柱前荧光标记结合高效液相色谱—质谱联用技术分析花粉中饱和及不饱和脂肪酸

以荧光试剂苯并[b]吖啶酮-5-乙基对甲苯磺酸酯(BAETS)作为柱前衍生化试剂,对27种饱和脂肪酸和7种不饱和脂肪酸进行了优化衍生.在Hypersil BDS C8色谱柱(4.6×200 mm i.d,5μm)上,采用梯度洗脱对34种混合脂肪酸(FFA)衍生物进行了分离及定性定量分析.荧光检测激发和发射波长分别为λex=273 nm,λem=503 nm.多数脂肪酸的线性回归系数大于0.9995,检测限在11.70-68.25 fmol.采用大气压化学电离源(APCI)的正离子模式,实现了花粉中FFA组分的质谱鉴定.建立的方法具有良好的重现性,对实际样品测定结果满意.

超高效液相色谱—质谱联用法测定藏药萨热十三味鹏鸟丸中乌头碱类含量

目的 建立测定萨热十三味鹏鸟丸中乌头碱、次乌头碱及新乌头碱含量的超高效液相色谱-质谱联用法。方法 采用显微特征鉴别法鉴别成药中的铁棒锤,色谱柱为AcQuity UPLC BEH C_（18）柱,流动相A为甲醇,流动相B为0.1%甲酸溶液,梯度洗脱,采用电喷雾离子源（ESI）、正离子扫描（ES＋）及多反应监测（MRM）测定萨热十三味鹏鸟丸中乌头碱、次乌头碱及新乌头碱的含量。结果 萨热十三味鹏鸟丸成药粉末中可见铁棒锤特征性伞状或盔帽状淀粉粒;乌头碱进样量在13.15～2 630.00 ng范围内与峰面积线性关系良好（r=0.999 4）,平均回收率为97.34%,RSD=1.79%（n=9）;次乌头碱进样量在32.06～3 205.89 ng范围内与峰面积线性关系良好（r=0.999 9）,平均回收率为96.09%,RSD=1.94%（n=9）;新乌头碱进样量在10.23～2 046.00 ng范围内与峰面积线性关系良好（r=0.999 3）,平均回收率为95.94%,RSD=1.75%（n=9）。结论 该显微鉴别法简单易操作,显微特征明显,结果易辨识;该乌头碱类含量测定方法结果准确,重复性好,可用于同时测定萨热十三味鹏鸟丸中3种乌头碱类物质的含量。

清代团鹤纹石青缎的染料鉴定及色彩分析

纺织品文物是人类历史文化的珍贵遗产,色彩是纺织品文物重要的外在表现,而染料是色彩表现的基本内核。染料考古通过对文物的色彩、染料进行测试,结合古文献记载,可获得染料来源、染色工艺、内在审美、商品流通、文物年代和产地等重要历史信息。本文以中国丝绸博物馆馆藏清代团鹤纹石青缎为例,运用高效液相色谱—质谱联用技术检测丝织品文物上的染料,成功鉴别出红色染料苏木,蓝色染料靛青,黄色染料姜黄、黄檗、黄荆等,并结合相关历史文献对清代纺织品色彩的使用进行了分析。苏木与姜黄套染可得杏黄色,黄檗、黄荆与靛青套染可得绿色。该文物是在清代纺织品中发现使用黄荆染料的首个案例。该文物的鉴别结果为清代丝织品染色研究提供了科学依据,结合色彩分析有助于研究清代时期的经济、文化历史,亦可为清代丝织品色彩复制和文物修复及展示方法提供参考。

基于UPLC-Orbitrap-MS/MS技术的通络益晴方化学成分分析

目的通过超高效液相色谱—质谱联用(ultra-performance liquid chromatography-orbitrap-mass spectrometry/mass spectrometry,UPLC-Orbitrap-MS/MS)对通络益晴方的化学成分进行快速分析及初步鉴定。方法使用ZORBAX Eclipse Plus C 18色谱柱,以乙腈-0.1%甲酸水梯度洗脱,流速0.4 mL/min,柱温35℃;采用电喷雾离子源,正、负离子模式扫描,通过保留时间、精确相对分子质量和二级质谱裂解碎片,结合参考文献,对所得成分进行分析与初步鉴定。结果根据建立的色谱条件,从通络益晴方中初步鉴定出94个化学成分,其中有黄酮类化合物31个、酚酸类化合物14个、脂肪酸类化合物9个、皂苷类化合物6个、异黄酮类化合物5个、氨基酸类化合物4个、三萜类化合物4个、醛类化合物4个、多肽类化合物3个、苯丙素类化合物3个、醇类化合物3个,以及其他类化合物8个;正、负离子扫描模式下得到8个重复的成分。结论UPLC-Orbitrap-MS/MS技术能快速、初步鉴定出通络益晴方中化学成分,可为通络益晴方物质基础研究和新药研发提供依据。

UPLC-MS/MS法测定头孢哌酮钠舒巴坦钠及其与转化糖电解质配伍稳定性研究

目的建立同时测定头孢哌酮及舒巴坦含量的超高效液相色谱—质谱联用法(UPLC-MS/MS),并考察其与转化糖电解质注射液配伍后的稳定性。方法以氯唑沙宗作为内标,以Acquity UPLC BEH C_(18)色谱柱(2.1 mm×100 mm,1.7μm)分离,乙腈—水(含0.1%甲酸)为流动相行梯度洗脱,柱温25℃,流速0.2 ml/min,进样体积5μl。采用多反应监测(MRM),电喷雾离子化负离子(ESI-)方式检测,头孢哌酮m/z 644.2>115.1,舒巴坦m/z 232.0>139.9,内标氯唑沙宗m/z 168.0>132.1。结果头孢哌酮及舒巴坦在0.1~10μg/ml范围线性关系良好(r^(2)≥0.9964),回收率97.80%~104.70%,日内和日间精密度RSD 0.70%~2.22%;最低检测限头孢哌酮为0.05μg/ml(S/N≥10),舒巴坦0.02μg/ml(S/N≥10)。在考察的12 h内,头孢哌酮与舒巴坦含量为98.09%~100.40%,配伍液pH值4.18~4.37。配伍液无色变,无沉淀及结晶、气泡等可见性变化。结论此法适用于同时测定头孢哌酮及舒巴坦含量,准确便捷。头孢哌酮钠舒巴坦钠与转化糖电解质注射液配伍后,12 h内稳定。

盐胁迫下小麦甜菜碱和脯氨酸含量变化

运用高效液相色谱-质谱(HPLC-MS)联用技术 分析了耐盐性强、中、弱3个小麦品种SW12、宁春4 号和中国春苗期5个NaCl浓度胁迫下甜菜碱和脯氨酸 含量的变化。方差分析表明盐胁迫下3个小麦品种之间 甜菜碱的含量差异达到极显著水平(P<0.01),SW12的 含量最高,宁春4号次之,中国春最低,与小麦耐盐性 表现相一致;脯氨酸在叶片中的含量差异不显著,在 根中宁春4号和中国春的含量有显著差异(P<0.05)。结 果表明:小麦叶和根中甘氨酸甜菜碱含量与小麦盐胁 迫呈正相关,是小麦体内抵御盐胁迫的渗透调节物质 之一,可作为小麦耐盐性鉴定指标。

Identification of Pigments from Jujube Fruit Skin

[Objective]The aim was to identify the composition of pigments from Jujube fruit skin.[Method]Pigments were extracted from＇Lubei Dongzao＇,＇Lajiao Zao＇,＇Chengwu Dongzao＇,＇Dabailing＇and identificated by using high performance liquid chromatography-mass spectrometry（HPLC-MS）.[Result]The results showed that eight flavanols and four to five flavonols were detected,no anthocyanins was detected.The contents of flavonoids were differnt in four varieties.The contents of flavanols（11 mg/g） and flavonols（1.78 mg/g） in＇Dabailing＇ were one-time higher than other varieties.Quercetin 3 rutinoside was the major flavonol.[Conclusion]The research provided theoretical basis for further study on mechanism of Jujube pigment turnning into the red.

野地瓜茎正丁醇萃取物中主要抗氧化活性成分的筛选

探清野地瓜茎不同极性萃取物的抗氧化活性,筛选并鉴定抗氧化活性较高萃取物的主要化学成分。通过系统溶剂法对野地瓜茎提取物进行萃取,获得石油醚、二氯甲烷、乙酸乙酯、正丁醇相提取物及剩余上层被萃取水相提取物;采用1,1-二苯基-2-三硝基苯肼(DPPH)自由基清除能力、2,2’-联氮基-双-(3-乙基苯并噻唑-6-磺酸)二铵盐(ABTS)自由基清除能力和总还原力(TRPA)试验综合评价其不同极性萃取物的抗氧化活性;结合在线高效液相色谱—质谱—二苯基三硝基苯肼(HPLC-DAD-ESI/MS n-DPPH)快速筛选并鉴定活性较高萃取物中的抗氧化活性成分。结果表明:正丁醇萃取物具有较强的抗氧化活性(P<0.05),随着质量浓度的增大呈明显的剂量依赖效应,正丁醇萃取物对DPPH自由基、ABTS自由基清除能力的半数抑制浓度(IC 50)分别为(23.28±0.21),(76.30±1.13)μg/mL。经液相色谱、质谱、文献报道和对照品的综合分析,从野地瓜茎正丁醇萃取物中筛选的3种抗氧化活性化合物为5-O-咖啡酰奎宁酸、3-O-咖啡酰奎宁酸和4-O-咖啡酰奎宁酸。

High Performance Liquid Chromatography-Electrospray Ionization-Mass Spectrometric Analysis of Bilobalide and Ginkgolides in Ginkgo biloba L. Leaves

The ginkgo terpenoids including bilobalide and ginkgolides are the main pharmaceutical components in the leaves or extracts of Ginkgo biloba L. In this paper, the analysis of bilobalide and ginkgolides in leaves of Ginkgo biloba L. by high performance liquid chromatography (HPLC)-electrospray ionization (ESI)-mass spectrometry (MS) was carried out. The separation was performed on Inertsil ODS3 column with methanol-water (36:64) as mobile phase, with 1 mL·min -1 of flow rate at 35℃. Then the mass spectrum analysis was conducted by ZMD micromass electrospray ionization (ESI)-mass spectrometer (MS). The HPLC total ion chromatogram and selected ion chromatogram (with 325, 407, 423, 439 of m/z) of the sample and ESI-/MS mass spectra of the peaks in the chromatograms were obtained. So bilobalide, ginkgolide A, B, C and J in Ginkgo biloba L. leaves were identified. The method is easy and rapid, with a good accuracy.

HPLC-ESI-MS法测定大鼠脑组织中神经递质L/D-丝氨酸的含量

建立一种检测大鼠脑组织中L-丝氨酸和D-丝氨酸的高效液相色谱—电喷雾离子化—质谱联用技术（HPLC-ESI-MS）的测定方法.大鼠脑组织样品匀浆及离心后,取上清液并加入Marfey试剂对样品中L/D-丝氨酸进行衍生化.HPLC流动相为甲酸铵和乙腈,梯度洗脱;质谱采用电喷雾离子源,在负离子模式下进行定性定量分析.结果显示,L-丝氨酸和D-丝氨酸在22 min内得以分离,在2.5～500 ng/mg和1.2～250 ng/mg浓度范围内分别与各自的色谱峰面积呈良好线性关系;L/D-丝氨酸的最低定量限分别为2.5 ng/mg和1.2 ng/mg,方法回收率均在81％～89％％范围内.本法具有省时快速,灵敏度和选择性高等优点.将此法运用于成年和老年大鼠海马及皮层中L-丝氨酸和D-丝氨酸含量测定,结果表明,与成年鼠相比,老年鼠海马和皮层中L-丝氨酸的含量基本不变,而D-丝氨酸含量则明显减少,提示D-丝氨酸的变化与正常的衰老过程密切相关.

Detection of 36 antibiotics in coastal waters using high performance liquid chromatography-tandem mass spectrometry

Among pharmaceuticals and personal care products released into the aquatic environment, antibiotics are of particular concern, because of their ubiquity and health effects. Although scientists have recently paid more attention to the threat of antibiotics to coastal ecosystems, researchers have often focused on relatively few antibiotics, because of the absence of suitable analytical methods. We have therefore developed a method for the rapid detection of 36 antibiotic residues in coastal waters, including tetracyclines （TCs）, sulfanilamides （SAs）, and quinolones （QLs）. The method consists of solid-phase extraction （SPE） and liquid chromatography-tandem mass spectrometry （LC-MS/MS） analysis, using electrospray ionization （ESI） in positive mode. The SPE was performed with Oasis HLB and Oasis MCX cartridges. Chromatographic separation on a Cr8 column was achieved using a binary eluent containing methanol and water with 0.1% formic acid. Typical recoveries of the analytes ranged from 67.4% to 109.3% at a fortification level of 100 ng/L. The precision of the method, calculated as relative standard deviation （RSD）, was below 14.6% for all the compounds. The limits of detection （LODs） varied from 0.45 pg to 7.97 pg. The method was applied to detemaine the target analytes in coastal waters of the Yellow Sea in Liaoning, China. Among the tested antibiotics, 31 were found in coastal ＇waters, with their concentrations between the LOD and 212.5 ng/L. These data indicate that this method is valid for analysis of antibiotics in coastal waters. The study first reports such a large number of antibiotics along the Yellow Sea coast of Liaoning, and should facilitate future comprehensive evaluation of antibiotics in coastal ecosystems

Determination of Sulfadimidine in Royal Jelly by C_(18)-functionalized Magnetic Silica Nanoparticles Solid Phase Extraction-High Performance Liquid Chromatography-Tandem Mass Spectrometry

[Objective] This study aimed to develop a method of C_18-functionalized magnetic silica nanoparticles solid phase extraction-high performance liquid chro- matography-tandem mass spectrometry for the determination of sulfadimidine in royal jelly. [Method] The royal jelly samples were pretreated by MCX SPE column and C_18-functionalized magnetic silica nanoparticles, and the purified samples were de- tected by HPLC-MS/MS. [Result] The detection method showed a good linear rela- tionship in the range of 5-80 ugkg （r=0.993 1）. The recovery ranges were between 93%- 104% with the relative standard deviations （RSD） below 11.3%. [Conclusion] Combined with automation equipment, the method is simple, fast, time-saving, and easy to real- ize the automation of sulfadimidine in the royal jelly samples before determination.

Quick valence analysis method of vanadium toward accurate toxicity assessment of vanadium-containing hazardous wastes

In order to develop a quick, efficient and sensitive valence analysis method of vanadium(Ⅴ), the highperformance liquid chromatography(HPLC) was utilized to separate and quantify EDTA-complexed Ⅴ(Ⅲ), Ⅴ(Ⅳ) and Ⅴ(Ⅴ) ions. The influence of EDTA, TBAOH, solution pH and organic modifier on retention behavior of V-EDTA complexes was investigated. Complexed Ⅴ(Ⅲ), Ⅴ(Ⅳ) and Ⅴ(Ⅴ) ions can be separated and quantified in 5 min, with detection limits of 0.04 mg/L Ⅴ(Ⅲ), 0.07 mg/L Ⅴ(Ⅳ), and 0.06 mg/L Ⅴ(Ⅴ), respecti vely. The established method is applied to analyzing the hazardous waste of V-Cr-bearing reducing slag and results demonstrate 49.94% of its Ⅴ element to be toxic Ⅴ(Ⅴ). This work opens a new avenue for quick and accurate toxicity assessment of hazardous wastes containing multivalent heavy metals.

A Study on Triacylglycerol Composition and the Structure of High-Oleic Rapeseed Oil

The composition of fatty acids in triacylglycerides （TAGs） and their position on the glycerol backbone de- termine the nutritional value of vegetable oil. In this study, gas chromatography and high-performance liquid chromatography-tandem mass spectrometry （HPLC-MS/MS） were used to analyze the compo- sition and distribution of fatty acids in TAGs of different rapeseed oils. Our results show the content of oleic acid in higb-oleic-acid rapeseed oil to be about 80%. In terms of the number of acyl carbon atoms （CN）, TAGs with CN52-54 were most abundant, with a maximum concentration at CN54 （80%）. The main type of TAG was oleic-oleic-oleic （OOO）, accounting for 71.75%, while oleic-oleic-linoleic （OOL） accounted for ？.56%, oleic-oleic-linolenic （OOLn） accounted for 4.81%, and stearic-oleic-oleic （SO0） accounted for 4.74%. Oleic acid in high-oleic-acid rapeseed oil was distributed in the following order of preference： sn-2 〉 sn-1/3. In high-erucic-acid rapeseed oil, however, oleic acid was enriched at the sn-1/3. These data show that the content of oleic acid can be as high as about 80% in high-oleic-acid material. This finding suggests that high-oleic-acid rapeseed oil has high nutritional value.

Analysis of phospholipids in microalga Nitzschia closterium by UPLC-Q-TOF-MS

Precise structural identification of phospholipids in the microalga Nitzschia closterium has been established using ultra performance liquid chromatography-electrospray ionization-quadrupole-time of flight-mass spectrometry (UPLC-ESI-Q-TOF-MS) for direct analysis of total lipid extracts.Mass spectrometry was performed in reflective time-of-flight using electron spraying ionization in negative mode.Phospholipid molecular species identification was based on the characteristic product ions and neutral loss yielded by different phospholipids under ESI-MS/MS mode.The molecular species were confirmed by the carboxylate anions produced by phospholipids in negative mode;the regiospecificity of the two acyl chains was determined from the ratio of sn-1 to sn-2 carboxylate anion abundances.As a result,18 lipid molecular species were identified for the first time in this microalga,comprising seven phosphatidylcholines (PC),two phosphatidylethanolamines (PE),two phosphatidylinositols (PI),and seven phosphatidylglycerols (PG).Lipid standards of PC,PE,PI,and PG were added to the total lipids as internal standards for semiquantitative analysis,revealing concentrations of phospholipids in this species between 0.09 and 3.37 nmol/mg.This method can produce a full structural profile of intact phospholipid molecular species and can be used for study of the physiological and ecological functions of lipids by monitoring their individual changes over time.

Differentiating Trachemys scripta elegans Shell Glue from Chinemys reevesii Shell Glue by UPLC-QTOF/MS Coupled with Binary Compare Tool of UNIFI

Objective This study was conducted to develop an method for identification of Trachemys scripta elegans(Ba Xi Gui,巴西龟)shell glue from Chinemys reevesii(Zhong Hua Cao Gui,中华草龟)shell glue.Methods In this research,an ultra-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry(UPLC-QTOF/MS)method coupled with Binary Compare tool of UNIFI software was validated to differentiate Trachemys scripta elegans(Ba Xi Gui,巴西龟)shell glue from Chinemys reevesii(Zhong Hua Cao Gui,中华草龟)shell glue.The gelatins were digested enzymatically into peptides using trypsin.The UPLC-QTOF/MS data of the trypsin digested samples was subjected to Binary Compare of UNIFI software in order to screen out the unique peptides.PEAKS■Studio software was utilized to identify the sequence of the marker peptides.Results It was found that m/z 641.3 was the marker peptide in samples of Trachemys scripta elegans(Ba Xi Gui,巴西龟)shell glue,and m/z 649.3 was the marker peptide in samples of Chinemys reevesii(Zhong Hua Cao Gui,中华草龟)shell glue,with possible amino acid sequence of GEAGPSGPAGPTGAR and GESGPSGPAGPTGAR respectively.Conclusions The results will be helpful for the differentiating between these 2 gelatins,and it can be also used for quality control of Tortoise shell glue(Gui Jia Jiao,龟甲胶).

Mass Spectrometric Characterization of a Thermolabile Metabolite of Camazepam

Incubation of camazepam [3-(N,N-dimethyl) carbamoyloxy-7-chloro-1- methyl-1,3-dihydro-5-phenyl-2H-1,4-benzodiazepin-2-one] with rat liver microsomes and cofactors produced a 3-(N-methyl-N-hydroxymethyl) carbamoyloxy derivative as the most abundant metabolite.This metabolite was thermally unstable and was isolated from a metabolite mixture by normal-phase High-Performance Liquid Chromatography.Its struc- ture was established by chemical ionization and ^(252)Cf plasma desorption time-of-flight mass spectral analyses.

Changes of Metabolites and Macro- and Micro-elements in Hungarian Potatoes under Organic and Conventional Farming

To study the effect of cultivation system （conventional and organic） on potato tuber components, 42 parameters （anti-nutritives, micro- and macro-elements and 23 metabolites） were studied in three multi-resistant Hungarian potato varieties for three years in 2007-2009. Discriminant analysis of data proved that all investigated factors （farming technology, genotype and season/year） had significant effect on metabolites. Reversed phase high performance liquid chromatographic （HPLC-DAD, HPLC-MS） and elemental analysis methods have been adapted to quantify the major components, i.e., steroidal alkaloids, nitrite, nitrate, sugars, amino acids and micro-elements, in potato tubers. The absolute amount and changes of tuber components were influenced differentially by the technology, genotype and season in a complex manner. Any examined component, except nitrate content, was found to be significantly higher or lower consistently in relation to the production practice （organic or conventional） during the three years trials. Under the examined circumstances, no consequent positive effect of organic fanning on the total amount of anti-nutritive components, vitamins or micro- and macro-elements of potato tubers could be proven.

Determination of Forechlorfenuron Residue in Fruits and Vegetables by QuEChERS Extraction and HPLC-MS/MS

[Objective] A quick extraction method of QuEChERS-HPLC-MS/MS was established to determine forechlorfenuron in fruits and vegetables. [Method] Fruits and vegetables were extracted with 0.1% acetic acid of acetonitrile solution and pu- rified by QuEChERS, and then forechlorfenuron residues were determined by HPLC- MS/MS. [Result] The limits of detection （LODs） and low determination limit （LOQ） for the forechlorfenuron was 1.0 vg/kg and 5.0 pg/kg in fruits and vegetables, re- spectively. Regression equations of these hormones had a good linear relationship （FF〉0.999） within 2.0-100.0 vg/L. The average recoveries of forechlorfenuron was in the range of 72.0-115. 0% with the coefficients of variation between 1.5% and 9.8% at the spiked levels of 10.0-500.0 μg/kg. [Conclusion] The method can be applied for the determination of the forechlorfenuron in fruits and vegetables.

Removal of Pharmaceutically Active Compounds in Sequencing Batch Reactor

Biological treatment efficiency of six pharmaceutical compounds （acetazolamide, metronidazole, opipramol, piracetam, salicylamide and tinidazole） was evaluated using lab-scale Sequencing Batch Reactor （SBR）. Comparative biological degradation processes of two types of activated sludge from municipal and pharmaceutical industry sewage treatment plants were examined. Three different organic loadings （0.05 g COD/g MLSS.d, 0.1 g COD/g MLSS.d and 0.2 g COD/g MLSS-d） and reaction time on the efficiency of Active Pharmaceutical Ingredient （API） decomposition were examined. Chemical oxygen demand, non-purgeable organic carbon as well as ammonium nitrogen contents were monitored by standard methods. Percentage of API decomposition was analysed by High Performance Liquid Chromatography （HPLC）. The overall API removal efficiency was strictly dependent on the type of activated sludge origin. The main biodegradation products were identified using HPLC-MS,1H NMR and 13C NMR methods as e.g. （{4-[3-（5H-dibenzo[b,f]azepin-5-yl]piperazin-l-yl}methanamine） and （2-amino-1,3,4-thiadiazol-5-sulfonamide） for opipramol and acetazolamide respectively.