高效除草剂快杀捭标准物质的制备及表征

从快杀捭工业品出发，经活性炭纯化、硅胶柱层分离制得快杀稗标准物质，并进行熔点、高效液相色谱、紫外光谱、元素分析、红外光谱、质谱、核磁共振等方法的表征，以高效液相色谱法测得该标准品的纯度在99%以上。     

杀螨威中阿波罗的高效液相色谱分析方法研究

研究建立了杀螨威中阿波罗的高效液相色谱分析方法 ,利用紫外光谱方法确定了阿波罗的峰位置。所建方法具有灵敏、重复的优点 ,检出限为0.35mg/L,相对标准偏差小于2.0% ,用于样品测定 ,结果满意。     

反相高效液相色谱与紫外光谱对硝基苯类化合物的联合定性

结合高效液相色谱和紫外光谱各自的优点和信息，建立了有机化合物的高效液相色谱和紫外光谱联合定性方法。在高效液相色谱中，二极管阵列检测器实时在线地提供样品组分的紫外光谱，由此建立紫外光谱谱图库，并发展了谱图库检索算法，同时测定了硝基苯类化合物的反相色谱用热力学参数ａ、ｃ值。结果表明，该法是可行的，满足定性所需的精度。     

高效液相色谱/大气压化学电离质谱快速分析水中痕量有机磷农药

用反相液谱短柱实现了６种有机磷农药（乙酰甲胺磷、甲基对硫磷、杀螟硫磷、喹硫磷、二嗪农、辛硫磷）的高效液相色谱／大气压化学电离质谱（ＨＰＬＣ／ＡＰＣＩＭＳ）快速分析。此技术可以很好地实现水中痕量有机磷农药的测定,一次联机分析仅需１０ｍｉｎ。文中还讨论了二嗪农的碰撞诱导解离（ＣＩＤ）碎片谱。二嗪农和喹硫磷的检出限可低达０．０９ｎｇ和０．１ｎｇ。     

高效离子交换膜色谱介质制备及其对蛋白质的分离

制备了一种以纤维素膜为基质,以二乙胺为配基的高效液相离子交换膜色谱介质,并考察了不同柱长、不同洗脱梯度、不同流速下其对几何标准蛋白的分离情况。与高效液相柱色谱相比,这种高效液相膜色谱柱可以更快速的达到蛋白质的分离。即使在较高流速下,柱压仍较低。实验表明,这种高效液相膜分谱柱适合于蛋白质的快速分离。     

高效液相色谱法同时测定含脂羊毛中残留的除虫脲和杀铃脲

建立了同时测定含脂羊毛中除虫脲和杀铃脲的反相高效液相色谱方法。样品用正己烷-乙醚混合溶剂提取,经凝胶渗透色谱柱和固相萃取柱净化后,采用反相高效液相色谱-二极管阵列检测器检测,外标法定量。除虫脲和杀铃脲分别在0.41～41 mg/L和0.38～38 mg/L范围内线性关系良好,相关系数分别为0.9996和0.9999。最低检出限:除虫脲为0.22 mg/kg,杀铃脲为0.18 mg/kg;最低定量限:除虫脲为0.73 mg/kg,杀铃脲为0.60 mg/kg。在添加水平为0.76～10.25 mg/kg的除虫脲和杀铃脲时,平均加标回收率为86.3%～96.7%,相对标准偏差为4.2%～8.7%。该方法杂质干扰小、回收率高、重现性好,能够对含脂羊毛中除虫脲和杀铃脲残留量进行准确的定性定量分析。     

高效液相色谱-荧光检测法同时测定全血中5种香豆素类杀鼠剂

建立了同时测定全血中杀鼠灵、杀鼠迷、溴敌隆、氟鼠灵与溴鼠灵等5种香豆素类杀鼠剂的简便、灵敏、准确的高效液相色谱-变波长荧光分析方法。全血样品经乙酸乙酯提取后,在XDB C18柱(150 mm×2.1 mm, 5 μm)上以甲醇-0.2%乙酸水溶液(体积比为88∶12)混合液为流动相,采用荧光变波长程序检测,同时通过建立各杀鼠剂的荧光光谱库,利用谱库检索,提高定性的准确度。各杀鼠剂的线性范围为0.01~10.00 mg/L（杀鼠灵为0.05~10.00 mg/L）,检出限为0.01~0.05 mg/L,方法的加标回收率为81%～98%,其相对标准偏差（RSD）为3.8%～8.5%。该法适用于中毒病人的中毒诊断检测。     

抗氧剂168的质量控制分析及杂质鉴定

抗氧剂168的质量控制分析及杂质鉴定;抗氧剂168;二叔丁基苯酚;液相色谱-质谱联用;高效液相色谱;紫外-可见光谱     

环境样品中硝基苯类化合物的分析方法研究进展

主要介绍了我国近年来在环境样品中硝基苯类化合物的分析研究进展,内容包括:光度法(还原-偶氮光度法、阻抑动力学光度法、化学计量学分光光度法、人工神经网络-分光光度法)、气相色谱法(固相微萃取-毛细管气相色谱法、树脂吸附-气相色谱法、液-液微萃取气相色谱法、超声萃取-气相色谱法)、高效液相色谱法(反相高效液相色谱法、固相萃取-高效液相色谱法)和极谱法等分析方法。     

藏药镰形棘豆中2',4'-二羟基查尔酮对照品的制备和鉴定

采用乙醇提取、乙酸乙酯萃取、普通硅胶柱色谱和反相硅胶柱色谱分离纯化2',4'-二羟基查尔酮,采用紫外光谱、红外光谱、核磁共振波谱、质谱等技术鉴定结构,应用薄层色谱法、高效液相色谱-二极管阵列检测法、高效液相色谱-蒸发光散射检测法、超高效液相色谱-质谱联用法进行纯度检测。结果从镰形棘豆中分离得到纯度大于99.0%的2',4'-二羟基查尔酮。表明该制备方法简便,制备量大,所制得的2',4'-二羟基查尔酮纯度高,可作为镰形棘豆药材及其复方药的质量控制的对照品。     

磷酸三(2-氯乙基)酯标准物质的研制

研制了有机磷阻燃剂磷酸三(2-氯乙基)酯(TCEP)标准物质。采用硅胶柱层析法对TCEP原料进行纯化,得到纯度大于99%的TCEP纯品。通过红外光谱和气相色谱–质谱准确定性分析后,利用气相色谱法和气相色谱–质谱法结合热重分析法分别对TCEP纯物质进行纯度定值。将制备的50 g TCEP纯品分装到100个小瓶中,每瓶0.5g,从中随机选取10瓶,进行均匀性和稳定性实验,结果表明,研制的TCEP标准物质均匀性良好,在半年内是稳定的。研制的有机磷阻燃剂磷酸三(2-氯乙基)酯标准物质的纯度定值为99.56%,扩展不确定度为1.18%(k=2)。研制的磷酸三(2-氯乙基)酯标准物质满足国家二级标准物质标准的要求。     

Identifying N-nitrosofenfluramine in a nutrition supplement

The analytical data for identifying an unknown substance that was found in a nutrition supplement is presented. The unknown substance is purified using thin-layer chromatography and then measured using high-resolution mass spectrometry (HRMS) giving the exact mass from which the structure of the unknown substance was proposed. The procedure for synthesizing N-nitrosofenfluramine from fenfluramine is described. The extracted, synthesized, and standard N-nitrosofenfluramine are compared using HRMS, high-performance liquid chromatography (HPLC)-MS, HPLC-UV, Fourier transform IR spectroscopy, gas chromatography-MS, TLC, and NMR (1H NMR and 13C NMR). All analytical data obtained confirm that the unknown peak in the nutrition supplement is N-nitrosofenfluramine and that the synthetic procedure described can easily provide the N-nitrosofenfluramine reference substance for identification.     

阿维菌素B1a纯物质的制备纯化研究

本研究致力于制备纯化出高纯阿维菌素B1a,为核磁定量及质量平衡法提供计量溯源纯物质,从而给阿维菌素标准物质(研制中)纯度定值时提供纯度参考标准。利用制备型液相色谱对阿维菌素原料(B1a含量为95.71%)进行纯化,除去痕量杂质,真空干燥及冷冻干燥后得到阿维菌素B1a高纯物质。建立了基于制备液相色谱-真空干燥的阿维菌素B1a高纯物质的制备纯化工艺:采用Agilent Prep HT XDB-C18型制备柱,流动相为水/甲醇(15∶85),进样量500μL,流速20.0m L/min。经超高效液相色谱(UPLC)检测,产品纯度达到99.74%,可以满足核磁定量及质量平衡法的要求,并利用液相色谱串联质谱以及核磁共振法对产品进行定性分析。     

高纯硅溶胶成分标准物质的制备

采用离子交换法实现了高纯硅溶胶主成分与众多杂质离子的分离,并制备了高纯硅溶胶标准物质。多家实验室采用原子吸收光谱、电感耦合等离子体发射光谱、离子色谱等不同原理的方法协同定值;利用称量法对二氧化硅含量进行定值;用方差统计方法对定值结果进行数据处理和不确定度评定。     

Preparation and certification of tea leaves reference material

Summary Tea leaves reference material was prepared and certified for elemental composition. Japanese green tea leaves were ground, sieved to pass a 80-mesh screen, blended and bottled. The prepared material satisfied the homogeneity criteria for a reference material. Trace element analysis of the material was carried out by flame and graphite furnace atomic absorption and inductively coupled plasma atomic emission spectrometry.Certification of the material was performed using the data obtained by various analytical techniques and certified values are provided for Al, Ca, Cd, Cu, K, Mg, Mn, Na, Ni, Pb and Zn. The elemental composition of the tea leaves reference material is considered typical of Japanese green tea leaves.     

Preparation and calibration of a 231Pa reference material

A ²³¹Pa reference material has been characterized for amount of protactinium. This reference material is primarily intended for calibration of ²³³Pa tracers produced for ²³⁵U–²³¹Pa model age measurements associated with nuclear forensics and nuclear safeguards. Primary measurements for characterization were made by isotope dilution mass spectrometry of a purified ²³¹Pa solution using a ²³³Pa isotopic spike. The spike was calibrated by allowing multiple aliquots of the ²³³Pa spike solution to decay to ²³³U and then measuring the ingrown ²³³U by isotope dilution mass spectrometry using a certified uranium assay and isotopic standard as a reverse-spike. The new ²³¹Pa reference material will simplify calibration of the ²³³Pa isotope dilution spikes, provide metrological traceability, and potentially reduce the overall measurement uncertainty of model ages.

     

Certification of the chlorine content of the isotopic reference materials IRMM-641 and IRMM-642

The Slovak Institute of Metrology and the Institute for Reference Materials and Measurements have collaborated in the certification of the two chlorine reference materials IRMM-641 and IRMM-642. Until now no isotopically enriched chlorine isotopic reference material certified for isotopic composition and content has been available commercially. The isotopic reference materials IRMM-641 and IRMM-642 described herein are certified for isotopic composition and for chlorine content. The chlorine content of the reference material IRMM-641 was certified by use of high-precision argentometric coulometric titration at the Slovak Institute of Metrology. The base material used for IRMM-641 is NIST Standard Reference Material 975. The chlorine content of the reference material IRMM-642 was measured by isotope dilution, using negative thermal ionization mass spectrometry at the Institute for Reference Materials and Measurements. Both standard reference materials were prepared by dissolving NaCl in water. The reference material IRMM-641 contains 0.025022 +/- 0.00011 mol kg(-1) chlorine of natural isotopic composition with an n(37Cl)/n(35Cl) ratio of 0.31977 +/- 0.00082. The reference material IRMM-642 contains 0.004458 +/- 0.000028 mol kg(-1) chlorine with an n(37Cl)/n(35Cl) ratio of 0.01914 +/- 0.00088.     

Electrospray ionization mass spectrometry for the quantitation of albumin in human serum

Capillary reversed-phase liquid chromatography was coupled to electrospray ionization mass spectrometry for determining the concentration of human serum albumin (HSA) in a fresh frozen serum reference material. A biotinylated HSA (bHSA) was prepared and used as an internal standard for the serum albumin determination. The average HSA concentration of the serum sample was determined by mass spectrometry to be 41.5 ± 2.8 g/L at the 95% confidence limit for the measured value. The HSA concentration of the fresh frozen serum was also assayed using the bromocresol green dye-binding method, producing a value of 42.3 ± 1.5 g/L. Calibration curves generated from HSA standards spiked with bHSA showed excellent linearity and the relative standard deviation for replicate analysis of a bHSA spiked serum sample was less than 3%.     

河豚毒素标准样品的研制

采用质谱、核磁、红外及紫外对河豚毒素样品进行结构确证,采用柱后衍生高效液相荧光法对该纯度标准样品进行定值并进行了均匀性、稳定性检验。标准样品经国内6个具有分析资质的实验室进行协同定值,定值结果为99.45%,其扩展不确定度(95%置信区间)为0.51%。该标准样品达到国家标准样品的技术要求,可用于有关河豚毒素的方法校正和质量控制。     

Solid-phase synthesis of bleomycin group antibiotics. Elaboration of deglycobleomycin A(5)

The solid-phase syntheses of two deglycobleomycin A(5) analogues were achieved using a commercially available polystyrene resin containing triphenylmethyl-linked spermidine. The final products were deblocked and released from the resin, analyzed, and purified by C(18) reversed phase HPLC and characterized by high-field (1)H NMR spectroscopy and mass spectrometry. The purified products relaxed supercoiled plasmid DNA in a concentration-dependent fashion and to the same extent as authentic material derived from natural BLM A(5).