气相色谱-质谱联用法测定烟火药剂中的苦味酸

建立了气相色谱-质谱联用测定烟火药剂中的苦味酸含量的分析方法。根据烟火药剂的组成特点,在前处理技术方面做出了优化,改进了对氯化衍生产物-氯化苦的萃取方法,将正交实验应用于碳粉中脱附苦味酸的处理步骤,对升温、冲洗、超声波和置换等4个脱附条件做了考查。结果表明:苦味酸的质量浓度在1.0~50.0μg/mL时与色谱峰面积之间线性关系良好(相关系数r=0.9998);仪器检出限(S/N=3)为0.043 mg/kg;方法检出限(3.143δ)为0.543 mg/kg。对3类烟火药剂样品进行5,20,50μg/g 3个不同浓度水平的添加回收,回收率为83.0%~90.0%。     

凝胶渗透色谱-高效液相色谱-串联质谱法同时测定烟草中3种抑芽剂残留

建立了用凝胶渗透色谱净化-液相色谱-串联质谱分析烟草中3种抑芽剂残留的方法。卷烟中的待测抑芽剂组分用V(乙酸乙酯)∶V(环己烷)=1∶1超声提取后通过凝胶渗透色谱净化;凝胶色谱柱为Biobeads S-X3玻璃柱(50 g,400 mm×25 mm),流动相为V(乙酸乙酯)∶V(环己烷)=1∶1溶液,流速5 mL/min;收集第10~25 min流出的液体用液相色谱色谱-三重四极杆串联质谱仪测定。在0.5~100 ng/mL的质量浓度范围内,各种抑芽剂标准溶液的线性相关系数均大于0.99。在样品中添加3种抑芽剂(添加水平为5,20,100μg/kg)的混合标准溶液,平均回收率在86.2%~108.4%之间,3种抑芽剂的RSD在1.1%~7.5%之间;方法的检测限在0.01~0.06μg/kg之间。     

超声辅助提取-固相萃取土壤中头孢菌素C的高效液相色谱法定量检测

建立了一种采用超声辅助提取(UAE)、强阴离子交换固相萃取(SAX-SPE)净化、高效液相色谱(HPLC)测定土壤中残留头孢菌素C(CPC)简单、快速方法。 样品以超纯水为提取剂,超声辅助提取,SPE柱子以3 mL甲醇和3 mL水活化,采用5 mL的10%甲醇水溶液作为淋洗液,2 mL的5%甲酸水溶液/甲醇溶液(体积比50：50)进行洗脱,高效液相色谱紫外检测器(HPLC-PDA)测定,检测波长λ=254 nm,柱温30 ℃ ,流动相为0.1%甲酸水溶液/甲醇溶液(体积比95：5)对土壤中不同加标浓度的CPC进行检测,方法的回收率在77.9%~98.9%,标准偏差范围为5.0%~6.3%(n=5),方法检出限(LOD)为340.4 μg/kg,定量限(LOQ)为1126.8 μg/kg。 同时采用此方法检测分析新疆某药厂附近阳性土壤样品,不同批次土壤样品结果分别为:检出(低于定量限)、1532.1 μg/kg。     

土壤中多种有机磷及氨基甲酸酯类农药残留量的气相色谱-质谱法测定

建立了气相色谱-质谱法测定土壤中12种有机磷和氨基甲酸酯类农药残留分析方法。以丙酮-石油醚(4∶1,V/V)为提取剂,采用超声波提取土壤中农药残留,经弗罗里土层析柱净化,气相色谱-质谱(选择离子模式)法同时测定了土壤中多种有机磷和氨基甲酸酯类农药。该法对0.1μg/mL和0.5μg/mL两个浓度添加水平的回收率分别为70.1%~119.0%和78.1%~119.1%,相对标准偏差分别为6.30%~9.80%和5.20%~8.23%。     

双波长UPLC同时测定桃金娘根中没食子酸和鞣花酸

建立了超高效液相色谱(UPLC)结合二极管阵列检测器(PDA)同时测定桃金娘根中没食子酸和鞣花酸的方法。样品经过甲醇超声提取,过滤,蒸干甲醇,残渣用二甲基亚砜定容。采用Waters BEH C18色谱柱(2.1×100 mm1.7μm),以乙腈-0.2%H2PO4溶液为流动相进行梯度洗脱,流速0.25 m L/min,检测波长为271 nm和253 nm。没食子酸在0.686~68.600μg/m L,鞣花酸在0.504~50.373μg/m L浓度范围内呈良好线性关系,相关系数分别为0.9999,0.9999;样品加标平均回收率分别为97.2%~99.0%、96.2%~98.9%;没食子酸和鞣花酸峰面积的RSD分别为1.1%和1.9%,迁移时间RSD为0.9%和1.3%;检出限分别为0.45和0.23 ng/m L。     

HPLC法同时测定茶叶中多酚、咖啡因和维生素C

采用高效液相色谱法(HPLC)建立了同时检测茶叶中咖啡因、没食子酸、烟酸、绿原酸和维生素C含量的方法。色谱条件为:Lichrospher C18反相柱(250 mm×4.6 mm,5μm),以甲醇和0.2%甲酸水溶液为流动相,梯度洗脱,流速为1.0 m L/min,测定温度为35℃,检测波长为275nm。咖啡因、没食子酸、烟酸、绿原酸和维生素C在0~70μg/m L浓度范围内被测组分浓度对被测组分面积呈良好的线性关系,其相关系数均在0.9995以上;加标回收率在95.10%~104.82%之间;相对标准偏差均在1.3%~5.5%之间。该方法可作为评价茶叶及其相关产品的质量控制提供参考依据。     

高效液相色谱法检测溴化丁基胶塞中11种抗氧剂及游离硫的浸出量及迁移量

采用Inertsil ODS-SP C18(250×4.6 mm,5μm)色谱柱,以0.1%乙酸水-甲醇-乙腈为流动相,进行梯度洗脱,流速为1.0 mL/min,检测波长为277 nm。胶塞提取溶剂分别为无水乙醇和模拟药液。11种抗氧剂及游离硫的分离度均大于1.5;在2.47~54.51μg/mL浓度范围内,线性关系良好(R^2均大于0.999);检出限为0.021~0.403μg/mL;以无水乙醇为提取溶剂时,加标回收率为82.8%~115.3%,相对标准偏差为1.1%~6.1%;以模拟药液为提取溶剂时,加标回收率为62.9%~103.2%,相对标准偏差为1.4%~5.6%。该方法可用于包材相容性试验中实际样品的检测。     

超高效液相色谱法测定绿茶中5种儿茶素

建立了绿茶中儿茶素、表儿茶素、表儿茶素没食子酸酯、表没食子儿茶素和表没食子儿茶素没食子酸酯含量的超高效液相色谱紫外检测方法。样品采用70℃甲醇-水溶液热水浴下提取。色谱柱为Waters Acquity-BEH C18柱(1.7μm,50 mm×2.5 mm);流动相为乙腈和0.1%甲酸,采用梯度洗脱,乙腈洗脱浓度和时间为:9%(0 min)-9%(4 min)-12%(6 min)-25%(8 min)-9%(9 min)-9%(9.5 min);流速0.25 mL/min;柱温30℃;进样量10μL;检测时间9.5 min;二极管阵列检测器;检测波长278 nm。实验结果表明,在该色谱条件下,5种儿茶素能达到较好的基线分离效果,样品回收率在95.0%～105.0%之间,相对标准偏差(RSD)为1.7%～3.0%(n=5)。     

超临界二氧化碳流体萃取法测定玩具中15种致敏芳香化合物

该文以欧盟新玩具指令中限用或禁用的15种致敏芳香化合物为研究目标,研究了超临界二氧化碳萃取压力、温度、夹带剂等条件对萃取效率的影响,建立了超临界流体萃取/气相色谱-质谱联用仪测定玩具中15种致敏芳香化合物的分析方法。最佳萃取条件为:萃取温度50℃,压力300 bar,二氧化碳流速30g/min,夹带剂甲醇含量3%,动态萃取30 min,静态萃取30 min。萃取物经DB-17MS色谱柱分离后,采用质谱仪进行检测,内标法定量。15种化合物在0.02~60μg/mL范围呈良好线性,相关系数为0.993 2~0.999 9,检出限(S/N=10)为0.02~0.09μg/mL。该法检测聚丙烯(PP)、聚乙烯(PE)、丙烯腈-丁二烯-苯乙烯(ABS)塑料的回收率分别为79.6%~114.5%、75.0%~118.9%、72.7%~114.9%,相对标准偏差为3.2%~11.0%、0.6%~11.6%、3.5%~11.0%。建立的方法灵敏、环保,可用于玩具中致敏芳香化合物的检测。     

柱前衍生高效液相色谱法测定二乙醇胺脱氢产物亚氨基二乙酸和甘氨酸

以对甲苯磺酰氯(PTSC)为衍生剂,建立了柱前衍生高效液相色谱(HPLC)测定二乙醇胺脱氢产物中亚氨基二乙酸(IDA)和甘氨酸(Gly)含量的分析方法。IDA和Gly与衍生剂在碱性(pH 11)条件下于45℃反应15 min,进行柱前衍生,并利用高效液相色谱-质谱对衍生产物进行定性分析。衍生化产物采用VP-ODS色谱柱(200 mm×4.6 mm,5μm)分离,以0.03 mol/L醋酸铵溶液(pH 5.5)为流动相A、乙腈为流动相B(体积比为87∶13),进行等度洗脱,流速为1 mL/min,并采用配有紫外检测器的高效液相色谱仪测定,检测波长为235 nm。该法在IDA质量浓度为900~2 100 mg/L、Gly质量浓度为20~100 mg/L的范围内线性关系良好,相关系数(R2)均大于0.999。IDA和Gly的检出限(LOD)分别为0.089 7 mg/L和0.026 2 mg/L,加标回收率分别为98.7%~99.3%和98.0%~99.5%,相对标准偏差(RSD)分别为0.89%~1.23%和0.95%~1.11%(n=3)。该法具有反应条件温和、准确性高的特点,可用于工艺生产中IDA和Gly含量的测定。     

高速逆流色谱法分离制备中药诃子中的没食子酸

利用高速逆流色谱法从100 mg诃子醇提物中一次性分离制备得到8.6 mg没食子酸。通过分析型高速逆流色谱对5种溶剂系统进行筛选,确定以正己烷-乙酸乙酯-甲醇-水(体积比为1:5:1:5)为两相溶剂体系并放大到制备型上,以上相为固定相,下相为流动相,在主机转速850 r/min、流动相流速2 mL/min、检测波长254 nm的条件下进行分离制备,获得4个分离峰(组分Ⅰ、Ⅱ、Ⅲ、Ⅳ)。经高效液相色谱检测,按照面积归一法计算,其中组分Ⅲ的纯度达96.40%。经电喷雾电离质谱分析,并结合与没食子酸标准品的高效液相色谱测定结果的对比,确定组分Ⅲ为没食子酸。该方法简便、快速、重复性好,适合于诃子中没食子酸的分离制备。     

Reversed phase-HPLC for rapid determination of polyphenols in flowers of rose species

A rapid, simple, sensitive, robust, and improved HPLC method was developed and validated for determination of 10 polyphenols, namely gallic acid, catechin, epicatechin, rutin, m-coumaric acid, quercitrin, myricetin, quercetin, apigenin, and kaempferol in fresh flowers of Rosa bourboniana and R. brunonii and in both fresh flowers and marc (left after industrial distillation of rose oil) of R. damascena. Six polyphenols, gallic acid, rutin, quercitrin, myricetin, quercetin, and kaempferol, were detected and quantified in all extracts. The chromatographic separation of 10 polyphenols was achieved in less than 16 min by RP-HPLC (Phenomenex, Luna C18 (2) column, 5 microm, 250 mm x 4.6 mm) using linear gradient elution of water and acetonitrile (0.02% trifluroacetic acid) with a flow rate of 1 mL/min at lambda 280 nm. Standard calibration curves were linear in the range of 0.39-500 microg/mL. Good results were achieved with respect to repeatability (RSD <3%) and recovery (98.6-100.8%). The method was validated for linearity, accuracy, repeatability, LOD, and LOQ.     

HPLC法测定脂质体松萝酸中松萝酸的含量

建立了HPLC测定脂质体松萝酸中药物松萝酸的方法。以Kromasil C18反相色谱柱(250 mmⅹ4.6 mm,5μm)为分离柱,流动相组成为V(甲醇)∶V(磷酸盐缓冲液(pH 5.0))=7∶3,流速1 mL/min,紫外检测,波长284 nm。松萝酸在10~50μg/mL的范围内有很好的线性关系(r=0.9994)。加样回收率为100.1%±0.6%,RSD为0.54%±0.07%。本方法适用于脂质体松萝酸中药物松萝酸的测定。     

HPLC法测定怀菊花中没食子酸的含量

为建立HPLC法测定怀菊花中没食子酸含量测定方法,采用Agilent C18柱(150 mm×4.6mm,5μm),以V(甲醇)+V(超纯水+0.1%磷酸)=25+75为流动相,流量:0.5 mL·min1;柱温为25℃,检测波长:258 nm;进样量:10μL,进行测定。结果表明,回归方程为y=3.054 2 x-2.207 1,r2=0.999 1(n=6),线性范围0～20μg,平均回收率97.28%,RSD为3.39%。样品中没食子酸质量分数为3.17 mg/g。方法快速、简便、准确、重现性较好,结果可靠,可为怀菊花中没食子酸的质量评价提供依据。     

Simultaneous determination of catechins, rutin, and gallic acid in Cistus species extracts by HPLC with diode array detection

A simple high-performance liquid chromatography method using a diode array detector (DAD) is developed for the simultaneous analysis of five major catechins: (+)-catechin (C), (-)-epicatechin (EC), (-)-gallocatechin (GCT), (-)-epigallocatechin (EGC), (-)-epigallocatechin gallate (EGCG), and the phenolic plant metabolites gallic acid (GA) and rutin (RT) in lyophilized extracts of Cistus species. The optimal analytical conditions are investigated to obtain the best resolution and the highest UV sensitivity for the quantitative detection of catechins. The optimized conditions (acetonitrile-phosphate buffer 50mM, pH 2.5, gradient elution system on a C(18) reversed-phase column with a flow rate of 1 mL/min and UV absorbance at 210 nm) allowed a specific and repeatable separation of the studied analytes to be achieved. All compounds are successfully separated within 32 min. Calibration curves are linear in the 2-50 microg/mL range for GCT, C, and EGCG and in the 5-50 microg/mL range for GA, EGC, EC, and RT. The limit of detection values ranged from 0.24 to 0.74 microg/mL. The limit of quantitation limit values ranged from 0.77 to 1.94 microg/mL. The validated method is applied to the determination of the specific phytochemical markers GA, GCT, C, and RT in Cistus incanus and Cistus monspeliensis lyophilised extracts. The recovery values ranged between 78.7% and 98.2%. The described HPLC method appears suitable for the differentiation and determination of the most common catechins together with the glycoside rutin and the phenolic compound gallic acid and can be considered an effective and alternative procedure for the analyses of this important class of natural compounds.     

双水相萃取-高效液相色谱法测定酵母细胞中麦角固醇含量

建立了乙醇-水双水相萃取-高效液相色谱法测定酵母细胞中麦角固醇含量的分析方法。先使酵母细胞在KOH-乙醇溶液中于85℃~90℃回流皂化2 h,冷却后加入适量分相剂Na3PO4.12H2O使其形成双水相体系,经振摇萃取,麦角固醇进入乙醇相,萃取效率为95%~102%。用高效液相色谱法(HPLC)测定醇相中麦角固醇含量,采用DiamonsilTMC18色谱柱(200×4.6 mm,5μm),流动相为甲醇,流速为1.0 mL/min;紫外检测波长为281 nm,进样量为20μL。方法线性范围为30.15~2010μg/mL,检出限为1.3μg/mL;用其测得酵母细胞中麦角固醇含量为2.74 mg/g,RSD为2.1%(n=5),加标回收率为91.6%~96.9%。     

Antioxidant and antimicrobial attributes and phenolics of different solvent extracts from leaves, flowers and bark of Gold Mohar [Delonix regia (Bojer ex Hook.) Raf

This paper describes the antioxidant and antimicrobial activities and phenolic components of different solvent (absolute methanol, absolute ethanol, absolute acetone, 80% methanol, 80% ethanol, 80% acetone and deionized water) extracts of leaves, flowers and bark of Gold Mohar [Delonix regia (Bojer ex Hook.) Raf.]. The extract yields from leaves, flowers and bark ranged from 10.19 to 36.24, 12.97 to 48.47 and 4.22 to 8.48 g/100 g dry weight (DW), respectively. Overall, 80% methanol extract produced from the leaves exhibited significantly (P < 0.05) higher antioxidant activity, with high phenolic contents (3.63 g GAE/100 g DW), total flavonoid contents (1.19 g CE/100 g DW), inhibition of peroxidation (85.54%), DPPH scavenging capacity (IC(50) value 8.89 μg/mL) and reducing power (1.87). Similarly, this 80% methanol leaves extract also showed superior antimicrobial activity. HPLC analysis of the 80% methanol extracts for individual phenolics revealed the presence of gallic, protocatechuic and salicylic acid in leaves; gallic, protocatechuic, salicylic, trans-cinnamic and chlorogenic acid in flowers, and gallic acid in bark as the main (amount > 1.50 mg/100 g DW) phenolic acids. Besides, small amounts ( < 1.50 mg/100 g DW) of some other phenolic acids such as sorbic, sinapic, p-coumaric, m-coumaric, ferulic, caffeic, 3-hydroxybenzoic, 4-hydroxycinnamic and 4-hydroxybenzoic acids were also detected. The extracts of the tested parts of Gold Mohar, especially, the leaves, might be valuable for functional food and therapeutic applications.     

高效液相色谱-荧光分析法同时测定人体尿液中黄蝶呤与异黄蝶呤

建立了高效液相色谱-荧光法同时测定癌症病人尿液中黄蝶呤及异黄蝶呤的新方法。选择荧光检测波长λex=345nm,λem=420nm。以磷酸盐缓冲溶液(pH=7.5)-甲醇(体积比为98∶2)为流动相,流速1.0mL/min,黄蝶呤与异黄蝶呤含量分别在0.0013～0.945μg/mL及0.00017～0.118μg/mL范围内与色谱峰面积呈良好的线性关系,线性相关系数分别为0.9999和0.9996,检出限分别为0.5ng/mL和0.05ng/mL,加标平均回收率在86.2%～107.5%之间。方法应用于癌症病人尿样分析,取得了较好的结果。     

流动注射在线预富集-高效液相色谱法测定四种硝基类化合物

建立了以香烟过滤嘴纤维作吸附剂,在线固相萃取-高效液相色谱（SPE—HPLC）测定水中邻硝基苯甲酸、对硝基苯胺、邻硝基苯酚、3-氯硝基苯四种硝基类化合物的方法。邻硝基苯甲酸、对硝基苯胺、邻硝基苯酚、3-氯硝基苯分别在0．006～4．80、0．003～2．40、0．002～1．60、0．002～1．60mg／L范围内峰面积与浓度呈线性关系,相关系数分别为0．9994、0．9996、0．9997和0．9996;检出限（S／N=3）分别为1．0、0．8、0．6,0．6μg／L;富集倍数分别为28．2、176．6、172．1、153．3。该法用于河水中四种硝基类化合物的测定,回收率为85．41％～116．44％,相对标准偏差在1．1％～5．4％范围内。     

Microencapsulated mycelium-bound tannase from Aspergillus niger

Microencapsulated Aspergillus niger with mycelium-bound tannase activity was employed to investigate the esterification of propyl gallate from gallic acid and propanol in organic solvents. The effects of various organic solvents (log P:−1.0 to 6.6) on the enzymatic reactions showed that benzene (log P:2.0) was the suitable solvent, for which the conversion reached 26.8%. The optimum catalyst concentration and water concentration was found at 25 capsules in 10 mL of benzene and 0.04 g of water/capsule. The external mass transfer effect could be eliminated at stirring speeds of 180 rpm or higher. Both substrates 1-propanol and gallic acid had significant inhibition effects on the tannase activity. Maximum molar conversion (36.2%) was achieved with 9.1% (v/v) 1-propanol and 8 mM gallic acid and decreased with increasing amounts of substrates.