Estimation of the Postmortem Interval Using Chromatographic Fingerprints of Volatile Organic Compounds from Muscle

Estimation of the postmortem interval(PMI)is a crucial task in the field of forensic pathology and has unfortunately not been properly resolved.In this study,we analyzed volatile organic compounds(VOCs)in rat muscle samples collected at different PMIs and studied the feasibility of muscle VOC fingerprinting as a new method for PMI estimation.In total,110 rats were sacrificed and stored at a constant temperature(25℃).Rat skeletal muscle samples were collected at 0-10‑day postmortem,and then the VOCs were determined using a method of headspace solid‑phase microextraction coupled with gas chromatography‑mass spectrometry.The correlations between the VOCs(species and quantities)and PMIs were carefully analyzed and standard muscle VOC fingerprints at 25℃were established for different PMIs.To further test the accuracy of muscle VOC fingerprinting as a method for PMI estimation,ten additional rats with known PMIs were studied.We identified 15 kinds of VOCs and the number of VOC species increased with the PMI.The total peak areas of the VOCs increased significantly with the postmortem day(adjusted R^(2)=0.96-0.97).The mean error of the VOC fingerprinting for PMI estimation was 0.5 days and the mean relative error was 8.33%.We concluded that muscle VOC fingerprinting combining the use of VOC species and peak areas is accurate and effective and could be used as an alternative approach for PMI estimation in forensic practice.Although the preliminary results are encouraging,further studies in human cadavers under real case conditions are needed.

Evaluation of reservoir connectivity using whole-oil gas chromatographic fingerprint technology: A case study from the Es_3~3 reservoir in the Nanpu Sag, China

In this study, whole-oil gas chromatographic fingerprint analyses were performed on oils from the Es3^3 reservoir in the Liubei area of the Nanpu Sag. The gas chromatographic peaks of cyclic and branched alkanes with relatively high resolution from nCl0 to nC25 were selected to establish a database of whole-oil gas chromatographic peak height ratio fingerprints. Reservoir fluid connectivity was identified by using clustering analysis. This method can reflect the gas chromatography fingerprint information accurately and entirely, and avoid the one-sidedness of the star diagram method which only selects several fixed gas chromatographic peaks.

Study on chromatographic fingerprint of sarcandra glabra (Thunb.) by microwave-assisted extraction coupled to HPLC/DAD

Microwave-assisted extraction(MAE)was used for extraction of effective components of sarcandra glabra(Thunb.),and then chromatographic fingerprint of sarcandra glabra(Thunb.)was studied by high performance liquid chromatography/diode array detector(HPLC/DAD).The conditions of MAE were optimized by an orthogonal experiment,and then the authentication and validation of the chromatographic fingerprint were conducted.Nine peaks were identified as common peaks in the fingerprint chromatograms,and isofraxidin was considered as a reference compound and quantified.Relative standard deviations of retention time and peak area of each component were less than 3% and 8%,respectively.Similarity and difference analysis were conducted by use of PCA and relation coefficient.Twenty batches of sarcandra glabra(Thunb.)samples from two different producing areas could be classified into two different groups in the PCA model.The results showed that MAE-HPLC/DAD method was simple,efficient and stable for the study of complex chromatographic fingerprint of sarcandra glabra(Thunb.),which could provide more reliable and precise information for quality evaluation.

Quality evaluation of Huaijiao pill by chromatographic fingerprint and simultaneous determination of its major bioactive components

For quality control purpose,an approach of combining chromatographic fingerprint of Huaijiao pill（HP）and simultaneous determination of its major bioactive components was developed using high performance liquid chromatography coupled with diode array detector（HPLC-DAD）.For fingerprint analysis,16 peaks were selected as the characteristic peaks to evaluate the similarities of different samples collected from different batches of three manufacturers.The similarities of 17 Huaijiao pill samples were beyond 0.966,indicating that samples from different batches and manufacturers were,to some extent,consistent.Additionally,simultaneous quantification of seven bioactive markers,namely sophoricoside,baicalin,naringin,genistein,rutin,quercetin and 5-O-methylvisammioside,in HP was performed to interpret the quality consistency.The validation of the proposed approach was acceptable,with the accuracy of 90.2%-106.9%in recovery test.The intra-day and inter-day precisions of the method were evaluated and the RSD values were less than 2.81%.The results from the quantitative data showed that the contents of six marker compounds（except for 5-O-methylvisammioside） were quite consistent between batches produced by one manufacturer and significantly distinctive among different manufacturers.The proposed approach was expected to be developed as a powerful tool for the quality control of HP.

烟用香精的GC-MS指纹图谱

在卷烟生产中,烟用香精对卷烟的风格起着决定作用[1],所以稳定的烟用香精质量对卷烟内在品质的控制非常重要.目前,烟用香精的质量控制以物理指标[2]方法为主,对质量的变化反映不显著,给质量控制带来困难.……

Improvement of Similarity Measure： Pearson Product-Moment Correlation Coefficient

Aim To study the reason of the insensitiveness of Pearson product-momentcorrelation coefficient as a similarity measure and the method to improve its sensitivity. MethodsExperimental and simulated data sets were used. Results The distribution range of the data setsinfluences the sensitivity of Pearson product-moment correlation coefficient. Weighted Pearsonproduct-moment correlation coefficient is more sensitive when the range of the data set is large.Conclusion Weighted Pearson product-moment correlation coefficient is necessary when the range ofthe data set is large.

Chemical fingerprinting of Su-He-Xiang-Wan and attribution of major characteristic peaks for its quality control by GC-MS

A simple and facile gas chromatography-mass spectrometer （GC-MS） fingerprint of Su-He-Xiang-Wan （SHXW） was developed, the similarity analysis was conducted, and attribution of the major characteristic peaks was identified for SHXW quality control. GC-MS analysis was performed on a QP2010 instrument （Shimadzu, Japan） equipped with a capillary column of RTX-5MS. The column temperature was initiated at 50℃, held for 5 min, increased at the rate of 3 ℃/min to 120 ℃, held for 2 min, and then increased at the rate of 4 ℃/min to 220℃, held for 10 min. Helium carrier gas was used at a constant flow rate of 1.3 mL/min. Mass conditions were ionization voltage, 70 eV; injector temperature, 250℃; ion source temperature, 250 ℃; splitting ratio, 30：1; full scan mode in the 40-500 Da mass ranges with rate of 0.2 s per scan. Attribution of the major characteristic peaks was identified for SHXW by comparing the chemical standards, references of Chinese herbal medicines and the negative controls of prescription samples （NC） of SHXW. With the help of the temperature-programmed retention indices （PTRIs） used together with mass spectra and chemical standards, 25 major characteristic peaks have been identified. Nine volatile medicinal materials were identified in the prescription of SHXW by attributing to the 27 major characteristic peaks. The results demonstrate that the proposed method is a powerful approach to quality control of complex herbal medicines.

Study of Linearization of Hill Dose-Effect Curve with Metabolic Velocity Instead of Drug Concentration

Objective To explore the velocity-effect relationship in order to the establish linearization of effect on an equation with regard to the consistency of the Hill dose-effect expression with the metabolic kinetics of receptors.Methods The linear velocity-effect expression was obtained by solving multivariant differential equation groups,which were established to compare the coincidences and basic relations between the Hill dose-effect and metabolic kinetic Michaelis-Menten equation for receptors.The validation test was conducted with acetylcholine,adrenaline,and their mixture as model drugs.Results The linear velocity-effect modelling was represented in vivo or in vitro,for single and multidrug systems.Pharmacodynamic parameters,especially suitable for multicomponent CMM formulas,could be determined and calculated for single or multicomponent formulas at high saturating or low linear concentration for receptors.The validation test showed that the pharmacodynamic parameters of acetylcholine were:k,2.675×10^-3s^-1;ka,5.786×10^-9s^-1;km,2.500×10^-7s^-1;α,4.619×10^9张s·mg^-1;E0,13张(P<0.01)and those of adrenaline were:k,1.415×10^-3s^-1;ka,5.846×10^-9s^-1;km,2.300×10^-7s^-1;α,-1.627×10^9张s·m g^-1;E0,9.2张(P<0.01).For the mixture of the two components,the values were:α,1.375×1010张s·m g^-1;-6.150×10^9张s m g^-1for acetylcholine and adrenaline,respectively,and E0was7.08张in both,with the other parameters unchanged(P<0.01).Conclusion The velocity-effect equation can linearize the Hill dose-effect relationship,which can be applied to study the pharmacodynamics and availability of CMM formulations in vivo and in vitro.

High-performance liquid chromatographic fingerprint analysis of Oxytropis falcata Bunge and Oxytropis chiliophylla Royle

A simple, sensible and reliable HPLC-DAD fingerprint analysis method for the raw materials of Oxytropisfalcata and Oxytropis chiliophylla, both of which were used as ＂Er-Da-Xia＂ in Tibetan medicines, was developed and then subsequently applied to analyze samples collected from different locations or times. 19 common fingerprint peaks for O. falcata, 24 for O. chiliophylla, and 11 for the two herbs were designated respectively, including 7 identified characteristic peaks existing in both herbs and 1 uniquely presenting in O. chiliophylla. Although there were some slight differences in the chemicals of O. falcata and O. chiliophylla, the main components of both herbs were consistent generally. The results provided scientific basis, at least from the chemical point of view, for the reasonablity of two herbs being used as the same drug in Tibetan medicines and for the necessary of further investigation on their detailed chemical and pharmacological differences.

Chromatographic fingerprint analysis of Bupleuri Radix by HPLC-ELSD

To facilitate the species identification and quality assessment of Chaihu （Bupleuri Radix）, a simple and valid chromatographic fingerprint method was developed. The method uses high-performance liquid chromatography coupled with evaporative light scattering detector （HPLC-ELSD） and the data analysis is assisted by professional analytical software recommended by the State Food and Drug Administration （SFDA）. The results indicate that Nan Chaihu raw materials and Chaihu decoction pieces vary markedly in chemical quality, while Bei Chaihu raw materials are relatively more stable. Furthermore, it is obvious that Nan Chaihu is chemically very different from Bei Chaihu, suggesting that Nan Chaihu may not be suitable for medicinal use. In addition, the obvious differences between the chromatograms of decoction pieces and raw materials, especially the peaks between 30 and 40 rain and after 45 rain, indicate possible effects of the processing procedures on the chemicals. By analyzing the fingerprints of all samples, 12 main saponin-like fingerprint peaks, of which at least three are characteristic peaks of saikosaponins a, c, and d, are proposed to be considered for further characterization and quality evaluation of Chaihu.

Chromatographic fingerprint analysis and quantitative evaluate the rhizomes of Alpinia officinarum Hance(lesser galangal)

The rhizome of Alpinia officinarum Hance is a well-known traditional Chinese medicine(TCM)and has been widely used for the remedy of gastrointestinal diseases.In the present study,a simple and rapid HPLC-DAD was developed for the quality control of the rhizomes of A.officinarum.Its chemical fingerprint was established using raw material of 15 different origins in China.Similarity analysis(SA)and hierarchical clusting analysis(HCA)were applied to select the qualitative markers.Principal components analysis(PCA)was conducted to select the quantitative markers of the rhizomes of A.officinarum samples from different origins.The constituents were confirmed by(+)electrospray ionization LC-MS.12 constituents were selected as common peaks and 10 of them were confirmed by(+)electrospray ionization LC-MS.Six bioactive constituents including DPHA,galangin flavanone,galangin,galangin 3-methylether,DPHB and DPHC were simultaneous determination by using the HPLC-DAD analysis.The developed method was able to determine the bioactive components with excellent resolution,precision and recovery.The results indicated that chromatographic fingerprint combination with multi-components determination method is suitable for quality assessment of the rhizomes of A.officinarum.

Study of Tea Digitized Chromatographic Fingerprint Spectra Using Micellar Electrokinetic Chromatography

This paper described the principle of digitized chromatographic fingerprint spectrum and established digitized chromatographic fingerprint spectra of ten brands of Chinese famous tea by the micellar electrokinetic chromatography. This work was done using a 25 mmol·L -1 sodium dodecylsulfate in a 20 mmol·L -1 borate (pH 7 0) solution as running buffer, 20 kV applied potential and detection at 280 nm. The chromatographic fingerprint spectra were digitized by the relative retention value ( α ) and the relative area ( S r), and were analyzed to identify the tea samples. In the absence of the standard samples, the present method was easy setup and inexpensive, and provided the applicable information for the quality assessment of teas.

Chromatographic Fingerprint Analysis of Herbal Medicines

Thin-layer and High Performance Liquid Chromatography of Chinese Drugs Wagner H;Bauer R;Melchart D;Xiao PG;Staudinger A(Eds.) Originally published by Verlag für Ganzheitliche Medizin,Dr.Erich Wühr GmbH,2004 2nd ed.,revised,enlarged,2011,XL,1024 p.376 illus.,100 in color.In 2 volumes, not available separately Hardcover,ISBN

The spectrum-effect relationship——a rational approach to screening effective compounds, reflecting the internal quality of Chinese herbal medicine

Since the chromatographic fingerprint was introduced, it has been accepted by many countries to assess the quality and authenticity of Chinese herbal medicine （CHM）. However, solely using the chromatographic fingerprint to assay numerous chemicals is not suitable for the assessment of the whole internal quality and pharmacodynamics of CHM. Consequently, it is necessary to develop a rational approach to connecting the chromatographic fingerprint with effective components to assess the internal quality of CHM. For this purpose, a spec^tun-effect relationship theory was proposed and accepted as a new method for the assessment of CHM because of its potential use to screen effective components from CHM. In this paper, we systematically reviewed the application of the spectrum-effect relationship theory in the research of CHM, including research mentality, different chromatographic analysis techniques, data processing technologies, and structure determination.

Fingerprint analysis of Zhimu-Huangbai herb pair and simultaneous determination of its alkaloids, xanthone glycosides and steroidal saponins by HPLC-DAD-ELSD

AIM: To develop and validate a high performance liquid chromatography(HPLC) coupled with diode array and evaporative light scattering detectors(DAD-ELSD) method for the quantitative determination and fingerprint analysis of ten active constituents in three chemical classes(namely, xanthone glycosides, steroidal saponins, and alkaloids) in Zhimu-Huangbai herb pair(ZB). METHOD: Chromatographic separation was performed on a Diamonsil C18 column(4.6 mm × 250 mm, 5 μm, Dikma) by gradient elution using acetic acid in acetonitrile solution at a flow rate of 1.0 mL·min–1 at 260 nm. The drift tube temperature of ELSD was set to 60 ℃ and nebulizer gas pressure was 4.0 Bar. Method validation was performed to assure its linearity, limits of detection and quantification, precision, repeatability, stability, and accuracy. RESULTS: The HPLC-DAD-ELSD method allowed the quantification of ten compounds(phellodendrine, jatrorrhizine, palmatine, berberine, neomangiferin, mangiferin, timosaponin E-I, timosaponin B-II, timosaponin B, and timosaponin A-III), and was successfully applied to fingerprint analysis for ten batches of ZB samples. CONCLUSION: This was the first time to apply the combination of DAD and ELSD for the simultaneous determination of ten active ingredients in ZB. The results showed that the combination of quantitative analysis for marker ingredients and chemical fingerprint for the TCM herb pair provides a potentially powerful, widely introduced, and internationally accepted strategy for assessment of complex TCM formulas.

TANG Li-da

Thin-layer and High Performance Liquid Chromatography of Chinese Drugs Wagner H;Bauer R;Melchart D;Xiao PG;Staudinger A(Eds.) Originally published by Verlag für Ganzheitliche Medizin,Dr.Erich Wühr GmbH,2004 2nd ed.,revised,enlarged,2011,XL,1024 p.376 illus.,100 in color.In 2 volumes, not available separately Hardcover,ISBN 978-3-7091-0762-1