苦黄注射液中乙酸乙酯萃取物成分表征

用薄层分析、熔点测定、质谱、经外、核磁共振方法对苦黄注射液中酯溶性部分（乙酸乙要互可溶性部分）进行了成分分析,共鉴定了5种晶体,它们分别是大黄酚、大黄素甲醚、大黄酸、咖啡酸和没食子酸。     

苦黄注射液中挥发性成分总含量的测定

苦黄注射液是由国家卫生部批准生产的中药复方静脉注射液，属国家二类中药新药。处方由大黄、苦参、茵陈、柴胡等中药组成。具有清热利湿、疏肝褪黄的功能。临床上适用于因湿热内蕴而引起的病毒性黄疸型肝炎患者的退黄。药理研究表明，其挥发性成分为其有效活性成分之一。本文对苦黄注射液中挥发性成分的总含量加以测定，从而对苦黄注射液的质量控制提供了一个科学依据。     

GC/MS法研究苦黄注射液中挥发油成分

利用气相色谱-质谱联用装置分析了苦黄注射液中挥发油的化学成分及相对含量。共鉴定了55个化合物，其中以单萜和倍半萜为主，占已鉴定的挥发油种类的56．36％和3．63％，为挥发油的主要成分。     

中药大黄中羟基蒽醌类成分的分离

依据正交试验设计方法，研究了用乙醇和乙醚等溶剂分离中药大黄中羟基蒽醌类成分（蒽甙及游离羟基蒽醌类成分）及游离羟基蒽醌类成分的最佳分离条件，试验表明，乙醇的用量及回流次数对提取产率有很大影响，而回流时间的影响相对较小，100g大黄干粉的最佳分离条件是：用90mL95%乙醇浸润，再用150－175ml乙醇回流，回流3次，每次30－40min，即可较充分发将羟基蒽醌类成分总量的84％及游离羟基蒽醌类成分总量的82％提取出来。     

火焰原子吸收光谱法测定苦黄注射液及其中药材中五种金属元素

用硝酸和过氧化氢消化样品，通过基体改进剂，使用火焰原子吸收光谱法测定苦黄注射液及其中药材大黄、茵陈、柴胡、苦参中铜、铁、锌、钾和钠的含量。方法的回收率在92．6％～112．1％之间，相对标准偏差小于4％。     

石墨炉原子吸收光谱法测定苦黄注射液及其中药材中的铅和镉

应用石墨炉原子吸收光谱（GF-AAS）法测定了苦黄注射液及其生中药材中铅及镉量。试样用浓硝酸及过氧化氢消解。对仪器的工作条件,包括波长、光谱带宽、灰化温度及原子化温度,作了试验和优化。选用柠檬酸作为基体改进剂,对大黄、茵陈、柴胡、苦参及“苦黄”注射液等试样中的铅及镉量作了测定,分析结果的相对标准偏差均小于4．4％。按标准加入法作了回收率试验,测得值在96%～110％之间。     

反相高效液相色谱法测定大黄药材中游离及结合型蒽醌类衍生物的含量

建立了同时测定大黄药材中蒽醌类衍生物含量的RP HPLC法。色谱柱为HypersilC1 8柱 (2 5 0mm×4 6mmi.d .,1 0 μm) ,流动相为甲醇 乙腈 水 (3∶5∶2 ,磷酸调pH 2 .8) ,流速为 1 .0mL min ,柱温为 2 5℃ ,检测波长为 2 2 5nm。在此色谱条件下 ,各组分在 2 0min内均得到良好分离。平均回收率为 98.83 %～ 1 0 0 .9% ;相对标准偏差 0 .68%～ 1 .5 8%。     

茵栀黄注射液及其药材中5种金属元素含量的faas法测定

火焰原子吸收光谱法;金属元素;茵栀黄注射液; 干扰消除剂     

溶剂浮选法分离富集大黄中的有效成分

采用溶剂浮选法对大黄提取液中的芦荟大黄素、大黄素、大黄酚以及大黄素甲醚进行了分离富集,并用高效液相色谱法分别测定了其含量。考察了料液浓度、浮选溶剂、浮选时间、浮选液pH值、氮气流速和电解质NaCl浓度对浮选效率的影响,并与泡沫浮选法和溶剂萃取法进行了比较。结果表明：溶剂萃取效果最差,泡沫浮选次之,溶剂浮选法分离富集效果最好。当料液浓度为6．4mg／mL,浮选时间为30min,浮选液pH一1～2,氮气流速为20mL／min,电解质NaCl浓度为0．4mol／L时,溶剂浮选效率最佳。     

Temperature-assisted ionic liquid dispersive liquid-liquid microextraction combined with high performance liquid chromatography for the determination of anthraquinones in Radix et Rhizoma Rhei samples

In this article, a novel method termed as temperature-assisted ionic liquid dispersive liquid-liquid microextraction (TA IL-DLLME) combining high performance liquid chromatography with diode array detection (HPLC-DAD) was developed for the determination of anthraquinones in Radix et Rhizoma Rhei samples. The ionic liquid (1-hexyl-3-methylimidazolium hexafluorophosphate) was used to replace volatile organic solvent as an extraction solvent for the extraction of anthraquinones (aloe-emodin, rhein, emodin, chrysophanol and physcion) from Radix et Rhizoma Rhei. Several important parameters influencing the extraction efficiency of TA IL-DLLME such as the type and volume of extraction solvent and disperser solvent, sample pH, extraction time, extraction temperature, centrifugation time as well as salting-out effects were optimized. Under the optimal conditions, the spiked recovery for each analyte was in the range of 95.2-108.5%. The precisions of the proposed method were varied from 1.1% to 4.4% (RSD). All the analytes exhibited good linearity with correlation coefficients (r²) ranging from 0.9986 to 0.9996. The limits of detection for all target analytes were ranged from 0.50 to 2.02 μg L⁻¹ (S/N = 3). The experimental results indicated that the proposed method was successfully applied to the analysis of anthraquinones in Radix et Rhizoma Rhei.     

色谱指纹谱用于中药大黄抗肿瘤活性成分的筛选

采用液相色谱-质谱联用方法分析了中药大黄经过SD大鼠肝匀浆体外代谢前后的指纹谱中色谱峰面积、保留值的差异。指出5种游离型蒽醌化合物在SD大鼠肝匀浆体外代谢体系中只有大黄酚发生代谢反应转化为芦荟大黄素。考察了体外代谢条件下,肝匀浆浓度与代谢时间对大黄酚转化及其代谢产物的影响。SD大鼠体外抗肿瘤试验表明,大黄代谢物对于人宫颈癌(HeLa)细胞的抑制活性略高于其提取物。通过比较芦荟大黄素、大黄酸、大黄素、大黄酚、大黄素甲醚的活性,并结合大黄酚的体外代谢反应的考察,解释了大黄代谢物对肿瘤细胞活性的抑制率的提高是由大黄酚的代谢产物芦荟大黄素浓度的增加引起的。     

基于多指标含量测定结合化学计量学的不同产地丹参品质差异分析

为对比分析产地对丹参中酚酸类和丹参酮类成分的影响,采用超高效液相色谱（UPLC）及超高效液相色谱－三重四极杆质谱联用技术（UPLC－QQQ－MS）同时测定来自山东、河南、陕西、四川、安徽共408份丹参中23种化学成分的含量,并对数据进行多元统计分析。研究发现17种酚酸类及6种丹参酮类成分在不同产地丹参中均存在显著差异。山东的丹参样品中丹参酮类成分含量最高,四川的样品中丹酚酸B含量最高,安徽丹参的紫草酸、丹酚酸Y、丹酚酸A、丹酚酸D和丹酚酸E等的含量最高。多种模式识别方法均可用于不同产地丹参的判别分析,线性判别分析（LDA）为产地溯源的最佳模型。正交偏最小二乘法判别分析（OPLS－DA）表明不同产地丹参的化学成分差异较大,不同来源丹参的质量差异标志物不仅限于丹酚酸B、丹参酮Ⅰ、隐丹参酮、丹参酮ⅡA,其他丹酚酸类及丹参酮类也是重要的质量标志物。该研究对全国不同主产区的栽培丹参进行多指标含量测定及建模分析,所建立的定量方法专属性强、准确高效,可为不同产地丹参的质量控制及产地判别提供参考。     

Novel Carbon Dots Derived from Glycyrrhizae Radix et Rhizoma and Their Anti-Gastric Ulcer Effect

Glycyrrhizae Radix et Rhizoma (GRR) is one of the commonly used traditional Chinese medicines in clinical practice, which has been applied to treat digestive system diseases for hundreds of years. GRR is preferred for anti-gastric ulcer, however, the main active compounds are still unknown. In this study, GRR was used as precursor to synthesize carbon dots (CDs) by a environment-friendly one-step pyrolysis process. GRR-CDs were characterized by using transmission electron microscopy, high-resolution TEM, fourier transform infrared, ultraviolet-visible and fluorescence spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction and high-performance liquid chromatography. In addition, cellular toxicity of GRR-CDs was studied by using CCK-8 in RAW264.7 cells, and the anti-gastric ulcer activity was evaluated and confirmed using mice model of acute alcoholic gastric ulcer. The experiment confirmed that GRR-CDs were the spherical structure with a large number of active groups on the surface and their particle size ranged from 2 to 10 nm. GRR-CDs had no toxicity to RAW264.7 cells at concentration of 19.5 to 5000 μg/mL and could reduce the oxidative damage of gastric mucosa and tissues caused by alcohol, as demonstrated by restoring expression of malondialdehyde, superoxide dismutase and nitric oxide in serum and tissue of mice. The results indicated the explicit anti-ulcer activity of GRR-CDs, which provided a new insights for the research on effective material basis of GRR.     

Determination of fifteen bioactive components in Radix et Rhizoma Salviae Miltiorrhizae by high-performance liquid chromatography with ultraviolet and mass spectrometric detection

A high-performance liquid chromatographic (HPLC) method coupled with ultraviolet (UV) and electrospray ionization time-of-flight mass spectrometry (ESI-TOF/MS) was established for simultaneous qualitative and quantitative determination of nine phenolic acids and six diterpenoids in Radix et Rhizoma Salviae Miltiorrhizae (RRSM). The optimal chromatographic conditions were achieved on a Zorbax C(18) column by gradient elution with 0.1% (v/v) aqueous formic acid and acetonitrile as mobile phase at the flow rate of 1.0 mL/min. The detection wavelength at 281 nm was chosen to determine the 15 bioactive components, namely danshensu (1), protocatechuic acid (2), protocatechuic aldehyde (3), caffeic acid (4), rosmarinic acid (5), lithospermic acid (6), salvianolic acid B (7), salvianolic acid A (8), salvianolic acid C (9); dihydrotanshinone I (10), cryptotanshinone (11), tanshinone I (12), methylene tanshiqunone (13), tanshinone IIA (14) and miltirone (15). Additionally, LC-ESI-TOF/MS was used to make definite identification of the constituents in samples in comparison with those reference compounds. The validation of the method included tests of linearity, sensitivity, repeatability, stability and recovery. The proposed method was successfully applied to quantify the 15 components in 21 samples; significant variations were demonstrated in the contents of the samples from diverse species and origins. The developed method could be used to effectively and comprehensively evaluate the quality of RRSM for its clinical safety and efficacy.     

Screening epidermal growth factor receptor antagonists from Radix et Rhizoma Asari by two‐dimensional liquid chromatography

Radix et Rhizoma Asari is a traditional Chinese medicine, and has many pharmacological effects, such as calming, analgesia, anti‐inflammation, antiarrhythmic, antihypertensive, antivirus, etc. But few studies have screened the active compounds from extracts of Radix et Rhizoma Asari for tumor therapy. In this study, a two‐dimensional liquid chromatography system was built to screen active compounds acting on epidermal growth factor receptor (EGFR) from Radix et Rhizoma Asari. The screening result showed that asarinin from Radix et Rhizoma Asari was the targeted component that could act on EGFR specificity. The competitive binding assay and molecular docking assay results showed asarinin binding with EGFR in similar manner as with gefitinib, which was used as a positive control drug. Then the antitumor effect of asarinin was studied through cell growth assay in vitro. The results showed that gefitinib and asarinin could inhibit highly expressed EGFR cell growth in a dose‐dependent manner in the range of dose from 0.10 to 102.4 μM. This two‐dimensional liquid chromatography system will be a useful method in drug discovery from natural medicinal herbs for searching potential antitumor candidates.     

Classification of Rhizoma et Radix Notoperygii by HPLC Fingerprints with the Aid of Chemometrics

Chromatographic profiles of Rhizoma et Radix Notoperygii (RRN, “Qianghuo” in Chinese), a complex traditional Chinese medicine (TCM), were collected by high-performance liquid chromatography with diode array detection (HPLC-DAD) at 330 nm. These data profiles were used as fingerprints to investigate quality control classification modeling of the RRN samples. In contrast to the classical methods for discrimination of TCMs, that is, just using common HPLC peaks, all chromatographic profile data were pre-processed by the correlation optimized warping method and polynomial functions; then, these data were submitted as fingerprints (variables) for classification on the basis of sample origin. Chemometrics methods used for calibration modeling and subsequent sample classification-least square support vector machine (LS-SVM), artificial neural network (ANN), and partial least square discriminant analysis (PLS-DA); all produced satisfactory calibrations as well as classification results.     

Rapid optimization of dual-mode gradient high performance liquid chromatographic separation of Radix et Rhizoma Salviae Miltiorrhizae by response surface methodology

An approach for rapid optimization of dual-mode gradient high performance liquid chromatography (HPLC) by response surface methodology (RSM) was developed for fast simultaneous separation of hydrophilic and hydrophobic components in Radix et Rhizoma Salviae Miltiorrhizae (Danshen) and its preparations. The aim of this study was to achieve a high throughput RSM optimization using a short ultra-high performance liquid chromatographic (UHPLC) column to simultaneously optimize flow rate and solvent gradient, and then transfer the optimized method to conventional HPLC for routine analytical purposes. The optimization was designed with Box Behnken design (BBD) and the global Derringer's desirability was used for describing the multicriteria response variables. Sixty-two designed experiments were performed by UHPLC with a short sub-2 μm column (2.1 mm × 50 mm, 1.7 μm) and a total running time of only 5 h. The predicted gradient profile was further transferred to a long UHPLC column (2.1 mm × 100 mm, 1.7 μm) and a conventional HPLC columns (2.1 mm × 100 mm, 3.5 μm and 4 mm × 100 mm, 5 μm, respectively). Compared to the published methods, the newly developed dual-mode gradient is faster and more efficient at simultaneously separating hydrophilic and hydrophobic components in Danshen and its preparations.