酱油中3-氯-1,2-丙二醇检测能力验证

为了解国内实验室在3-氯-1,2一丙二醇检测领域的能力,中国国家认证认可监督管理委员会(CNCA)组织了酱油中3一氯一1,2-丙二醇检测能力验证活动,有19个省、市、自治区的34个实验室参加.测试结果满意的实验室占73.5%.     

用GC-M S-SI M法测定酱油中的3-氯-1,2丙二醇

利用气相色谱 -质谱联用离子选择检测法 (GC -MS-SIM)测定酱油中3 -氯 -1,2 -丙二醇(3_CPD),样品用苯硼酸衍生化处理 ,正己烷抽提 ,用HP-112m×0.2mm毛细管色谱柱分离 ,选择基峰离子m/z147进行测定 ,检出限0.001×10-6。该法操作简单 ,快捷 ,灵敏度高。     

酱油中3-氯-1,2-丙二醇的气相色谱-质谱分析

建立测定酱油中的痕量3-氯-1，2-丙二醇（3-MCPD）的方法。用PR小柱预分离试样，用苯基硼酸作为衍生化试剂，气相色谱-质谱联用测定。其线性范围为0.001-10mg/kg；相对标准偏差为1.5％；检测下限为0.001mg/kg。该方法已成功应用于酱油中痕量3-MCPD的检测。     

顶空衍生化固相微萃取法测定酱油中3-氯-1,2丙二醇

建立顶空衍生化固相微萃取测定酱油中3-氯-1,2丙二醇(3-MCPD)的方法。聚乙二醇-二乙烯基苯(CW-DVB)萃取纤维先顶空吸附苯基硼酸,然后同时萃取和衍生化样品顶空气体中的3-MCPD和内标物d5-3-MCPD,衍生化产物在进样口热解吸,GC-MS检测,内标法定量,特征离子为m/z196、201。结果表明,样品中3-MCPD质量浓度为0.01~1mg/kg时,工作曲线的线性良好(r=0.9994),添加回收率为89%~104%,检出限为0.01mg/kg。     

同位素稀释气相色谱-质谱法快速测定酱油中3-氯-1,2-丙二醇量

采用同位素稀释气相色谱-质谱联用(GC-MS)法,快速测定酱油中3-氯-1,2-丙二醇(3-MCPD)的含量。试样中加入3-氯-1,2-丙二醇的氘代同位素作为内标,经超声混匀后加入到自行填装的弗罗里硅土柱中,以乙醚洗脱,洗脱液经氮气吹干后在正己烷溶剂中进行衍生化,衍生化试剂采用七氟丁酰咪唑。GC-MS采用选择离子监测(SIM)模式进行定性定量分析。结果表明,本方法的添加回收率为95.0%~101.0%;相对标准偏差为3.2%~4.8%;检出限达到0.010mg/kg。本方法步骤简单,溶剂用量少,定性定量准确可靠。可快速测定酱油等调味品中3-氯-1,2-丙二醇的含量。     

同位素稀释气相色谱-谱法快速测定酱油中3-氯-，2-二醇量

采用同位素稀释气相色谱－质谱联用（GC－MS）法，快速测定酱油中3－氯－1，2-丙二醇（3-MCPD）的含量。试样中加入3－氯－1，2-丙二醇的氘代同位素作为内标，经超声混匀后加入到自行填装的弗罗里硅土柱中，以乙醚洗脱，洗脱液经氮气吹干后在正己烷溶剂中进行衍生化，衍生化试剂采用七氟丁酰咪唑。GC-MS采用选择离子监测（SIM）模式进行定性定量分析。结果表明，本方法的添加回收率为95．0％－101．0％；相对标准偏差为3．2％～4．8％；检出限达到0．010mg／kg。本方法步骤简单，溶剂用量少，定性定量准确可靠。可快速测定酱油等调味品中3－氯－1，2-丙二醇的含量。     

酱油中3-氯-1,2-丙二醇(3-MCPD)的暴露评估

通过对世界各国和国际组织对3-氯-1,2-丙二醇（3-MCPD）的评估结果分析和研究,结合我国酱油调查消费数据以及生产和检测3-MCPD的含量数据,采用国际食品添加剂联席会议（JECFA）和食品科学委员会（SCF）均推荐的毒性值进行暴露评估,评估结果为：将我国酱油中3-MCPD最高允许量设置为0．4mg／kg,对于人类健康及满足国际贸易的要求是适宜的。     

固相萃取-气相色谱-质谱法测定酱油中3-氯-1,2-丙二醇

建立了酱油中3-氯-1,2-丙二醇(3-MCPD)残留量的同相萃取-气相色谱-质谱(GC/MS)分析方法.利用SampliQ OPT固相萃取柱净化样品,考察了乙醇、丙酮、乙醚、乙醚-正已烷(9:1,V/V)4种洗脱液对3-MCPD回收效果的影响.洗脱液在室温下经氮气吹干后用双(三甲基硅烷基)三氟乙酰胺-三甲基氯硅烷(B...     

致癌物3-氯-1,2-丙二醇的毛细管电泳/电导分离检测

利用硼酸能与3-氯-1,2-丙二醇(3-MCPD)上的2个邻位羟基进行键合生成配合阴离子、从而增加多羟基化合物的负电荷的特性,在15 mmol/L 三羟甲基氨基甲烷(Tris)-10 mmol/L H3BO3(pH 8.3)介质中,采用毛细管电泳/电导检测法分离检测了3-MCPD,该方法的线性范围为0.5-20 mg/L,检出限为0.1 mg/L(S/N=3)。对缓冲溶液的种类、浓度、pH值以及硼酸与3-MCPD的相互作用对分离检测的影响作了探讨。应用于水解植物蛋白(HVP)中的3-MCPD的分离检测     

氯化亚铜催化3-氯-1-丁烯异构为1-氯-2-丁烯研究

采用一价铜盐为催化剂、二甲基甲酰胺为溶剂,在均相体系中催化3-氯-1-丁烯异构化生成1-氯-2-丁烯.考察了溶剂、反应温度、催化剂种类和加入量对反应的影响,研究发现反应温度和催化剂的加入量对异构化反应有较大影响.在最优条件3-氯-1-丁烯1 mL,二甲基甲酰胺9 mL,CuCl 0.10 g,60℃反应5 h,产物和原料的浓度比为3.88 mmol L-1.采用在线红外光谱对反应过程进行监测,检测到有红外吸收峰在反应过程中先增加后减少的变化过程,提出了可能的反应机理.     

Molecular sensing of 3-chloro-1,2-propanediol by molecular imprinting

A covalent interaction-based molecularly imprinted polymer (MIP) material for 3-chloro-1,2-propanediol (3-MCPD), a post-testicular anti-fertility agent and possible carcinogen and mutagen in food products containing acid-hydrolyzed vegetable proteins, has been successfully fabricated using 4-vinylphenylboronic acid as the functional monomer. Rebinding assay revealed that the binding constant, K_B, for the receptor sites and non-specific sites are 1.93±0.1×10⁴ and 2.74±0.7×10² M⁻¹, respectively. The estimated number of receptor site, B_max, imprinted is 123.3±3 μmol/g of MIP. The MIP material is able to act as a potentiometric chemosensor for 3-MCPD via increase in Lewis acidity of the receptor sites upon reaction of the arylboronic acid with 3-MCPD to form the more acidic arylboronic acid esters. A simple pH glass electrode is sufficient to monitor the analyte-specific rebinding. In unbuffered aqueous media, linear potentiometric response from 0 to 350 ppm of 3-MCPD can be achieved. The MIP-based chemosensing in a soya sauce matrix has also been attempted. It is found that the dynamic range of the potentiometric chemosensing response of the MIP material is much reduced, probably due to the blocking or deactivation of receptor sites by interferents in soya sauces. Nevertheless, the present work demonstrated the feasibility of using MIP-based chemosensors as semi-quantitative analytical tools for screening purposes in quality control of food products.     

Determination of 3-chloro-1,2-propanediol in biological samples by quick-easy-cheap-effective-rugged-and-safe extraction coupled with gas chromatography-mass spectrometry and its biodistribution in rats

3-Chloro-1,2-propanediol is a common food contaminant, but reports on its determination in biological tissues are lacking. In the present study, a method was developed to detect 3-chloro-1,2-propanediol contents in rat tissues by quick-easy-cheap-effective-rugged-and-safe extraction and gas chromatography-mass spectrometry analysis. Biological samples were extracted with ethyl acetate and purified with adsorbents. The optimized adsorbent for each sample was selected from 4–5 combinations of N-propylethylenediamine, octadecylsilane, graphitized carbon black, strong anion exchange, and florisil. Extracted 3-chloro-1,2-propanediol was derivatized with heptafluorobutyric anhydride and subjected to gas chromatography-mass spectrometry. This method had good linearity (correlation coefficients >0.99) in the range of 2–2000 ng/g for blood, kidney, liver, testis, and brain samples. The limits of detection were under 0.8 ng/g; the limits of quantification were 2 ng/g; the recovery rates were 85%–102%; and the matrix effects were 1.98%–7.67%. This method also had good precision. The dynamic changes in 3-chloro-1,2-propanediol in rats gavaged with 20 mg/kg b.w. for 24 h were detected using this method. The 3-chloro-1,2-propanediol content in each tissue sharply increased to a peak, rapidly decreased within 2 h, and stabilized at 12 h. 3-Chloro-1,2-propanediol persisted in the kidney, testis, and liver 24 h after gavage.     

Determination of rate constants and activation energy of 3-chloro-1,2-propanediol hydrolysis by capillary electrophoresis with electrochemical detection

A method based on capillary electrophoresis with electrochemical detection (CE-ED) to calculate the rate constants and activation energy of 3-chloro-1,2-propanediol (3-MCPD) hydrolysis was described. Effects of several factors, such as the pH value and the concentration of the running buffer, separation voltage, injection time and the potential applied to the working electrode, were investigated to find the optimum conditions. With a 50 cm length of 25 microm diameter fused-silica capillary at a separation of 10 kV, well-defined separation of 3-chloro-1,2-propanediol from glycerol was achieved in 30 mmol/l borax (pH 9.24) within 13 min. Operated in a wall-jet configuration, a 328 microm copper-disk electrode used as the working electrode exhibits good response at 0.65 V (versus SCE) for 3-MCPD and glycerol. The rate constants of 3-MCPD hydrolysis at different temperatures were determined by monitoring the concentration changes of 3-MCPD. At 80, 85 and 90 degrees C, the measured rate constants of 3-MCPD hydrolysis were 3.8 x 10(-3) min(-1), 7.1 x 10(-3) min(-1) and 11.5 x 10(-3) min(-1), respectively. The activation energy for 3-MCPD hydrolysis was calculated to be 118.1 kJ/mol, which is in good agreement with the value in the literature.     

Asymmetric synthesis of L-carnitine from (R)-3-chloro-1,2-propanediol

A practical chemical synthesis of L-carmtine(1) has been accomplished from(R)-3-chloro-1,2-propanediol((R)-4),which is a main by-product originated from(R,R)-Salen Co(Ⅲ) catalyzed hydrolytic kinetic resolution(HKR) of(±)-epichlorohydrin.(R)-4 was utilized as a chiral starting material to prepare the key intermediate cyclic sulfite((R)-S).The new synthetic approach demonstrated an efficient utilization of organic by-product for the asymmetric synthesis of bioactive compounds.     

固相萃取/液相色谱-串联质谱法测定油脂中的3-氯-1,2-丙二醇棕榈酸二酯

建立了固相萃取/液相色谱-串联质谱检测油脂中3-氯-1,2-丙二醇棕榈酸二酯(3-MCPD-DP)的分析方法。油脂经溶解后,以自填装PSA+C_(18)吸附剂的固相萃取柱净化,ThermoFisher Accucore C_(18)色谱柱分离,以10 mmol/L甲酸铵甲醇溶液和10 mmol/L甲酸铵异丙醇溶液为流动相梯度洗脱,电喷雾正离子模式扫描,多反应监测模式定性分析,内标法定量。对离子化条件、固相萃取吸附剂用量、洗脱条件、定容溶液等条件进行了考察。在优化条件下,3-MCPD-DP在0.5～1 000 ng/mL范围内线性关系良好(r~20.999),方法检出限(S/N≥3)与定量下限(S/N≥10)分别为0.025 mg/kg和0.050 mg/kg。在橄榄油样品中加标量为0.1～0.5 mg/kg时,3-MCPD-DP的平均回收率为90.8%～102%,相对标准偏差(RSD,n=6)为1.1%～3.0%。该方法前处理简单快速、灵敏度较高,可满足油脂中3-MCPD-DP的检测要求。     

超高效合相色谱-串联质谱法测定食用植物油和油条中15种3-氯-1,2-丙二醇脂肪酸酯

建立了超高效合相色谱-三重四极杆质谱(UPC²-MS/MS)测定食用植物油和油条中15种3-氯-1,2-丙二醇脂肪酸酯(3-MCPDE)含量的方法。3-MCPDE的结构与甘油酯极为相似,因此很难将其从植物油中分离出来。为降低基质干扰,实验以不同极性的溶剂依次洗脱载有样品的氨基填料层析柱,用UPC²和ACQUITY QDa质谱检测器分析每单元洗脱液以绘制洗脱曲线。分段收集的洗脱液经混合、浓缩和过滤后,以Viridis HSS C18 SB色谱柱(150 mm×2.1 mm, 1.8μm)为分析柱,超临界CO₂和40%乙腈甲醇溶液(含0.1%甲酸)为流动相梯度洗脱,以97%异丙醇水溶液(含0.2%氨水)为补偿液,用配备电喷雾电离源的三重四极杆质谱在正离子、多级反应监测模式下测定,外标法定量。结果表明:15种3-MCPDE在各自范围内线性关系良好(相关系数(r²)≥0.997 3),检出限为0.01～0.68μg/L(S/N=3),定量限为0.04～1.74μg/L(S/N=10);在3个加标水平下的平均...