牛蒡苷与牛蒡苷元的荧光性质及中药牛蒡子中牛蒡苷的荧光法测定

牛蒡苷和牛蒡苷元的三维荧光图谱中均呈现2个荧光峰,激发波长λex分别为230 nm和280 nm,发射波长(λem)均为310 nm。牛蒡苷的荧光远强于牛蒡苷元的荧光。溶液酸度对牛蒡苷和牛蒡苷元的荧光强度有明显影响。在pH13.0时,牛蒡苷的荧光增强,而牛蒡苷元的荧光猝灭。牛蒡子药材的三维荧光图谱和薄层荧光色谱表明,牛蒡子的荧光成分主要为牛蒡苷,而牛蒡苷元及其他共存组分在强碱性条件下对牛蒡苷的荧光无影响。据此,以甲醇为溶剂制备牛蒡子样品提取液,用水适当稀释并调节至pH 13.0,在λex/λem=280 nm/310 nm波长下测定牛蒡苷的含量。在0.014 5~2.03 mg·L-1范围内,荧光强度与牛蒡苷浓度间呈良好线性,其线性方程为IF=2.7+148.7ρ(mg·L-1),相关系数(r)为0.999。用本法测得牛蒡子对照药材中牛蒡苷的含量为6.01%,平均加标回收率为98.1%。用薄层荧光扫描法对本方法进行验证,结果表明,本法结果可靠,可用于牛蒡子药材的质量检验。     

牛蒡苷与牛蒡苷元的荧光性质及中药牛蒡子中牛蒡苷的荧光法测定

牛蒡苷和牛蒡苷元的三维荧光图谱中均呈现2个荧光峰,激发波长λex分别为230 nm和280 nm,发射波长（λem）均为310 nm。牛蒡苷的荧光远强于牛蒡苷元的荧光。溶液酸度对牛蒡苷和牛蒡苷元的荧光强度有明显影响。在pH>13.0时,牛蒡苷的荧光增强,而牛蒡苷元的荧光猝灭。牛蒡子药材的三维荧光图谱和薄层荧光色谱表明,牛蒡子的荧光成分主要为牛蒡苷,而牛蒡苷元及其他共存组分在强碱性条件下对牛蒡苷的荧光无影响。据此,以甲醇为溶剂制备牛蒡子样品提取液,用水适当稀释并调节至pH 13.0,在λex/λem=280 nm/310 nm波长下测定牛蒡苷的含量。在0.014 5~2.03 mg?L-1范围内,荧光强度与牛蒡苷浓度间呈良好线性,其线性方程为IF=2.7+148.7ρ(mg?L-1),相关系数（r）为0.999。用本法测得牛蒡子对照药材中牛蒡苷的含量为6.01%,平均加标回收率为98.1%。用薄层荧光扫描法对本方法进行验证,结果表明,本法结果可靠,可用于牛蒡子药材的质量检验。     

牛蒡子中木脂素的薄层扫描测定

在高效硅胶薄层板上分离了牛蒡子中４种２,３－苄基丁内酯型木脂素──牛蒡甙元（Ｉ）、牛蒡素Ｂ（Ⅱ）、牛蒡酚Ａ（Ⅲ）、牛蒡酚Ｆ（Ⅳ）。流动相为二氯甲烷－乙醚－甲醇－己烷（４：１：０．４：１）,室温放置,自然显色。薄层扫描法定量,各木脂素的线性范围在０．４５１～４．６０８μｇ,回收率为９９．９０％～１００．９０％,并用此法测定了不同产地牛蒡子中木脂素的含量。方法简便、快速,样品用量少。     

固态发酵-水煮耦合炮制牛蒡子提高牛蒡子苷元含量

研究了黑曲霉Aspergillus niger ZJUT712菌株固态发酵和水煮工艺相耦合炮制牛蒡子. 结果表明,该工艺提高了牛蒡子中有效成分牛蒡子苷元的含量,从而有利于促进牛蒡子摄入体内迅速起效. 最佳固态发酵炮制条件为: 0.5 g牛蒡子粉、 3 g麸皮、 2 g甘蔗渣、 0.3 g蛋白胨和10 ml Mandels营养液,固液比1∶3.6 g/ml, 初始pH 5.6, 30 ℃发酵 7 d. 牛蒡子苷元产率随底物初始浓度的增加而降低. A.niger ZJUT712转化0.174 mmol/L牛蒡子苷的产率可达93.0%. 7 d时间内A.niger ZJUT712水解牛蒡子苷的过程符合Monod方程,反应动力学常数为Vm=0.083 7 mmol/(L·d), Km=0.16 mmol/L.     

水母雪莲化学成分的研究（Ⅱ）

前文已报道从水母雪莲(Saussurea Medusa Maxim)中分得4种黄酮甙,本文报道另外6种化合物的分离和鉴定。 1 化合物Ⅰ—Ⅳ物化性质及分离鉴定 1.1 化合物Ⅰ 黄色结晶,m.p.:249～251℃,水解所得甙元鉴定为木樨草素,纸层析检出鼠李糖和葡萄糖。MS(FAB):m/z 595(M~++1),287(M~++H-葡萄糖基-鼠李糖)。化合物I与木樨草素的~(13)C NMR比较,C_6、C_8、C_(10)分别向低场位移1.1、1.0、1.8 ppm,而C,向高场移动     

聚酰胺柱层析/反相高效液相色谱/电喷雾离子质谱法分离鉴定牛蒡叶中两种黄酮苷

1　引　　言菊科植物牛蒡 (ArctiumlappaL .)富含木脂体 (lignans)、硫乙炔化合物 (sulfur containingacetyleniccompounds)及聚乙炔化合物 (polyacetylenes)、咖啡酰奎尼酸衍生物 (caffeoylquinicacidderivatives)、抑肿瘤因子 (antimutagenicfactor)、可食性纤维(dietaryfiber)、菊粉 (inulin)及牛蒡苦素 (arctiopicrin)等几类具有重要药理作用的化学成分。有关牛蒡化学组成的研究主要取材于牛蒡种子和根。而牛蒡叶的化学组成还甚少报道。本文建立了一种分离、鉴定牛蒡叶中两种黄酮苷、槲皮素葡萄糖鼠李糖苷 (quecertin 3 O rutinoside)…     

嘧啶衍生物对牛蒡子苷元片段修饰的研究

用一系列具有生物活性的嘧啶衍生物修饰牛蒡子苷元,旨在寻找增强牛蒡苷元子抗肿瘤活性的同时又能降低嘧啶抗肿瘤副作用的先导化合物.本研究通过把卤代后的嘧啶衍生物与牛蒡子苷元酚羟基相接,合成得到11个新的化合物,通过1H NMR与LC-MS表征确定其结构.最终,增加了牛蒡子苷元抗肿瘤化合物库中化合物的数量,为接下来的体外活性筛选做准备.     

超高压辅助离子液体提取/HPLC分析牛蒡子中牛蒡苷与牛蒡苷元

通过离子液体类型与浓度、提取压力、时间、料液比等单因素实验确定了超高压辅助离子液体提取牛蒡子中牛蒡苷和牛蒡苷元的最佳工艺。结果表明,超高压离子液体提取最佳工艺为以0.80 mol/L溴化1-十二烷基-3-甲基咪唑溶液为溶剂,提取压力200 MPa,提取时间2 min,料液比1∶20(g/mL),牛蒡苷和牛蒡苷元的提取率分别为37.15、8.04 mg/g。与传统提取方法相比,超高压提取时间只需2 min,是超声方法的1/15、加热回流方法的1/60,极大地节省了提取时间,提高了工作效率,且不污染环境,是提取牛蒡苷和牛蒡苷元的一种简单有效的方法。     

阿拉善马先蒿植物中单萜环烯醚甙的研究

阿拉善马先蒿(Pedicularis alaschania maxim)系玄参科马先蒿属植物,民间可代替夏枯草入药,主治淋巴结核、淋巴腺炎、高血压和甲状腺肿大等疾病。其化学成分研究尚未见报道。我们从马先蒿中分离得到2个单萜环烯醚甙P1和P2。P2经质谱(FAB MS)、核磁共振谱(~1H和~(13)C NMR)和红外光谱等数据与文献对照确定为桃叶珊瑚甙(aucubin)。P1为一新化合物。本文报道它们的分离与鉴定。     

杜仲中京尼平甙酸的硅胶柱色谱分离纯化及反相高效液相色谱/液相色谱-电喷雾质谱/核磁共振鉴定

建立了杜仲中京尼平甙酸的硅胶柱色谱分离纯化及反相高效液相色谱/液相色谱-电喷雾质谱/核磁共振(RP-HPLC/LC-ESI-MS/NMR)鉴定方法。杜仲皮经粉碎后,用70%乙醇提取,提取液经减压蒸馏至干,再用甲醇溶解,然后吸附于硅胶上,并以不同体积比的氯仿-甲醇混合液按洗脱剂的极性由小到大进行洗脱,以RP-HPLC法检测洗脱液中物质的种类和含量。结果表明:洗脱剂为氯仿-甲醇（体积比为8∶1）的洗脱液经分析为单一组分,其保留时间为5.142 min;以对照品京尼平甙酸添加法测定,其峰高增加;相关紫外光谱和红外光谱检测结果与京尼平甙酸对照品基本一致;结合LC-ESI-MS、 1H-NMR和13C-NMR等测定,确定该洗脱组分为京尼平甙酸。     

Unified chromatography: Fundamentals,instrumentation and applications†

The concept of unified chromatography has been in existence for 50 years after the work of Giddings proposing that all modes of chromatography (gas chromatography, liquid chromatography, supercritical fluid chromatography and so on) may be treated together under a single unified theory. His idea was partially fulfilled 23 years later by Ishii, Takeuchi and colleagues, who demonstrated for the first time the possibility to analyze a complex sample containing substances with a wide range of boiling points and polarities in the same instrument and column, just by varying the mobile phase pressure and temperature to change from one chromatographic mode to another. This approach has been demonstrated through application to the separation of complex mixtures in several areas including crude oil, edible oils and polymers. Still, unified chromatography has not yet been fully developed. In the present work, we will review the fundamentals, instrumentation and several applications of the technique. Also discussed are the drawbacks that still hinder development, as well as the recent developments and trends in instrumentation and columns that suggest the most feasible ways forward to the full development of unified chromatography.     

Simultaneous determination of aflatoxin B1, B2, G1, and G2 in corn powder,edible oil,peanut butter,and soy sauce by liquid chromatography with tandem mass spectrometry utilizing turbulent flow chromatography

A novel fully automated method based on dual column switching using turbulent flow chromatography followed by liquid chromatography with tandem mass spectrometry was developed for the determination of aflatoxin B₁, B₂, G₁, and G₂ in corn powder, edible oil, peanut butter, and soy sauce samples. After ultrasound‐assisted extraction, samples were directly injected to the chromatographic system and the analytes were concentrated into the clean‐up loading column. Through purge switching, the analytes were transferred to the analytical column for subsequent detection by mass spectrometry. Different types of TurboFlow^TM columns, transfer flow rate, transfer time were optimized. The limits of detection and quantification of this method ranged between 0.2–2.0 and 0.5–4.0 μg/kg for aflatoxins in different matrixes, respectively. Recoveries of aflatoxins were in range of 83–108.1% for all samples, matrix effects were in range of 34.1–104.7%. The developed method has been successfully applied in the analysis of aflatoxin B₁, B₂, G₁, and G₂ in real samples.     

Preparation,evaluation, and application of a novel reversed-phase/zwitterionic/hydrophilic interaction liquid chromatographic mixed-mode stationary phase

The present study described the preparation and application of a reversed-phase/zwitterionic/hydrophilic interaction liquid chromatography stationary phase, named as SIL-PS. The SIL-PS was prepared through a four-step reaction, chemical bonding, nucleophilic addition, SN1 substitution, and sulfonation on the silica matrix. It was featured with C₁₂ alkyl chain, quaternary ammonium, tertiary amine, and sulfonate groups. After SIL-PS was packed into the stainless steel column (150?× 2.1 mm i.d.), chromatographic parameters, including acetonitrile content, pH, and ionic strength of the mobile phase, and the column temperature, were systematically investigated to study the retention mechanism. Electrostatic adsorptive/repulsive, partition, and hydrogen-bonding interactions were demonstrated to contribute to the retention. The stability of the SIL-PS was satisfactory, with relative standard deviations of retention factors of 1.93, 2.08, and 1.90% for loxoprofen, adenosine, and liquiritin, respectively. Additionally, to investigate the separation selectivity, the non-steroidal anti-inflammatory drugs, nucleobases/nucleotides, and alkaloids/glycosides were separated; the HPLC fingerprinting of the Cortex phellodendri extract was also conducted, and the separation performance was superior to that of the C18 column in terms of peak shape, resolution, and analytical time. The results revealed that the prepared SIL-PS possessed multifunctionalities for multiretention and could be promising for complicated samples.     

A unified approach to the chromatography-FTIR interface: GC-FTIR,SFC-FTIR,and HPLC-FTIR with subnanogram detection limits

The results described in this paper demonstrate that Identifiable FTIR spectra of components separated by gas, supercritical fluid, and liquid chromatography can be measured in real time using a common approach. The sensitivity of each Interface is comparable with that obtained by interfacing the corresponding technique with a bench-top mass spectrometer. The combination of these two spectroscopic techniques should lead to an even more powerful means of Identification of volatile, semi-volatile, and non-volatile components of mixtures.     

Facile extraction of berberine from different plants,separation, and identification by thin-layer chromatography,high-performance liquid chromatography,and biological evaluation against Leishmaniosis

The extraction of berberine was carried out from Berberis vulgaris, Berberis aquifolium, and Hydrastis canadensis plants using ethanol and water (70:30, v/v). The extracted berberine was characterized by ultraviolet-visible and Fourier-transform infrared spectroscopy. The purity of berberine was ascertained by thin-layer chromatography using n-propanol-formic acid-water (95:1:4) and (90:1:9) solvents. hR_f values were in the range of 44–49 with compact spots (diameter 0.2–0.4 cm). HPLC was carried out using ammonium acetate buffer and acetonitrile in gradient mode with Zodiac (4.6 × 150 mm, 3 μm) column. The flow rate was 1.0 mL/min and detection was at 220 nm. The values of separation and resolution factors of the standard and the extracted berberine were in the range of 1.13–1.16 and 1.40–1.71, respectively. A comparison has shown that both thin-layer chromatography and high-performance liquid chromatography (HPLC) methods found applications in different situations and requirements. The extracted berberine samples were used to treat Leishmaniosis and the results showed better activity of berberine in comparison to the standard drug Amphotericin B. Briefly, the reported research is a novel and may be used to extract berberine from plants, separation and identification of berberine by thin layer chromatography and HPLC and to treat Leishmaniosis.     

Purification and identification of PEGlated hemoglobin, a potential blood substitute, by chromatography and capillary electrophoresis

Summary Bovine hemoglobin (Hb) has been chemically modified, by reaction of its lysine residues with the active ester of poly(ethylene glycol) (PEG,M _w=5000), to produce a potential blood substitute for human therapy. Covalent attachment of PEG chain to the protein produced a heterogeneous mixture of Hb from the mixture. This paper describes the use of cation-exchange chromatography (IEC), in flow-through mode, and size-exclusion chromatography (SEC) for purification of the PEG-Hb mixture. The highly modified Hb flowed through the IEC column in the loading buffer without adsorption by the chromatographic medium. SEC was then used for further purification. These two steps were suitable for pilot-scale preparation or for analytical chromatography. The purified product was assessed by high-performance capillary electrophoresis (HPCE), which was also used to optimize the chromatographic parameters.     

Liquid chromatography on unmodified and modified spheron gels I. Nucleosides,bases and related compounds

Summary The ethylene glycol methacrylate gel Spheron and ion exchangers produced by the chemical modification of this gel (such as the cation exchanger Spheron S and anion exchanger Spheron DEAE) are compared with octadecylsilica as column packing materials for reversedphase chromatography of nucleic acid constituents and related compounds. The different separation selectivities of the individual materials can be utilized for the chromatographic separation of these compounds.     

Analysis of functionalized polyisobutylenes by capillary SFC, SEC, HPLC, and CGC-MS after fraction collection

Summary An analytical strategy has been developed for analysis of polyisobutylenes partially functionalized with isothiocyanate groups ( ) by capillary supercritical-fluid chromatography (CSFC), size- exclusion chromatography (SEC), and reversed-phase liquid chromatography (RPLC). Fractions collected from semi-preparative RPLC and SEC were further characterized by capillary GC-MS (gas chromatography coupled with mass spectrometry). Complete characterization of the polymer was achieved by comparing the results obtained from the different techniques. The degree of polymerization and the relative quantity of the different series of macromolecular chains of polyisobutylene were estimated.     

Rapid isolation,reliable characterization,and water solubility improvement of polymethoxyflavones from cold‐pressed mandarin essential oil

Polymethoxyflavones possess many biological properties, as lipid‐lowering, hypoglycaemic, anti‐inflammatory, antioxidant, and anticancer activities, therefore, they may be employed as nutraceuticals or therapeutic agents. The scarcity of pure polymethoxyflavones on the market as well as their low water solubility limited in vivo studies and the use of polymethoxyflavones as food or pharmaceutical supplements. Since mandarin peels are a rich source of polymethoxyflavones, tangeretin, nobiletin, sinensetin, tetra‐O‐methyl scutellarein, and heptamethoxyflavone were purified from a nonvolatile residue of a cold‐pressed mandarin essential oil using a multidimensional preparative liquid chromatographic system coupled with a photodiode array detector and a single quadrupole mass spectrometer. A new prototype, consisting of a nano‐liquid chromatography system coupled with an electron ionization mass spectrometer, was used for the characterization of the pure isolated molecules. Finally, due to the collection of highly pure nobiletin and tangeretin, the ability of 2‐hydroxypropyl‐β‐cyclodextrin to enhance the water solubility of both polymethoxyflavones was evaluated by phase solubility studies and Job's plot method.