Two new triterpenoids from Gardenia jasminoides fruits

A new cycloartane triterpenoid, named gardenolic acid C (1), a new ursane triterpenoid, named 3β,16β,21β,23,24-pentahydroxy urs-12,18,20-trien-28-oic acid γ-lactone (2), together with three know triterpenoids, gardenolic acid A (3), gardenolic acid B (4), and 3α,16β,23,24-tetrahydroxy-28-nor-ursane-12,17,19,21-tetraen (5) were isolated from the fruits of Gardenia jasminoides Ellis. The structures of these compounds were elucidated by analyses of spectroscopic data. All isolates were evaluated for their neuroprotective effects in vitro.

     

Four New Gallate Derivatives from Wine-Processed Corni Fructus and Their Anti-Inflammatory Activities

Four new gallate derivatives—ornusgallate A, ent-cornusgallate A, cornusgallate B and C (1a, 1b, 2, 3)—were isolated from the wine-processed fruit of Cornus officinalis. Among them, 1a and 1b are new natural compounds with novel skeletons. Their chemical structures were elucidated by comprehensive spectroscopy methods including NMR, IR, HRESIMS, UV, ECD spectra and single-crystal X-ray diffraction analysis. The in vitro anti-inflammatory activities of all compounds were assayed in RAW 264.7 cells by assessing LPS-induced NO production. As the result, all compounds exhibited anti-inflammatory activities at attested concentrations. Among the tested compounds, compound 2 exhibited the strongest anti- inflammatory activity.     

近红外漫反射光谱法定量分析连翘药材

利用近红外漫反射光谱技术和偏最小二乘法定量分析了连翘药材中连翘苷与连翘酯苷的含量。所建立校正模型内部交叉验证均方差(RMSEC)分别为0.327、0.273,交叉验证决定系数分别为0.968、0.978。利用该模型对10份未知样品进行预测,预测值和参考值之间的相关系数分别为0.929、0.986,预测均方差(RMSEP)分别为0.421、0.260,该法具有准确、快速、不破坏样品等优点。     

LC–MS methods combination for identification and quantification of trans-sinapoylquinic acid regioisomers in green coffee

The present study aims to both identify and quantify trans-sinapoylquinic acid (SiQA) regioisomers in green coffee by combined UHPLC-ESI-QqTOF-MS/MS and UHPLC-ESI-QqQ-MS/MS methods. Among the various mono-acyl chlorogenic acids found in green coffee, SiQA regioisomers are the least studied despite having been indicated as unique phytochemical markers of Coffea canephora (known as Robusta). The lack of commercially available authentic standards has been bypassed by resorting to the advantages offered by high-resolution LC–MS as far as the identification is concerned. SiQA regioisomers have been identified in several samples of Robusta and Coffea arabica (known as Arabica) commercial lots from different geographical origin and, for the first time, in different samples of coffee wild species (Coffea liberica and Coffea pseudozanguebariae). Quantification (total SiQA ranging from 3 to 5 mg/100 g) let to reconsider these chlorogenic acids as unique phytochemical markers of Robusta being present in the same quantity and distribution in C. liberica as well. Gardeniae Fructus samples (fruits of Gardenia jasminoides) have additionally been characterized as this matrix is recognized as one of the few naturally occurring SiQA sources. The SiQA regioisomer content (total SiQA about 80 mg/100 mg) fully supports the proposal to use this matrix as a surrogate standard for further studies.     

Optimization of the Extraction Conditions and Simultaneous Quantification by RP-LC of Six Alkaloids in Evodiae Fructus

A reversed phase liquid chromatographic (LC) method coupled with DAD (250 nm) has been developed and validated for simultaneous quantification of six alkaloids, dehydroevodiamine (1), wuzhuyuamide-I (2), 5-hydroxyrutaecarpine (3), 14-formyldihydrorutaecarpine (4), evodiamine (5) and rutaecarpine (6), in 12 batches evodiae fructus [the dried, unripe fruits of Evodia rutaecarpa (Juss.) Benth. or E. rutaecarpa (Juss.) Benth. var. officinalis (Dode) Huang, E. rutaecarpa (Juss.) Benth. var. bodinieri (Dode) Huang] as a traditional Chinese medicine. The method was carried out by a C₁₈ column (250 × 4.6 mm) with a gradient mobile phase of methanol, acetonitrile, and phosphoric acid–triethylamine–buffer solution. The contents of 1–6 in the evodiae fructus could easily be determined within 70 min. The experimental results were satisfactory for the intra-day and inter-day precision and accuracy of the method for simultaneous determination. The linear calibration ranges of 1–6 were 40–1,000, 20–500, 1–100, 10–500, 40–1,000 and 80–1,000 μg mL⁻¹. The recoveries of 1–6 were 97.43–103.73% with RSDs from 0.21 to 1.99%. The limits of detection for 1–6 were 2.0, 2.0, 0.1, 1.0, 5.0 and 5.0 μg mL⁻¹, and the limits of quantification were 6.6, 6.6, 0.3, 3.3, 16.5 and 16.5 μg mL⁻¹. The method was successfully applied to the quantification of six alkaloids in the evodiae fructus.     

Rapid quantification of iridoid glycosides analogues in the formulated Chinese medicine Longdan Xiegan Decoction using high-performance liquid chromatography coupled with mass spectrometry [corrected

Longdan Xiegan Decoction (LXD) is a formulated preparation composed of 10 ingredient herbs, with iridoids as the main bioactive components. In this study, a rapid, simple and reliable method of simultaneous determination of four iridoid glycosides in LXD using high-performance liquid chromatography (HPLC) coupled with electrospray ionization mass spectrometry (MS) was first developed and validated. The four iridoid glycosides references were isolated from LXD extract and purified using a preparative HPLC chromatography. The sample preparation for quantification comprised of a simple ultrasonic extraction and the satisfactory chromatographic separation of the four structurally similar iridoid glycosides was effected in less than three minutes on a CAPCELL PAK C(18) MGII column (3 microm, 100 mm x 2.0 mm), using an elution system of 10% methanol and their concentrations in different batches of LXD and ingredient herbs were simultaneously determined by HPLC-MS/MS using a multiple reaction monitoring (MRM) mode. The method was validated with respect to the overall intra- and inter-day variation (RSD less than 8%) and the limits of quantification for the four iridoid glycosides were 35, 20, 37 and 33 ng/mL, respectively.     

不同澄清剂对五味子水提物澄清效果的比较

以680nm处的透光率作为澄清度的指标,比较明胶、淀粉、蛋清和壳聚糖4种澄清剂在不同浓度、温度、处理时间下的澄清效果。结果表明:明胶和壳聚糖澄清效果较好,蛋清次之,而淀粉几乎无澄清作用。0.16%的明胶和0.08%的壳聚糖澄清效果最佳,透光率分别为84.02%和84.44%。蛋清的澄清速度较明胶和壳聚糖慢;温度对蛋清和壳聚糖几乎无影响,但明胶随处理温度升高透光率下降。     

Dispersive liquid-liquid microextraction based on a supramolecular solvent followed by high-performance liquid chromatographic analysis of lignans in Forsythiae Fructus

A supramolecular solvent-based dispersive liquid-liquid microextraction was proposed for the extraction and determination of lignans in Forsythiae Fructus combined with high-performance liquid chromatography. The supramolecular solvent, consisting of tetrabutylammonium bromide and n-hexanol, was mixed with the sample solution to extract the analytes by a vortex. After accomplishing the extraction, the extraction phase was separated by centrifugation and collected for high-performance liquid chromatography analysis. In this work, the important extraction variables such as the type and amount of extraction solvent, pH and salt amount in the sample phase, and extraction time were optimized. The synthesis of supramolecular solvent was studied and its microstructure was characterized by transmission electron microscopy. Under the optimal conditions, the analytes’ enrichment factors were between 6 and 170 for the proposed procedure. Satisfactory linear ranges (r ≥ 0.99), detection limits (0.025–0.4 ng/ml), precisions (< 9.2%), and accuracies (recoveries: 96.5%–104.8%) were obtained. The method has been successfully applied to the preconcentration of lignans in Forsythiae Fructus with simple and rapid operation, low cost, and environmental friendliness.     

枳实、枳壳用于复方治疗冠心病的临床疗效观察

目的观察枳实、枳壳用于复方治疗冠心病的临床疗效对比分析。方法观察260例冠心病心绞痛患者,随机分为对照组、复方组(分1~4小组)、阴性组(分a~d小组)、考察组(分Ⅰ~Ⅳ小组),疗程8周。结果各项评价指标显示,复方组(1~4)、考察组(Ⅰ、Ⅱ)明显优于对照组(P0.05),复方各小组与对应考察组比较无显著性差异(P0.05),但考察组(Ⅲ、Ⅳ)不良反应率高于对应的复方组。阴性组疾病疗效、心电图与对照组比较无显著性差异,中医症状改善明显优于对照组。复方组与对应阴性组比较有明显差异。结论枳实、枳壳用于复方中治疗冠心病心绞痛有重要作用,能明显缓解心绞痛症状,改善中医症状,提高疾病疗效,两者之间不可完全相互替代。     

Ionic liquid vortex‐simplified matrix solid‐phase dispersion for the simultaneous determination of terpenoids,crocins, quinic acid derivatives and flavonoids in Gardeniae fructus by UHPLC

A novel ionic‐liquid‐based vortex‐simplified matrix solid‐phase dispersion method using 2,6‐dimethyl‐β‐cyclodextrin was established by ultra high performance liquid chromatography coupled with a photodiode array detector. 2,6‐Dimethyl‐β‐cyclodextrin was first used as a promising adsorbent in this proposed method for simultaneous determination of eight compounds in Gardeniae fructus. These compounds are terpenoids (geniposidic acid, genipin‐1‐β‐D‐gentiobioside, geniposide, 8‐o‐acetyl shanzhiside methyl ester), crocins (crocin‐I, crocin‐II), quinic acid derivatives (chlorogenic acid), and flavonoids (isoquercitrin), respectively. Several parameters were investigated in the adsorption and desorption processes to obtain the optimal conditions, including 2,6‐dimethyl‐β‐cyclodextrin as sorbent, 0.5 mL 100 mM 1‐dodecyl‐3‐methylimidazolium hydrogen sulfate as the extraction solvent, 2:1 of sample/sorbent ratio, grinding for 2 min and vortexing for 60 s. The recoveries of the eight compounds ranged from 96.6 to 100% (<3.50%). The limits of detection and quantification were in the range of 0.02–0.30 and 0.06–1.25  μg/mL, respectively. Meanwhile, a good linearity was attained with r values (>0.9997). The established method showed higher extraction efficiency and less reagent consumption than traditional matrix solid phase dispersion and ultrasonic‐assisted extraction. Hence, it could be applied for sample preparation and analysis of natural products.