Variations of Chemical Constituents in Gardeniae Fructus Before and After Stir-frying by LCMS-IT-TOF / 中国实验方剂学杂志

Objective: To rapidly analyze chemical compositions in raw products and stir-fried products of Gardeniae Fructus,and determine the pharmacodynamic material basis of Gardeniae Fructus Praeparatus. Method: Liquid chromatography-ion trap-time-of-flight-mass spectrometry(LCMS-IT-TOF) was performed on ACQUITY UPLC HSS T3 column(2.1 mm×100 mm,1.8 μm),mobile phase was 0.005%formic acid aqueous solution(A)-acetonitrile(B) for gradient elution(0-5 min,10%-15%B;5-8 min,15%B;8-18 min,15%-95%B;18-20 min,95%B;20-22 min,95%-10%B;22-25 min,10%B),the column temperature was 30℃ and the flow rate was 0.4 mL·min-1,volume of sample injection was 2 μL;electrospray ionization(ESI) was applied for mass spectrometric analysis under positive and negative ion mode,the scanning ranges were m/z 100-1 000.The ion peaks were identified by comparison of control substances,mass spectrometry data analysis and literature references.The peak areas of some ion peaks before and after processing were compared,the changes of chemical compositions in Gardeniae Fructus after processing were investigated. Result: Based on the mass spectral data information and references,a total of 38 compounds were identified,no new compounds were produced after processing.The ion peak areas of main compounds were investigated during the stir-frying processing,the contents of geniposide,genipin-1-β-D-gentiobioside,shanzhiside,chlorogenic acid and crocin in Gardeniae Fructus Praeparatus were decreased;the contents of geniposidic acid and crocetin were increased. Conclusion: The method can rapidly and accurately identify the chemical constituents in Gardeniae Fructus Praeparatus.The changes of iridoids and crocins in Gardeniae Fructus during the stir-frying process may be related to hemostatic activity and protection of cardiovascular and cerebrovascular.

Reaction of Chlorogenic Acid with Sulfite and Its Application in Identification of Sulfur-fumigated Herbs / 中国实验方剂学杂志

Objective: To explore the structure and reaction sites of the reaction products of chlorogenic acid and sodium sulfite,and the chemical changes of chlorogenic acid in Lonicerae Japonicae Flos after sulfur fumigating. Method: Chlorogenic acid was reacted with sodium sulfite under mild conditions. Liquid chromatography-mass spectrometry-ion trap-time-of-flight (LC-MS-IT-TOF) and 1H nuclear magnetic resonance spectroscopy (1H-NMR) detection techniques were used to detect the reaction products,and the sulfur-fumigated and unsulfurized Lonicerae Japonicae Flos water extract was detected by LC-MS-IT-TOF. Result: After analyzing the mass spectrometry data of fragment ion,molecular cleavage and accurate molecular weight,according to the results of nuclear magnetic signals of chemical shift,peak intensity and peak splitting, the products of chlorogenic acid and sodium sulfite were preliminarily identified as chlorogenic acid α,β-unsaturated carbonyl addition product:3-((3-(3,4-dihydroxyphenyl)-2-sulfopropyl)oxy)-1,4,5-trihydroxycyclohexane-1-carboxylic acid or 3-((3-(3,4-dihy droxyphenyl)-3-sulfopropyl)oxy)-1,4,5-trihydroxycyclohexane-1-carboxylic acid,and the same characteristic fragments were detected as the addition product in the sulfur fumigated Lonicerae Japonicae Flos,but not found in the unsulfurized. Conclusion: It is the first time to demonstrate the structure and reaction sites of chlorogenic acid and sulfurous acid reaction products,and detect the chlorogenic acid sulfite addition product in sulfur-fumigated Lonicerae Japonicae Flos. Although it is still unclear how the sulfite addition compound produced by sulphur Lonicerae Japonicae Flos affects the efficacy and toxicological activity of Lonicerae Japonicae Flos,we shall still pay attention to the changes of active ingredients in sulphuric medicinal materials. Besides,this study can also provide reference for the studies of chemical composition changes after sulfuration of traditional Chinese medicine containing α,β-unsaturated carbonyl structure.

Difference evaluation of three kinds of root of Aconitum carmichaelii in Sichuan based on UPLC analysis of six alkaloids and chemometrics / 中国中药杂志

An ultra performance liquid chromatography (UPLC) method was established and validated to simultaneously determine the contents of six aconitum alkaloids in mother, daughter and fibrous roots of 19 batches of Aconitum carmichaelii from Sichuan province. The separation of the six alkaloids was achieved on a ACQUITY UPLC BEH C18 (2.1 mm x 100 mm, 1.7 microm) column at 40 degrees C with a mobile phase consisting of acetonitrile in 30 mmol x L(-1) ammonium acetate buffer solution (adjusted to pH 10.0 with aqueous ammonia) in gradient mode. The data and plots showed that the six aconitum alkaloids have different distributions. Four aconitum alkaloids were almost same in mother and daughter root except benzoylmesaconine and mesaconitine, while the fibrous root differed from the other two roots. The comparisons of significant differences of six aconitum alkaloids between the mother and daughter roots definitely demonstrated that benzoylmesaconine and mesaconitine were the representative components. The 38 detecting samples were classified as two clusters by hierarchical clustering analysis (HCA) and principle component analysis (PCA), the results indicated that the mother root was different from the daughter root on chemical material basis. The study might contribute to the reasonable clinical application of A. carmichaelii.

Research on ginsenosides composition in wild ginseng leaves in different growing years / 中国中药杂志

<p><b>OBJECTIVE</b>To analyze ginsenosides composition in wild ginseng leaves with different growth years.</p><p><b>METHOD</b>The analysis was performed on Acquity UPLC BEH Shield RP18 (2.1 mm x 100 mm, 1.7 microm) column, the mobile phase was acetonitrile-0.05% formic acid solution in gradient elution mode. The detection wavelength was at 203 nm. The flow rate was 0.4 mL x min(-1) and column temperature was set at 30 degrees C.</p><p><b>RESULT</b>Thirteen ginsenosides were determined by the established UPLC method. In 5-17th growth year ginseng leaf samples cultivated simulating wild conditions, the contents of ginsenosides in the 14th year have the highest content.</p><p><b>CONCLUSION</b>The established method is simple, accurate and reliable, can be used in ginsenosides determination and fingerprint research of Panax crude drug. The result provides reliable data for the accumulation of ginsenosides and sustainable utilization of ginseng resources.</p>

Studies on chemical constituents in root of Paeonia sinjiangensis / 中国中药杂志

<p><b>OBJECTIVE</b>To study the chemical constituents of the root of Paeonia sinjiangensis.</p><p><b>METHOD</b>The constituents were isolated by silica column chromatography, and their structures were identified on the basis of spectral analysis and their physical-chemical constants.</p><p><b>RESULT</b>Five compounds, paeoniflorin( I ), albiflorin (II), lactiflorin(III), daucosterol(IV), sucrose (V), were obtained.</p><p><b>CONCLUSION</b>All of the compounds were obtained from this plant for the first time.</p>

Three-dimensional spiral CT in advanced gastric cancer / 中华肿瘤杂志

<p><b>OBJECTIVE</b>To study the usefulness of three-dimensional spiral CT (3DCT) in the diagnosis of advanced gastric cancer (AGC).</p><p><b>METHODS</b>Between June 1999 and December 2000, 54 patients with AGC were consecutively examined. On the 3D Virtuoso workstation, source images were uploaded to create a 3DCT volume block that was then processed with volume rendering technology (VA30C) to achieve virtual-reality endoscopy (VE), clipped volume block (CVB), and ray sum (RS). After the above scanning, all the patients were examined by a two-phase enhanced spiral CT (2DCT). The visualization, manifestation, and Borrman's classification of lesions in VE, CVB, RS, and 2DCT were evaluated and correlated with gastroscopic, surgical, and pathological findings. Respiratory artifact and gastric residue were also observed.</p><p><b>RESULTS</b>(1) CVB showed the excellent visualization in 88.9% of cases, in contrast to VE and RS (50.0% and 38.9%) (P < 0.01). (2) The accuracy in evaluating mucous membrane, ulceration, lumen, wall, cardia, pylorus, and extension of the tumor were more than 90.0% except mucosa by RS (84.4%) and ulceration by VE (87.5%) or RS (81.6%) which was significantly different from CVB (96.0%) and 2DCT (96.1%) (P < 0.05). VE demonstrated an accuracy of 95.8% in diagnosis of mucosal abnormality. (3) The correct Borrman's classification was obtained in 83.3% cases by VE, 79.6% by CVB, 72.2% by RS, 88.9% by 2DCT and 85.2% by 3DCT with significant difference between 2DCT and RS (P < 0.05), but not between 3DCT and 2DCT (P > 0.05). (4) In addition to 2DCT which had no step-like artifacts, they were invisible in 53.7% of VE, 40.7% of CVB, and 81.5% of RS, with RS showing the least artifacts among 3DCT (P < 0.01). A few of gastric residues caused by pre-scanning intake of water to swallow effervescent agent could be found on 3DCT images which caused no evident influence on diagnosis.</p><p><b>CONCLUSION</b>Additional information on the diagnosis of AGC can be obtained by use of 3DCT, especially the visualization of a lesion in clipped volume block and the observation of mucosa in virtual-reality endoscopy.</p>