables the one-step fabrication of all-aqueous droplet-filled hydrogel microfibers with unique morphologies and adjustable configurations. By designing a pump-valve cycling system and selecting two immiscible fluids with stable water interfaces (dextran and polyethylene glycol), we successfully fabricated alginate microfibers with equidistantly arranged droplets through the ionotropic gelation reaction between sodium alginate and calcium chloride. The droplet size, interdroplet spacing, and microfiber dimensions could be flexibly controlled by adjusting the flow rates of the inner-phase, middle-phase, and outer-phase inlets. The results showed that the system enabled the high-throughput in situ formation of functional three-dimensional cell spheroids. The generated cell spheroids exhibited excellent cell viability and drug-testing functionality, indicating their potential applications in cell cultures. The developed technique offers strong support for future biomedical research and applications, and provides a new approach for the preparation of multifunctional hydrogel microfibers for materials science, tissue engineering, and drug testing.

水凝胶微纤维具有力学性能灵活、空间分布均匀、表面积大、生物相容性好等特点，在各种生物医学应用中具有巨大的潜力。然而，通过环境友好的方法制备具有高细胞负载能力和携带多种成分能力的异质水凝胶微纤维仍然具有挑战性。在这项研究中，我们开发了一种新型的气动泵辅助全水微流体系统，该系统能够一步制备具有独特形态和可调节配置的全水滴填充水凝胶微纤维。通过设计泵阀循环系统，并选择两种具有稳定水界面的不混溶流体（葡聚糖和聚乙二醇），我们成功地通过海藻酸钠和氯化钙之间的离子致凝胶化反应制备了具有等距排列液滴的海藻酸盐微纤维。液滴尺寸、液滴间距和微纤维尺寸可以通过调节内相、中相和外相入口的流速来灵活控制。结果表明，该系统能够高通量原位形成功能性三维细胞球体。所产生的细胞球体表现出优异的细胞活力和药物测试功能，表明其在细胞培养中的潜在应用。所开发的技术为未来的生物医学研究和应用提供了强有力的支持，并为制备用于材料科学、组织工程和药物测试的多功能水凝胶微纤维提供了一种新的方法。

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引用次数: 0

[Determination of 10 carbamate pesticide residues in liquid milk by ultra performance liquid chromatography-tandem mass spectrometry with pass-through solid-phase extraction purification]. [通过固相萃取纯化的超高效液相色谱-串联质谱法测定液态奶中10种氨基甲酸酯类农药残留量]。

IF 0.7 4区化学 Q4 CHEMISTRY, ANALYTICAL

色谱

Pub Date : 2023-09-01 DOI: 10.3724/SP.J.1123.2023.03017

Chao Yue, Chao-Qun Zhao, Si-Hao Mao, Zhan-Hua Wang, Bei Shi, Xin-Feng Xu, Jing-Jing Liang

Carbamates are used in broad-spectrum insecticides and herbicides, and have highly efficient, low-residue, and long-lasting characteristics. However, this type of pesticide exerts mutagenic, teratogenic, carcinogenic, and other adverse effects, and its frequent use can exceed the recommended scope and limits. Research on the determination of carbamate pesticides mainly focuses on foods of plant origin and pays less attention to foods of animal origin. The methods for carbamate determination described in the current national standards have complicated operating procedures and low efficiency. Therefore, highly efficient and accurate methods for carbamate detection in milk must be established. In this work, a rapid method based on pass-through solid-phase extraction (SPE) purification coupled with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed for the simultaneous determination of 10 carbamate pesticides in liquid milk. The pretreatment and instrument methods were systematically optimized. The milk sample was extracted with acetonitrile, and then purified using a Captiva EMR-Lipid filtration kit. The purified extract was separated on an ACQUITY UPLC BEH C18 column with mobile phase of methanol and 0.1% formic acid aqueous solution in gradient elution. The flow rate was 0.3 mL/min. Column temperature was 35 ℃. Quantitative analysis was performed using the external standard method with matrix matching curves. The 10 carbamate pesticides showed good linear relationships in the mass concentration range of 2-200 μg/L, with correlation coefficients greater than 0.999. The limits of detection (LODs) and quantification (LOQs) for the 10 carbamate pesticides were 0.045-0.23 and 0.15-0.77 μg/kg, respectively. Recovery tests were conducted using the blank-matrix method at three spiked levels of 15, 50, and 100 μg/kg, and good recoveries for the 10 carbamate pesticides were obtained. In particular, the recoveries for the three spiked levels of 15, 50, and 100 μg/kg were 68.7%-93.3% with relative standard deviations (RSDs) of 1.8%-8.0%. The proposed method is efficient, convenient, accurate, and suitable for the rapid detection of the 10 carbamate pesticides in liquid milk. Compared with the conventional NH2 and ENVITM-18 SPE columns used in the national standard determination method, the proposed method demonstrated better purification effects. The recoveries for aldicarb sulfoxide, aldicarb sulfone, methomyl, and carbaryl after purification using the Captiva EMR-Lipid kit increased from 60% to 80%. Thus, the proposed method is suitable for targets with strong polarity and gives measurement results with good repeatability and accuracy.

氨基甲酸酯用于广谱杀虫剂和除草剂，具有高效、低残留和持久的特点。然而，这类农药具有致突变、致畸、致癌和其他不良影响，其频繁使用可能超过建议的范围和限度。氨基甲酸酯类农药的测定研究主要集中在植物性食品上，较少关注动物性食品。现行国家标准中氨基甲酸酯的测定方法操作复杂，效率低。因此，必须建立高效、准确的检测牛奶中氨基甲酸酯的方法。本工作建立了一种基于固相萃取（SPE）纯化结合超高效液相色谱-串联质谱（UPLC-MS/MS）的快速方法，用于同时测定液态奶中10种氨基甲酸酯农药。对预处理和仪器方法进行了系统优化。牛奶样品用乙腈提取，然后用Captiva EMR脂质过滤试剂盒纯化。纯化的提取物在ACQUITY UPLC BEH C18柱上分离，流动相为甲醇和0.1%甲酸水溶液，梯度洗脱。流速为0.3mL/min。柱温为35℃。采用外标法和矩阵匹配曲线进行定量分析。10种氨基甲酸酯类农药在2-200μg/L的质量浓度范围内表现出良好的线性关系，相关系数大于0.999。10种氨基甲酸酯类农药的检出限（LOD）和定量限（LOQ）分别为0.045-0.23和0.15-0.77μg/kg。使用空白基质法在15、50和100μg/kg三种加标水平下进行了回收率测试，10种氨基甲酸酯农药的回收率良好。特别是15、50和100μg/kg三种加标水平的回收率为68.7%-9.3%，相对标准偏差为1.8%-8.0%。该方法高效、方便、准确，适用于液态奶中10种氨基甲酸酯类农药的快速检测。与国家标准测定方法中使用的传统NH2和ENVITM-18 SPE柱相比，该方法具有更好的纯化效果。使用Captiva EMR脂质试剂盒纯化后，涕灭威亚砜、涕灭碳砜、灭多威和西维因的回收率从60%增加到80%。因此，该方法适用于极性强的目标，并给出了具有良好重复性和准确性的测量结果。

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引用次数: 0

[Simultaneous determination of 36 mycotoxins in fruits by QuEChERS coupled with ultra performance liquid chromatography-tandem mass spectrometry]. 【QuEChERS-高效液相色谱-串联质谱法同时测定水果中36种真菌毒素】。

IF 1.2 4区化学 Q4 CHEMISTRY, ANALYTICAL

色谱

Pub Date : 2023-09-01 DOI: 10.3724/SP.J.1123.2022.12010

Rui Zhao, Qing-Wen Huang, Zhi-Ying Yu, Zheng Han, Kai Fan, Zhi-Hui Zhao, Dong-Xia Nie

Mycotoxins are secondary metabolites produced by toxigenic fungi under specific environmental conditions. Fruits, owing to their high moisture content, rich nutrition, and improper harvest or storage conditions, are highly susceptible to various mycotoxins, such as ochratoxin A (OTA), zearalenone (ZEN), patulin (PAT), Alternaria toxins, etc. These mycotoxins can cause acute and chronic toxic effects (teratogenicity, mutagenicity, and carcinogenicity, etc) in animals and humans. Given the high toxicity and wide prevalence of mycotoxins, establishing an efficient analytical method to detect multiple mycotoxins simultaneously in different types of fruits is of great importance. Conventional mycotoxin detection methods rely on high performance liquid chromatography (HPLC) coupled with mass spectrometry (MS). However, fruit sample matrices contain large amounts of pigments, cellulose, and minerals, all of which dramatically impede the detection of trace mycotoxins in fruits. Therefore, the efficient enrichment and purification of multiple mycotoxins in fruit samples is crucial before instrumental analysis. In this study, a reliable method based on a QuEChERs sample preparation approach coupled with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was established to determine 36 mycotoxins in fruits. In the optimal extraction method, 2.0 g of a sample was extracted with 10 mL of acetic acid-acetonitrile-water (1∶79∶20, v/v/v) in a 50 mL centrifuge tube, vortexed for 30 s, and ultrasonicated for 40 min. The mixture was then salted out with 2.0 g of anhydrous MgSO4 and 0.5 g of NaCl and centrifuged for 5 min. Next, 6 mL of the supernatant was purified using 85 mg of octadecylsilane-bonded silica gel (C18) and 15 mg of N-propylethylenediamine (PSA). After vigorous shaking and centrifugation, the supernatant was collected and dried with nitrogen at 40 ℃. Finally, the residues were redissolved in 1 mL of 5 mmol/L ammonium acetate aqueous solution-acetonitrile (50∶50, v/v) and passed through a 0.22 μm nylon filter before analysis. The mycotoxins were separated on a Waters XBridge BEH C18 column using a binary gradient mixture of ammonium acetate aqueous solution and methanol. The injection volume was 3 μL. The mycotoxins were analyzed in multiple reaction monitoring (MRM) mode under both positive and negative electrospray ionization. Quantitative analysis was performed using an external standard method with matrix-matched calibration curves. Under optimal conditions, good linear relationships were obtained in the respective linear ranges, with correlation coefficients (R2) no less than 0.990. The limits of detection (LODs) and quantification (LOQs) were 0.02-5 and 0.1-10 μg/kg, respectively. The recoveries of the 36 mycotoxins in fruits ranged from 77.0% to 118.9% at low, medium, and high spiked levels, with intra- and inter-day precisions in the range of 1.3%

真菌毒素是产毒真菌在特定环境条件下产生的次生代谢产物。水果由于水分含量高、营养丰富、收获或储存条件不当，对各种真菌毒素高度敏感，如赭曲霉毒素A（OTA）、玉米赤霉烯酮（ZEN）、棒曲霉素（PAT）、链格孢毒素等。这些真菌毒素可对动物和人类产生急性和慢性毒性作用（致畸性、致突变性和致癌性等）。鉴于真菌毒素的高毒性和广泛流行，建立一种有效的分析方法来同时检测不同类型水果中的多种真菌毒素具有重要意义。传统的真菌毒素检测方法依赖于高效液相色谱（HPLC）和质谱（MS）。然而，水果样品基质含有大量的色素、纤维素和矿物质，所有这些都极大地阻碍了水果中微量真菌毒素的检测。因此，在仪器分析之前，有效富集和纯化水果样品中的多种真菌毒素至关重要。本研究建立了一种基于QuEChERs样品制备方法，结合超高效液相色谱-串联质谱法（UPLC-MS/MS）测定水果中36种真菌毒素的可靠方法。在最佳提取方法中，2.0g样品在50mL离心管中用10mL乙酸-乙腈-水（1∶79∶20，v/v/v）提取，涡旋30s，超声处理40min。然后用2.0g无水MgSO4和0.5g NaCl盐析混合物，离心5min，使用85mg十八烷基硅烷键合硅胶（C18）和15mg N-丙基乙二胺（PSA）纯化6mL上清液。剧烈振荡和离心后，收集上清液并在40℃下用氮气干燥。最后，将残留物再溶于1mL 5mmol/L乙酸铵水溶液-乙腈（50∶50，v/v）中，并在分析前通过0.22μm尼龙过滤器。真菌毒素在Waters XBridge BEH C18柱上使用乙酸铵水溶液和甲醇的二元梯度混合物分离。注射量为3μL。在正电喷雾电离和负电喷雾电离的多重反应监测（MRM）模式下分析真菌毒素。定量分析采用外标法，采用矩阵匹配的校准曲线。在最佳条件下，在各自的线性范围内获得了良好的线性关系，相关系数（R2）不小于0.990。检测限（LOD）和定量限（LOQ）分别为0.02-5和0.1-10μg/kg。在低、中、高加标水平下，水果中36种真菌毒素的回收率在77.0%至118.9%之间，日内和日间精密度分别在1.3%至14.9%和0.2%至17.3%之间。采用经验证的方法调查了实际水果样品中的真菌毒素污染，包括草莓、葡萄、梨和桃（每种类型15个样品）。在样品中发现了11种真菌毒素，即altenuene（ALT）、altenusin（ALS）、交链孢醇甲醚（AME）、tenazonic acid（TeA）、tentoxin（Ten）、OTA、白僵菌素（BEA）、PAT、玉米拉隆酮（ZAN）、T-2毒素（T2）和霉酚酸（MPA）；三个样本被多种真菌毒素污染。真菌毒素在草莓、葡萄、梨和桃中的发生率分别为27%、40%、40%和33%。特别是链格孢毒素是这些水果中最常见的真菌毒素，发病率为15%。该方法简便、快速、准确、灵敏、重现性好、稳定性好；因此，它适用于同时检测不同水果中的36种真菌毒素。

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