Study on the Thermal Degradation Behavior of Tanshinones during the Process of Reflux Extraction

用甲醇作提取溶剂,在回流条件下考察了从丹参药材中提取丹参酮类有效成分的过程中,隐丹参酮、丹参酮I及丹参酮IIA等三种丹参酮的热降解行为。结果表明,回流提取过程中所考察的三种丹参酮均发生严重的热降解,降解速率:丹参酮IIA>丹参酮I>隐丹参酮,其热降解均具有零级反应动力学特征;同时,回流提取过程中丹参酮的热降解是在丹参酮共萃物存在下发生的。Thermal degradation behavior of cryptotanshinone,tanshinone I and tanshinone IIA has been studied during the process of reflux extraction of tanshinones from Salvia miltiorrhiza Bge.with methanol as extracting solvent.The obtained results showed that the thermal degradation of cryptotanshinone,tanshinone I and tanshinone IIA occurred obviously during reflux extraction in the order of degradation rate:tanshinone IIA>tanshinone I>cryptotanshinone,and their thermal degradation was featured with zero order reaction;meanwhile,it was under the existence of other components coextracted with tanshinones that the thermal degradation of cryptotanshinone,tanshinone I and tanshinone IIA occurred.国家自然科学基金重点项目(20235020

Ultrasound-assisted Extraction of Tanshinones from Analytical Samples of Salvia miltiorrhiza Bge.

为了提取丹参分析样品中隐丹参酮、丹参酮I及丹参酮IIA等有效成分,建立了以CH3OH-CH2Cl2为提取溶剂的超声波辅助提取法。优化的提取条件是,液/固比:133.3 mL/g,提取溶剂组成:φ(CH2Cl2)=0.2,提取时间:8 min。与几种常规提取法(如甲醇回流法、CH3OH-CH2Cl2室温浸取法)相比较,超声波辅助提取法具有提取时间短、丹参酮提取量高等优点,适用于丹参中隐丹参酮、丹参酮I及丹参酮IIA同时测定的样品前处理。An ultrasound-assisted extraction method for cryptotanshinone,tanshinone I and tanshinone IIA from analytical samples of Salvia miltiorrhiza Bge.was established.The optimal extraction conditions were obtained as follows:φ(CH_2Cl_2)=0.2 CH_3OH-CH_2Cl_2 as extracting solvents,8 min of extraction time and 133.3 mL/g of extracting solvent-to-sample ratio.Compared with conventional methods,such as methanol reflux extraction and CH_3OH-CH_2Cl_2 macerating at room temperature,the method of ultrasound-assisted extraction has the advantages of short extraction time and high efficiency for extracting tanshinones,which suggests that it is suitable for sample pretreatment in the simultaneous determination of cryptotanshinon,tanshinone I and tanshinone IIA in Salvia miltiorrhiza Bge..国家自然科学基金重点项目(20235020

Analysis of Diterpene Quinones in Danshen(Salvia Miltiorrhiza Bunge) by HPLC-ESI/TOFMS

采用高效液相色谱-电喷雾飞行时间质谱(HPLC-ESI/TOFMS)联用技术,研究4种丹参酮的分子结构与裂解规律间的关系,并对丹参酮中的脂溶性成分进行鉴定。采用反相C18色谱柱,以甲醇-0.1%乙酸+5mmol.L-1乙酸铵溶液为流动相,二元等度洗脱。通过与电喷雾飞行时间质谱联用,获得丹参中脂溶性成分的精确相对分子质量和分子式,采用质谱碰撞诱导解离技术获得各化合物碎片的裂解信息,并对丹参中的16种丹参酮类化合物进行了初步鉴定。研究结果表明,高效液相色谱-电喷雾飞行时间质谱联用技术能够简便、快速、有效地鉴别丹参中的丹参酮类化合物。The diterpene quinone components in lipid soluble fractions of Danshen were studied by HPLC-ESI/TOFMS.The lipid solubles were extracted with a mixture of chloroform and methanol(1∶4,V/V).The extract was dried by a gentle stream of nitrogen,and the residue was diluted in methanol for analysis.HPLC was performed on a reversed-phase C18 column using isocratic elution with a mixture of methanol and water with the addition of 0.1% acetic acid and 5 mmol·L-1 ammonium acetate.Accurate molecular weights of individual tanshinones were determined through ESI-TOF/MS on-line detection.The molecular formula and TOFMS fragmentation behavior of each compound were obtained through off-line analysis under different collision induced dissociation(CID) energies.Combining literature information with the observed data,16 tanshinones in lipid-soluble fractions of Danshen were tentatively identified in a run.The method demonstrates high potential as a rapid and effective method for the preliminary structural screening and speciation of bioactive tanshinone components in Danshen or other herbal extracts.国家自然科学基金“面上项目”(20675021);; 青岛共建生物医药研发测试中心项目(LS-05-KJZX-76)资

中药质量控制与安全性评价中的分析化学

本文论述了中药现代化实施中进行质量控制的“5P”(GAP、GCP、GLP、GMP、GSP)系统工程 ;结合本实验室近年来以“5P”指导中药质量控制与安全性评价所做的一些工作 ,阐明了将分析化学应用于中药质量控制与安全性评价的策略与方法 ,提出了分析化学在中药现代化系统工程及重大科学问题的解决中所能发挥的重要作用

Rapid Quality Control of Licorice in Its GAP Research

目的　建立甘草 GAP过程中的快速质量检验方法 ,为甘草药材的快速质量检测提供方法依据。方法　提出甘草中水溶性有效物质群的概念并建立其含量的比色测定方法。以甘草酸作为定量的标准物质 ,采用香草醛 -浓硫酸试剂作显色剂 ,用便携式小型光谱仪于 5 6 0 nm处检测。结果　回归方程为 Y=1.174 7C+0 .0 873,相关系数 r=0 .970 5 (n=3) ,回收率为 92 %～ 99% ,在 0 .0～ 0 .96 mg/m L 范围内仪器读数与甘草酸浓度呈线性关系。结论　该方法简单、快速、廉价 ,能够准确地反映甘草质量的优劣 ,适合在准确度要求相对较低的甘草生产基地推广使用Objective To develop a rapid method for the quality control of licorice in its GAP research.Methods Water-soluble triterpenoid saponins were defined as the active fraction in licorice and a colorimetric method using LED-based portable device has been developed for the first time to measure the content of this active fraction. The method was based on the specific color reaction occurring between triterpenoid saponins and vanillin-sulfuric acid reagent. Visible light absorption of 560 nm was chosen as the detection wavelength.Results The operating calibration curve(Y=1.174 7C +0.087 3 mg/mL) was found to be linear at the range of 0.0～0.96 mg/mL glycyrrhizic acid in water (r=0.970 5). The recovery is 92～99%.Conclusion The method is simple, rapid and low-cost and is recommendable to evaluate the quality of Glycyrrhiza uralensis Fisch. in its GAP research.内蒙梁外甘草 GAP研究与开发;; 国家自然科学基金 2 0 0 3重点项目 ( 2 0 2 3 5 0 2 0

Determination of trace elements in seawater and application for identification of source of trace metal contaminants

利用电感耦合等离子体质谱(ICP-MS)研究了胶州湾及莱州湾这两个海域中痕量元素污染水平,发展了ICP-MS海水环境中痕量元素的测定方法,同时找出海水环境中具有保守性的数种元素作为污染示踪元素。达到对于海水环境中痕量污染物被动示踪的目的。对18个真实样品进行了识别率试验,识别率可达90%以上,在选取3个海水样品及1个河水样品混合后的模拟分担率实验,也取得了满意的结果,其误差平均值仅有1.17%。Inductively coupled plasma-mass spectrometry(ICP-MS) was developed into an accurate and sensitive technique for the multi-element determinations in a range of sample matrices.The seawater samples in Lai zhou Bay and Jiaozhou Bay as a case was studied.The distribution of trace elements in seawater can be used in the source fingerprints for the identification of seawater samples from different locations.The probability of success for the source identification by the technique is better than 90%.The feasibility of trace metals in seawater as a tracer for the tracking of pollution sources has been evaluated.Combined with the chemo-metric analysis,3 seawater and 1 river samples were mixed,the error is only 1.17%.国家863项目(2005AA635250

The Determination of Polycyclic Aromatic Hydrocarbons in Sediments with ASE/GC-MS

建立了用加速溶剂萃取技术提取含硫沉积物中痕量多环芳烃的可靠方法,优化了不同萃取剂,不同提取程序等萃取条件,研究了沉积物中的硫化物对色谱分离的影响。15种多环芳烃的检出限为0.09~1.34ng/g,相对标准偏差(RSD,n=6)为12.5%~23.9%,15种多环芳烃的低浓度加标回收在74%~138%之间。高浓度加标回收率除吲哚芘为62%外,其余都在80%~122%之间。基本上达到了痕量分析的要求。用该方法分析山东半岛近岸海域沉积物中多环芳烃的含量,测得15种PAHs的总量为273~579 ng/g。与其它地区沉积物中多环芳烃含量相比,属轻/中度污染。An accelerated solvent extraction method for the extraction of polycyclic aromatic hydrocarbons(PAHs) in sediments was developed.The extraction conditions such as extraction solvent and program were optimized.The effects of sulfide on chromatographic separation were studied.The detection limits for the fifteen PAHs were 0.09-1.34 ng/g,and the relative standard deviations(RSDs) ranged from 12.5% to 23.9%.The recoveries of high level concentration ranged from 62% to 122% and those of low level concentration ranged from 74%-138%.The contents of PAHs in sediment samples collected in the coastal regions off the Shandong peninsula,China were analyzed by this method.The PAHs in these samples ranged from 273 ng/g to 579 ng/g.Overall,the PAHs levels were comparable to those reported in the literature for sediment samples collected from similar environments around the world.国家高技术研究发展计划(863)基金项目(2003AA635180);; 青岛科技将才计划基金项目(04-3-J.J-11

Distribution Characteristics of Polycyclic Aromatic Hydrocarbons in Seawater from the South Yellow Sea

2007年9月进行了2007南黄海海洋环境调查,并采集各个调查站位的表层、中层、底层海水及表层沉积物。利用液-液萃取法对采集到的样品进行前处理,并用气相色谱-质谱法检测海水中的多环芳烃。结果显示,监测站位中表层海水中总多环芳烃的含量范围是15.76--233.39ng/l,南黄海中部海水中多环芳烃的组成以2环的萘为优势组分;各种多环芳烃的含量与国际生物学组织或国家制定的评价水生生物暴露于水体的安全食用标准相比虽未超标,但个别组分如荧蒽的含量已达到生态毒理评价标准。Marine surface sediments and sea water samples from the surface, middle and bottom layers were collected from the South Yellow Sea of China.The samples were pretreated by liquid-liquid extraction and the 16 polycyclic aromatic hydrocarbons (PAHs) in the samples were determined by gas chromatography-mass spectrometry (GC-MS).The results show that the range of total PAHs is 15.76～233.39 ng/L in surface water and PAHs in the water samples from central South Yellow Sea are dominated by naphthalene (2 rings).Content of PAHs compounds don′t exceed the safety guidelines proposed by International Biology Organization or governments, but the individual compound, such as fluoranthene content has reached eco-toxicological evaluation criteria.国家海洋局节能减排专项资助;中国海监技术支撑项目资助;海洋公益性项目资助(200705011

固相微萃取-气相色谱-质谱联用测定海水和沉积物间隙水中的痕量多环芳烃

建立了固相微萃取(SPME)与气相色谱-质谱(GC-MS)联用同时测定海水中16种多环芳烃的分析方法,研究了萃取时间、盐度条件的影响．同时用SPME的方法研究了海水中的溶解有机物(DOM)对多环芳烃萃取的影响．计算出不同DOM浓度下多环芳烃KDOM与KOW的关系: CDOM=5 mg／L时,logKDOM=0．7944KOW+0．773(R2=0．91)．CDOM=10 mg／L时,logKDOM= 0．7905KOW+0．668(R2=0．97);CDOM=30 mg／L时,logKDOM=0．714KOW+1．0407(R2=0．91)．该法对16种多环芳烃的检出限为0．1-3．5 ng／L,相对标准偏差(RSD,n=5)为4％-23％．用该法分析海洋环境中的痕量多环芳烃,16种多环芳烃的平均回收率为88.2±20．4％,方法快速、灵敏、简单,适用于快速分析海水和沉积物间隙水样中的痕量多环芳烃．国家高技术研究发展计划(863)(批准号:2003AA635180);; 青岛科技将才计划(批准号:04-3-JJ-1)资助项

Determination of Salvianolic acid B by High Performance Liquid Chromatography with Fluorescence Detection

建立了丹酚酸B的高效液相色谱-荧光检测含量测定方法。色谱条件为:BACKMANODS柱( 4 6mmi.d .×2 5 0mm ,5 μm) ,以甲醇-0 5 %冰醋酸水溶液为流动相,流速为1 0mL/min ;荧光检测波长λEX=3 3 8nm ,λEM=44 3nm ;进样量5 μL。丹酚酸B进样量为0 12～1 2 μg时,其质量与峰面积呈良好的线性关系(r=0 9998) ;加样回收率为98 6%～10 8% ;最低检测限为0 0 13 μg/mL。该法具有更高的灵敏度,为丹酚酸B的药代动力学研究提供基础A new method for the determination of Salvianolic acid B by high performance liquid chromatography with fluorescence detection has been established.The column used was BACKMAN C 18 (4.6mm i.d.×250mm,5μm);The mobile phase was methanol-0.5% acetic acid solution with gradient condition at a flow rate of 1.0mL/min;The fluorescence detector was operated at λ EX =338nm and λ EM =443nm with the injection volume of 5μL.The result proved that Salvianolic acid B has a good linearity in the range of 0.12μg to 1.2μg with the correlation coefficient of 0.9998;The recoveries were 98.6%～108%;The limit of detection is 0.013μg/mL.This method has a higher sensitivity and can be used in the study of pharmic metabolize.国家自然科学基金重点项目(2 0 2 350 2 0