乌骨鸡黑素的元素组成与自由基状态初探

乌骨鸡(Gallina lanigera),又名白绒毛鸡,为我国特产的药用鸡种.远在唐代即知乌骨鸡能治风湿等病,明代李时珍在《本草纲目》中亦记载其药效.乌骨鸡的皮肤、肌肉、骨膜及内脏(除心、肝及肺外)中含有大量黑素,但其化学性质迄未鉴定.我们推测可利用黑素的自由基状态来探索黑素的理化性质及其与结构和功能的关系.Commoner 等于1954年最先发现在含黑素的组织(蛙卵)中自由基含量很     

UHPLC-ESI-MS/MS法测定动物源食物提取物中肌肽与鹅肌肽的含量

建立了一种同时测定动物源提取物中肌肽(Carnosine)和鹅肌肽(Anserine)含量的超高效液相色谱-电喷雾串联三重四极杆质谱(UHPLC-ESI-MS/MS)分析方法。采用超高效液相分离系统,借助Inertsil Amide HP色谱柱(2. 1 mm×100 mm,3μm)以0. 1%乙酸水溶液-乙腈为流动相,梯度洗脱分离,利用峰面积外标法定量。经过优化,肌肽和鹅肌肽在1. 95～500μg/L质量浓度范围内与峰面积呈良好的线性关系,相关系数(r)均大于0. 998。肌肽和鹅肌肽的检出限分别为0. 12、0. 47μg/L。以低浓度低聚肽原料为基质,在低、中、高3个加标浓度下,肌肽的回收率为99. 3%～109%,相对标准偏差(RSD,n=6)为0. 98%～1. 1%;鹅肌肽的回收率为100%～113%,RSD为1. 0%～1. 1%。该法前处理简单、快速,重现性好,准确度高,适用于动物源食物提取物中肌肽和鹅肌肽的同时快速检测。     

C18丙烯酰胺硅胶柱对肌肽分离能力的比较

建立了一种以牛肉中肌肽为代表,反相分离测定亲水性物质的方法.选用丙基酰胺键合硅胶亲水作用色谱柱,反相分析测定牛肉中亲水性成分-肌肽的含量,样品无需衍生处理.结合HPLC-MS联用技术确定了保留时间为10.276～10.609min的色谱峰就是肌肽峰.将该色谱柱与常规C18色谱柱进行对比后发现,该色谱柱对L-肌肽的保留能...     

《分析试验室》第26卷总目次

研究报告与简报1-1丙醇-水体系萃取浮选铜间接测定硫氰酸根……………………………………卫伟,钱予华,李全民*,刘国光1-5乌骨鸡肌肉中肌肽的鉴定与测定…………………………………………………田颖刚,谢明勇*,王维亚,吴红静1-9紫外分光光度法测定川芎中内酯的总量…………………………………………孙广平,杨学东*,王巧娥,丁明玉1-12进口铁矿砷量特征的内核密度分析与Bootstrap代表值估计纪雷*,孙健,林雨霏,蔡发,杜恒清,王岩……………………………………………………………………………………………………………………………………1-17三种…     

茶叶和蔬菜中铅的同位素稀释电感耦合等离子体质谱的测定

采用同位素稀释电感耦合等离子体质谱(ID-ICP-MS)法测定了铅的含量,通过对茶叶标准物质(GBW-07605)中铅的测定,考察了方法的准确度和精密度,比较了同位素稀释法与普通外标定量法的测定结果。在5mLHNO3～0.5mLHF～1mLH2O2的消解体系中,ID-ICP-MS法测量茶叶中铅的回收率可达97.7%,相对标准偏差(RSD)小于1.2%。实验对市售的12种茶叶和10种蔬菜中Pb进行测定,铅含量符合相应国家标准的样品分别占总样品数的83%和90%。该法适合于植物样品中微量铅的测定。     

反相高效液相色谱法同时测定4种氟喹诺酮类药物在鸡可食性组织中的残留

建立了一种可同时测定鸡可食性组织中环丙沙星、达氟沙星、恩诺沙星及沙拉沙星等多种残留的反相高效液相色谱 -荧光分析法。鸡的肌肉、皮和脂、肝、肾等4种组织经不同pH值的磷酸二氢钾缓冲溶液匀浆提取,上清液通过C18固相萃 取柱净化,以流动相洗脱。洗脱液经液相色谱分离后,用荧光检测器进行检测(激发波长280 nm, 发射波长450 nm),外标 法定量。对鸡的4种组织进行添加回收率测定,结果显示方法在添加水平为20~300 μg/kg时药物的回收率约为53.9%～93.4%,批间回收率测定值的相对标准偏差低于23%;环丙沙星、恩诺沙星、沙拉沙星 的定量检出限为20 μg/kg,达氟沙星为4μg/kg。方法简单、快速,能满足常规兽药残留检测的需要。     

免疫化学方法测定动物组织中呋喃唑酮残留标示物

以自制特异性抗体为核心试剂,建立了以苯甲醛为衍生试剂的呋喃唑酮残留标示物间接竞争ELISA方法.通过方阵滴定法和间接竞争法确定ELISA方法最佳反应条件:抗原最佳包被浓度200 μg/L,抗体最佳稀释倍数1:2.5×105,抗体与药物最佳工作配比40 μL: 60 μL,最佳竞争时间1 h.检出限为0.1 μg/L,检测范围0.1～25.6 μg/L,线性关系良好.在空白组织中(猪肌肉、猪肝脏、鸡肌肉、鸡肝脏、鱼肉)添加0.4、1.0和5.0 μg/kg AOZ,回收率55.8%～96.6%,相对标准偏差均小于20%.测定20份不同组织的空白样品,方法的检出限为0.4～0.5 μg/kg.以100 mg/kg呋喃唑酮饲喂动物,其组织样品同时经HPLC方法和本方法测定,数据表明本方法具有实际检出能力,测定结果与仪器方法的测定结果相近.通过与德国同类试剂盒比较实验表明,本方法的灵敏度、精密度、准确度接近于进口试剂盒水平,可用于动物可食性组织肝脏和肌肉中AOZ筛选.     

氟碳铈矿测氟样品处理新方法研究

用国标GB7483-87《水质氟化物的测定氟试剂分光光度法》不能准确测定氟碳铈矿中的氟量.原因在于该氟碳铈矿中的氟量比较高,一般达到9%～11%,易形成REF3沉淀,用一般的酸消解法很难将氟从矿样中全部蒸馏出来.本文采用加入Ca（OH）2,使氟转化CaF2,矿中的氟能完全被蒸出.并做了矿中氟测定的精密度实验,矿中的氟质量分数为9.02%,CV=0.4424.经加标矿中氟量的0.5、1和2倍等3个水平,其回收率在97.83%～99.44%范围,方法是对国标测氟法的重要补充.     

汽体流动量热计: 苯汽化热与苯汽体热容的测量

介绍了根据Pitzer型汽体流动量热计和Newsham型汽化热量热计建立的一套同时测定汽化热和汽态热容的汽体流动量热计. 该量热计可用于测定有机化合物及其混合物在不同温度下的汽化热、从沸点到200℃范围内的汽体热容. 量热计用苯标定, 汽化热的精度达到0.5%以上, 汽体热容的精度约1%.     

离子色谱-积分脉冲安培法测定肉类产品中鹅肌肽、高肌肽及肌肽

建立了一种离子色谱-积分脉冲安培（IC-IPAD）同时测定肉类样品中鹅肌肽、高肌肽及肌肽的分析方法。方法采用高效阴离子交换色谱柱AminoPac PA10（250 mm×2 mm）分离,以100 mmol/L NaOH为淋洗液,流速为0.2 mL/min,柱温为30℃。结果表明,3种目标化合物在15 min内可实现完全分离,且17种氨基酸对3种目标化合物不存在干扰。在最佳色谱条件下,鹅肌肽、高肌肽及肌肽在0.05~5.0 mg/L范围内呈良好的线性关系,线性相关系数（r）>0.99。3种目标化合物的检出限和定量限分别为8.9~22.1 μg/L和29.6~73.6 μg/L。对鸭胸及鹅胸样品进行分析,加标回收率为92.4%~104.5%。该方法简单方便,无需衍生化,灵敏度高,可用于肉类产品中相关营养成分的测定。     

Isolation and characterization of free haem from the shell gland of quail and hen

Free haem was isolated from the shell gland of the quail, Coturnix coturnix japonica, and of the fowl, Galinus domesticus, and characterized by HPLC‐ESI‐MS/MS. Quantification by HPLC gave values of 1.17–1.40 nmol/mg quail shell gland protein for haem, 1.66–2.17 nmol/mg protein for protoporphyrin and 0.25–0.40 nmol/mg protein for biliverdin. Possible implications of this previously unreported finding are discussed but they are not considered incompatible with the conclusion that all eggshell pigments are endogenously synthesized in the oviduct system. Copyright © 2011 John Wiley & Sons, Ltd.     

高效液相色谱法测定水潺中苯甲酸含量的不确定度评定

立了高效液相色谱法测量水潺中苯甲酸含量的不确定度评定方案,合理地赋予被测量值的分散性。根据JJF1059—1999技术规范要求,以高效液相色谱法测定水潺中苯甲酸含量为例,分析测量过程中引起不确定度的各种因素,评估各不确定度分量,评定合成标准不确定度,包含因子取2（P=95%）,计算扩展不确定度,以不确定度的形式报告测量结果。方法的扩展相对不确定度为2.6%,本例样品测量扩展不确定度为0.022 g/kg,测量结果为0.866±0.022 g/kg。评定方案同时适用于高效液相色谱法测定食品中苯甲酸、山梨酸、     

Normal phase high performance liquid chromatography for determination of paclitaxel incorporated in a lipophilic polymer matrix

A normal phase (NP) high performance liquid chromatography (HPLC) method was developed for analysis of paclitaxel incorporated in poly(sebacic-co-ricinoleic acid), a lipophilic polymer matrix utilized for preparation of an injectable formulation for the localized delivery of paclitaxel. Thin layer chromatography experiments revealed that separation of paclitaxel from the polymer is dependent on the eluting strength (solvent strength) of the mobile phase. The HPLC system consists of a Purospher STRAR Si analytical HPLC column (5 microm, 250mm x 4mm, Merck), and 1-2.5% (v/v) methanol in dichloromethane as the mobile phase. Detection was by UV absorbance at 240 and 254 nm. The effect of the mobile phase composition on paclitaxel retention, peak shape and column efficiency, and the influence of the sample loading on the shape of the paclitaxel peak were studied. The mobile phases used for the chromatography consisted of 1.5% (v/v) methanol in dichloromethane. Paclitaxel was determined in the formulation and in the samples from degradation studies using UV detection at a wavelength of 254 nm. UV detection at 240 nm has advantages for following polymer matrix degradation products due to higher detector response at this wavelength. The utility of the proposed NP HPLC approach was demonstrated by assessment of intra- and inter-batch content uniformity, and by the determination of paclitaxel content after 7 and 60 days exposure of the paclitaxel-loaded polymer matrix to in vitro and in vivo degradation.     

Qualitative analysis of Psoraleae Fructus by HPLC‐DAD/TOF‐MS fingerprint and quantitative analysis of multiple components by single marker

A variety of bioactive substances may account for the recognized efficacy and wide clinical application of Psoraleae Fructus in China. A high‐performance liquid chromatography–diode array detector (HPLC‐DAD) fingerprint method was developed to present the comprehensive phytochemical profile of the crude drug. Thirteen major compounds were separated and identified by HPLC coupled with time‐of‐flight mass spectrometry (HPLC/TOF‐MS), namely psoralenoside (PO), isopsoralenoside (IPO), psoralen (PS), isopsoralen (IPS), neobavaisoflavone (NBF), bavachin (BC), corylin (CN), bavachromene (BCM), psoralidin (PD), isobavachalcone (IBC), bacachinin (BCN), corylifol A (CA) and bakuchiol (BK). Then quantitative analysis of multiple components by single marker (QAMS) was applied in content determination of PO, IPO, PS, IPS, BC, IBC, BCN, CA and BK, with NBF as the internal standard. The calculation results indicated no significant difference from the traditional external standard method (p > 0.05, RSD < 2.62%), suggesting that QAMS is a reliable and convenient method for content determination of multiple chemical compositions, especially when there is a shortage of reference substances. In conclusion, simultaneous qualitative and quantitative analysis of Psoraleae Fructus may be fulfilled through the newly proposed method of QAMS combined with HPLC‐DAD/TOF‐MS fingerprint.     

溶剂棒微萃取-HPLC法快速测定常用蔬菜中的痕量尼古丁

建立了一种以溶剂棒微萃取为样品前处理技术,HPLC/UV法测定常用蔬菜中痕量尼古丁的方法。系统优化了溶剂棒微萃取条件以及HPLC法测定尼古丁的相关参数,方法的线性范围0.005~1 mg/L,相关系数为0.9999;检出限0.002 mg/L(S/N=3);在优化的实验条件下对尼古丁的富集倍数可达190倍。样品加标回收率72%~111%(除黄瓜加标样品为47%),相对标准偏差小于10.0%(n=3)。实验证明,本方法可用于常用蔬菜中痕量尼古丁的有效富集、测定。     

Determination of chloramphenicol in aquatic products by graphene‐based SPE coupled with HPLC‐MS/MS

An effective analytical protocol using graphene‐based SPE coupled with HPLC‐MS/MS for determination of chloramphenicol (CAP) in aquatic products has been developed. In the present work, graphene was evaluated as SPE sorbents for the analytes enrichment and clean up. The target analytes were quantified by a triple‐quadrupole linear ion trap MS in multiple‐reaction monitoring mode. In addition, the proposed method was validated according to Commission Decision 2002/657/EC. The calibration curve was linear over the range of 0.5–100 ng/mL. The mean values of RSD of intra‐ and interday ranging from 1.48 to 4.29% and from 3.25 to 7.42% were obtained, respectively. In the three fortified levels, the recoveries of CAP ranging from 92.3 to 103.4% with RSDs ≤ 5.58% were obtained. The proposed method has been successfully applied to the analysis of CAP in several aquatic product samples, indicating that graphene was a potential SPE sorbent for the enrichment of trace residues in food samples.     

离子交换固相萃取-高效液相色谱法研究吡虫啉在梨中的分布及残留动态

建立一种以固相萃取(SPE)、高效液相色谱(HPLC)为基础的测定梨果皮、果肉中吡虫啉残留量的方法。样品用乙腈进行提取,经二氯甲烷液液分配后用阳离子交换固相萃取(SCX-SPE)柱净化,高效液相色谱/二极管阵列检测法(HPLC/DAD)测定。各种添加水平(果皮:0.05、0.1、0.5、2 mg/kg;果肉:0.05、0.5、1mg/kg)的回收率为83%~103%,相对标准偏差(RSD)小于10%,方法的检出限为0.05 mg/kg。运用此方法分别对梨果皮和果肉中吡虫啉的残留动态进行研究,发现吡虫啉主要在梨果皮中残留,得到吡虫啉在果皮中的消解动态方程为:wt=w0×exp(-0.235t),半衰期是2.98 d。     

香港海域毒性微藻Alexandium tamarense的麻痹性贝毒研究

对从香港海域底坭分离并培养的毒性微藻塔玛亚历山大藻（Alexandiumtamareuse）的毒性和麻痹性贝毒素的组成进行研究。由生物试验测得其毒性为4．11×10－6MU／cell，用高效液相色谱分析毒素的组成，结果表明所含麻痹性贝毒成分主要是膝沟藻毒素－2（GTX2），含量为94.13pg／cell，本研究所用的微藻毒素提取方法和高效液相色谱分析方法都比较容易和有效。     

一种基于光谱信息计算解析的液相色谱滤噪新方法

提出一种基于光谱信息计算解析的高效液相色谱滤噪新方法.对于HPLC/DAD所获得的二维量测数据,取半峰高以上色谱数据点所对应的各列光谱数据进行计算处理,求得在检测波长下的单位标准光谱,并根据光谱维数据与单位标准光谱的关系,采用最小二乘法重构计算求出色谱维数据,从而去除色谱噪声.仿真实验和实测谱图的滤噪结果表明,该方法能有效滤除常见噪声,与中值滤波算法相比较,滤噪性能明显优于后者,是提高色谱定量分析准确度的有力工具.     

牙膏中三氯生的高效液相色谱法检测

利用甲醇超声提取牙膏样品中的三氯生,采用高效液相色谱法(紫外检测器)测定了其含量;探讨了最佳提取和色谱检测条件.结果表明,该方法对牙膏中三氯生的检出限为1.0μg/g,在三氯生浓度10.5～210mg/L范围内线性关系良好,相关系数R=0.999 98;样品加标回收率为99.81%～103.33%,相对标准偏差为0.03%.该方法具有简便、快速、准确、灵敏的优点,适用于牙膏中三氯生的测定.