As a new technology of analyzing crude oils,comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry(GC×GCTOFMS) has received much research attention.Here we present a case s...As a new technology of analyzing crude oils,comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry(GC×GCTOFMS) has received much research attention.Here we present a case study in the Junggar Basin of NW China.Results show that the hydrocarbons,including saturates and aromatics,were all well-separated without large coelution,which cannot be realized by conventional one-dimensional GC-MS.The GC×GC technique is especially effective for analyzing aromatics and low-to-middlemolecular-weight hydrocarbons,such as diamondoids.The geochemical characteristics of crude oils in the study area were investigated through geochemical parameters extracted by GC×GC-TOFMS,improving upon the understanding obtained by GC-MS.Thus,the work here represents a new successful application of GC×GCTOFMS,showing its broad usefulness in petroleum geochemistry.展开更多
Comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry(GC×GC-TOFMS) is commercially available in the 1990s,with the characteristics of large peak capacity,high resolution,h...Comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry(GC×GC-TOFMS) is commercially available in the 1990s,with the characteristics of large peak capacity,high resolution,high sensitivity,etc.However,its application to the petroleum and geological analyses is just emerging in China and overseas.In this research,the analytical method for petroleum aromatic fraction using GC×GC-TOFMS is set up,via the choice of the column system and optimization of setting parameters,such as temperature programming,modulation time,hot pulse time,flow rate of carrier gas,data acquisition rate and data processing.The results indicate that different polar compounds of aromatic fraction distribute as bands on structured GC×GC chromatogram.Within each band,homologous compounds appear as a roof-tile structure based on the number of substituent residues.The aromatic compounds are identified and characterized according to the GC×GC chromatogram and mass spectra.According to the polarity and the number of rings,aromatic compounds are spatially present on one chromatogram,which directly reflects the distribution characteristics of complex compounds of aromatic hydrocarbons.In addition,quantitative analysis is favored as some overlapped peaks on traditional GC-MS chromatogram have been separated completely on GC×GC.Some heterocyclic atom aromatic compounds at trace level can be clearly identified using this method,for polarity differences from other interfered aromatic compounds.The development of this method and chromatogram recognition offer petroleum geologists a practical example for the application performance of GC×GC-TOFMS.展开更多
To investigate the chemical transformation of volatile compounds in sulfur-fumigated Radix Angelicae Sinensis. A comprehensive two-dimensional gas chromatography (GCxGC) and high-resolution time-of-flight mass spectro...To investigate the chemical transformation of volatile compounds in sulfur-fumigated Radix Angelicae Sinensis. A comprehensive two-dimensional gas chromatography (GCxGC) and high-resolution time-of-flight mass spectrometry (HR-TOF/MS) with colorized fuzzy difference (CFD) method was used to investigate the effect of sulfur-fumigation on the volatile components from Radix Angelicae Sinensis. Twenty-five compounds that were found in sun-dried samples disappeared in sulfur-fumigated samples. Seventeen volatile components including two sulfur-containing compounds were newly generated for the first time in volatile oils of sulfur-fumigated Radix Angelicae Sinensis. The strategy can be successfully applied to rapidly and holistically discriminate sun-dried and sulfur-fumigated Radix Angelicae Sinensis. GCxGC-HR-TOF/MS based CFD is a powerful and feasible approach for the global quality evaluation of Radix Angelicae Sinensis as well as other herbal medicines.展开更多
Objectives:The ageing process has a significant impact on the aroma of Chinese Baijiu,which could strengthen the desirable flavor characteristics and reduce the undesirable ones.The aim of this study was to observe th...Objectives:The ageing process has a significant impact on the aroma of Chinese Baijiu,which could strengthen the desirable flavor characteristics and reduce the undesirable ones.The aim of this study was to observe the in itiation of mean in gful cha nges in volatile fracti on and locate the ageing markers during ageing storage of Chinese Highland Qingke Baijiu.Materials and Methods:Samples of Chinese Qingke Baijiu were aged for 0,1,2,3,4,5,6,7,8,9,10,and 11 mon ths before an alysis.The samples were isolated by liquid-liquid extraction and then analyzed by comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry.The acquired data were processed by untargeted and targeted metabolomics approach to locate the ageing markers.Results:The untargeted metabolomics analysis(hierarchical clustering analysis,HCA)shows that the chemical composition of Qingke Baijiu presents a statistically sigrdficant deviation from the reference scenario after 5 mon ths.Subsequently,supervised statistics analysis(orthogo nal partial least squares discrimination analysis)was performed to locate the markers,which changed sigrdficantly during ageing.Fifteen markers were located,and seven of them were acetals.Notably,1,1-diethoxy-propane,1,1-diethoxy-butane,and 1,1-diethoxy-3-methyl-butane are important contributors to the flavor of Chinese Baijiu.The identified markers were applied for the untargeted metabolomics(HCA),and the results revealed that these markers could divide the Qingke Baijiu into two ageing stages,0-5 months and 6-11 months.Conclusion:The results suggest that it is a valuable tool for monitoring the changes of volatile compounds and locating the age markers in Chinese Baijiu.展开更多
he use of an absorption trap off-line two-dimensional gas chromatography (2-DGC) in conjunction with a mass spectrometer greatly improved the separation andidefitification of minor constituents of a complex mixture su...he use of an absorption trap off-line two-dimensional gas chromatography (2-DGC) in conjunction with a mass spectrometer greatly improved the separation andidefitification of minor constituents of a complex mixture such as a natural essentialoil. The absorption trap device used as an interface of 2-DGC offered the advantageof convenient manipulation.展开更多
Comprehensive two-dimensional liquid chromatography platform(LC×LC)coupled with quadrupole time-of-flight(QTOF)mass spectrometry(MS)is developed to separate,identify and relatively determine the chemical constitu...Comprehensive two-dimensional liquid chromatography platform(LC×LC)coupled with quadrupole time-of-flight(QTOF)mass spectrometry(MS)is developed to separate,identify and relatively determine the chemical constituents of two types of tripterygium glycosides tablets(TGT).The types and relative contents of the constituents discovered in two kinds of TGT tablets were subsequently compared.C8andC18 column were used for the separation of the first展开更多
The Dabei gas field in the Kuqa Depression of the Tarim Basin is the most complex and deep continental condensate gas field in China. Comprehensive two-dimensional gas chromatography?time of flight mass spectrometer (...The Dabei gas field in the Kuqa Depression of the Tarim Basin is the most complex and deep continental condensate gas field in China. Comprehensive two-dimensional gas chromatography?time of flight mass spectrometer (GC×GC-TOFMS) analysis was conducted on five condensate oil samples from this field. The results show that the samples have n-alkane series in complete preservation and rich adamantanes. According to the methyladamantane index, the condensate oil is the product of the source rock with vitrinite reflectance (Ro) of 1.3%–1.6%. According to the gas maturity calculated through carbon isotope and vitrinite reflectance, the natural gas is corresponding to Ro of 1.3%–1.7%, reflecting that the natural gas and condensate oil are basically formed during the same period at the high maturity stage of source rock. The Dabei gas field has favorable geological conditions for hydrocarbon accumulation: thick salt rock in the Paleogene acts as a regional high-quality caprock directly overlying the high-quality sandstone reservoir of the Cretaceous, the coal source rocks have high hydrocarbon generation intensity and provide continuous oil and gas, and the subsalt thrust structures develop in rows with rich faults, providing migration pathways for oil and gas migration. These factors together controlled the formation of the Dabei gas field.展开更多
Traditional Chinese medicines(TCMs)possess a rich historical background,unique theoretical framework,remarkable therapeutic efficacy,and abundant resources.However,the modernization and internationalization of TCMs ha...Traditional Chinese medicines(TCMs)possess a rich historical background,unique theoretical framework,remarkable therapeutic efficacy,and abundant resources.However,the modernization and internationalization of TCMs have faced significant obstacles due to their diverse ingredients and unknown mechanisms.To gain deeper insights into the phytochemicals and ensure the quality control of TCMs,there is an urgent need to enhance analytical techniques.Currently,two-dimensional(2D)chromatography,which incorporates two independent separation mechanisms,demonstrates superior separation capabilities compared to the traditional one-dimensional(1D)separation system when analyzing TCMs samples.Over the past decade,new techniques have been continuously developed to gain actionable insights from complex samples.This review presents the recent advancements in the application of multidimensional chromatography for the quality evaluation of TCMs,encompassing 2D-gas chromatography(GC),2D-liquid chromatography(LC),as well as emerging three-dimensional(3D)-GC,3D-LC,and their associated data-processing approaches.These studies highlight the promising potential of multidimensional chromatographic separation for future phytochemical analysis.Nevertheless,the increased separation capability has resulted in higher-order data sets and greater demands for data-processing tools.Considering that multidimensional chromatography is still a relatively nascent research field,further hardware enhancements and the implementation of chemometric methods are necessary to foster its robust development.展开更多
Genetic algorithm and partial least square(GA-PLS),kernel PLS(KPLS) and Levenberg-Marquardt artificial neural network(L-M ANN) techniques were used to investigate the correlation between retention time(RT) and...Genetic algorithm and partial least square(GA-PLS),kernel PLS(KPLS) and Levenberg-Marquardt artificial neural network(L-M ANN) techniques were used to investigate the correlation between retention time(RT) and descriptors for 15 nanoparticle compounds obtained by the comprehensive two-dimensional gas chromatography system(GC × GC).Application of the dodecanethiol monolayer-protected gold nanoparticle(MPN) column was for a high-speed separation as the second column of GC × GC.The L-M ANN model with the final optimum network architecture of [13-5-1] gave a significantly better performance than the other models.This is the first research on the quantitative structure-retention relationship(QSRR) of nanoparticle compounds using the GA-PLS,GA-KPLS and L-M ANN.展开更多
Heavy biodegraded crude oils have larger numbers of coeluting compounds than nonbiodegraded oils, and they are typically not resolved with conventional gas chromatography(GC). This unresolved complex mixture(UCM) ...Heavy biodegraded crude oils have larger numbers of coeluting compounds than nonbiodegraded oils, and they are typically not resolved with conventional gas chromatography(GC). This unresolved complex mixture(UCM) has been investigated using comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry(GC×GC-To FMS) within a set of biodegraded petroleums derived from distinct sedimentary basins, including northwestern Sichuan(Neoproterozoic, marine), Tarim(Early Paleozoic, marine), Bohai Bay(Eocene, saline/brackish) and Pearl River Mouth(Eocene, freshwater). In general, the hydrocarbons that constitute the UCM in petroleum saturate fractions can be classified into three catalogues based on the distributions of resolved compounds on two dimensional chromatograms. Group 1 is composed mainly of normal and branched alkanes, isoprenoid alkanes and monocyclic alkanes; Group 2 comprises primarily terpanes ranging from two to five rings, and Group 3 is dominated by monoaromatic hydrocarbons such as tetralins and monoaromatic steranes. In addition, the UCM is source dependent and varies between oil populations. i.e., the UCM of petroleum derived from Precambrian and Early Paleozoic marine, Eocene saline/brackish and freshwater source rocks is specifically rich in higher homologues of A-norsteranes, series of 1,1,3-trimethyl-2-alkylcyclohexanes(carotenoid-derived alkanes), and tetralin and indane compounds, respectively.展开更多
The cause of black-streak defects on food-container screw caps is analyzed by two-dimensional gas chromatography time-of-flight mass spectrometry,morphological analysis,and energy-dispersive X-ray spectroscopy.An imme...The cause of black-streak defects on food-container screw caps is analyzed by two-dimensional gas chromatography time-of-flight mass spectrometry,morphological analysis,and energy-dispersive X-ray spectroscopy.An immersion experiment was conducted with the cap immersed in different concentrations of acetic acid to simulate the growth of black streaks.The experimental results show that the acetic acid concentration in food is closely related to the appearance of the black-streak defects.Acetic acid is speculated to permeate into the gaps of the cap,followed by the formation of ferric acetate(light brown solid).The ferric acetate then breaks through the paint surface and its color coincides with that of the paint,which leads to the formation of the black-streak defects.展开更多
基金funded by the Major State Basic Research Development Program of China(973 project,Grant No.2012CB214803)National Science and Technology Major Project of China(Grant No. 2016ZX05003-005)National Natural Science Foundation of China(Grant Nos.41322017 and 41472100)
文摘As a new technology of analyzing crude oils,comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry(GC×GCTOFMS) has received much research attention.Here we present a case study in the Junggar Basin of NW China.Results show that the hydrocarbons,including saturates and aromatics,were all well-separated without large coelution,which cannot be realized by conventional one-dimensional GC-MS.The GC×GC technique is especially effective for analyzing aromatics and low-to-middlemolecular-weight hydrocarbons,such as diamondoids.The geochemical characteristics of crude oils in the study area were investigated through geochemical parameters extracted by GC×GC-TOFMS,improving upon the understanding obtained by GC-MS.Thus,the work here represents a new successful application of GC×GCTOFMS,showing its broad usefulness in petroleum geochemistry.
基金sponsored by the Science and Technology Management Department of China National Petroleum Corporation
文摘Comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry(GC×GC-TOFMS) is commercially available in the 1990s,with the characteristics of large peak capacity,high resolution,high sensitivity,etc.However,its application to the petroleum and geological analyses is just emerging in China and overseas.In this research,the analytical method for petroleum aromatic fraction using GC×GC-TOFMS is set up,via the choice of the column system and optimization of setting parameters,such as temperature programming,modulation time,hot pulse time,flow rate of carrier gas,data acquisition rate and data processing.The results indicate that different polar compounds of aromatic fraction distribute as bands on structured GC×GC chromatogram.Within each band,homologous compounds appear as a roof-tile structure based on the number of substituent residues.The aromatic compounds are identified and characterized according to the GC×GC chromatogram and mass spectra.According to the polarity and the number of rings,aromatic compounds are spatially present on one chromatogram,which directly reflects the distribution characteristics of complex compounds of aromatic hydrocarbons.In addition,quantitative analysis is favored as some overlapped peaks on traditional GC-MS chromatogram have been separated completely on GC×GC.Some heterocyclic atom aromatic compounds at trace level can be clearly identified using this method,for polarity differences from other interfered aromatic compounds.The development of this method and chromatogram recognition offer petroleum geologists a practical example for the application performance of GC×GC-TOFMS.
基金Supported by the National Natural Science Foundation of China(No.81173546 and No.30940093)the Natural Science Foundation of Jiangsu Province,China(No.BK2009495)+4 种基金the International Science and Technology Cooperation Project of Jiangsu Province,China(No.BZ2011053)the Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD,No.2011ZYX2-001)the Postgraduate Research Innovation Project of Jiangsu Higher Education Institutions(No.KYLX_0975)the Chinese Medicine Research Program of Zhejiang Province,China(No.2014ZQ008)the Science Foundation of Zhejiang Chinese Medical University(No.2013ZZ12)
文摘To investigate the chemical transformation of volatile compounds in sulfur-fumigated Radix Angelicae Sinensis. A comprehensive two-dimensional gas chromatography (GCxGC) and high-resolution time-of-flight mass spectrometry (HR-TOF/MS) with colorized fuzzy difference (CFD) method was used to investigate the effect of sulfur-fumigation on the volatile components from Radix Angelicae Sinensis. Twenty-five compounds that were found in sun-dried samples disappeared in sulfur-fumigated samples. Seventeen volatile components including two sulfur-containing compounds were newly generated for the first time in volatile oils of sulfur-fumigated Radix Angelicae Sinensis. The strategy can be successfully applied to rapidly and holistically discriminate sun-dried and sulfur-fumigated Radix Angelicae Sinensis. GCxGC-HR-TOF/MS based CFD is a powerful and feasible approach for the global quality evaluation of Radix Angelicae Sinensis as well as other herbal medicines.
基金supported by the National Key Research and Development Program of China(2016YFD0400500)the National Natural Science Foundation of China(No.32001826).
文摘Objectives:The ageing process has a significant impact on the aroma of Chinese Baijiu,which could strengthen the desirable flavor characteristics and reduce the undesirable ones.The aim of this study was to observe the in itiation of mean in gful cha nges in volatile fracti on and locate the ageing markers during ageing storage of Chinese Highland Qingke Baijiu.Materials and Methods:Samples of Chinese Qingke Baijiu were aged for 0,1,2,3,4,5,6,7,8,9,10,and 11 mon ths before an alysis.The samples were isolated by liquid-liquid extraction and then analyzed by comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry.The acquired data were processed by untargeted and targeted metabolomics approach to locate the ageing markers.Results:The untargeted metabolomics analysis(hierarchical clustering analysis,HCA)shows that the chemical composition of Qingke Baijiu presents a statistically sigrdficant deviation from the reference scenario after 5 mon ths.Subsequently,supervised statistics analysis(orthogo nal partial least squares discrimination analysis)was performed to locate the markers,which changed sigrdficantly during ageing.Fifteen markers were located,and seven of them were acetals.Notably,1,1-diethoxy-propane,1,1-diethoxy-butane,and 1,1-diethoxy-3-methyl-butane are important contributors to the flavor of Chinese Baijiu.The identified markers were applied for the untargeted metabolomics(HCA),and the results revealed that these markers could divide the Qingke Baijiu into two ageing stages,0-5 months and 6-11 months.Conclusion:The results suggest that it is a valuable tool for monitoring the changes of volatile compounds and locating the age markers in Chinese Baijiu.
文摘he use of an absorption trap off-line two-dimensional gas chromatography (2-DGC) in conjunction with a mass spectrometer greatly improved the separation andidefitification of minor constituents of a complex mixture such as a natural essentialoil. The absorption trap device used as an interface of 2-DGC offered the advantageof convenient manipulation.
文摘Comprehensive two-dimensional liquid chromatography platform(LC×LC)coupled with quadrupole time-of-flight(QTOF)mass spectrometry(MS)is developed to separate,identify and relatively determine the chemical constituents of two types of tripterygium glycosides tablets(TGT).The types and relative contents of the constituents discovered in two kinds of TGT tablets were subsequently compared.C8andC18 column were used for the separation of the first
基金Supported by the China National Science and Technology Major Project(2016ZX05004-004)
文摘The Dabei gas field in the Kuqa Depression of the Tarim Basin is the most complex and deep continental condensate gas field in China. Comprehensive two-dimensional gas chromatography?time of flight mass spectrometer (GC×GC-TOFMS) analysis was conducted on five condensate oil samples from this field. The results show that the samples have n-alkane series in complete preservation and rich adamantanes. According to the methyladamantane index, the condensate oil is the product of the source rock with vitrinite reflectance (Ro) of 1.3%–1.6%. According to the gas maturity calculated through carbon isotope and vitrinite reflectance, the natural gas is corresponding to Ro of 1.3%–1.7%, reflecting that the natural gas and condensate oil are basically formed during the same period at the high maturity stage of source rock. The Dabei gas field has favorable geological conditions for hydrocarbon accumulation: thick salt rock in the Paleogene acts as a regional high-quality caprock directly overlying the high-quality sandstone reservoir of the Cretaceous, the coal source rocks have high hydrocarbon generation intensity and provide continuous oil and gas, and the subsalt thrust structures develop in rows with rich faults, providing migration pathways for oil and gas migration. These factors together controlled the formation of the Dabei gas field.
基金This work is financially supported by the Hunan 2011 Collaborative Innovation Center of Chemical Engineering&Technology with Environmental Benignity and Effective Resource UtilizationAdditional funding was provided by the Hunan Province Natural Science Fund(No.2020JJ4569 and 2023JJ60378)the Hunan Province College Students’Innovation and Entrepreneurship Training Program(No.S202110530044 and S202210530048).
文摘Traditional Chinese medicines(TCMs)possess a rich historical background,unique theoretical framework,remarkable therapeutic efficacy,and abundant resources.However,the modernization and internationalization of TCMs have faced significant obstacles due to their diverse ingredients and unknown mechanisms.To gain deeper insights into the phytochemicals and ensure the quality control of TCMs,there is an urgent need to enhance analytical techniques.Currently,two-dimensional(2D)chromatography,which incorporates two independent separation mechanisms,demonstrates superior separation capabilities compared to the traditional one-dimensional(1D)separation system when analyzing TCMs samples.Over the past decade,new techniques have been continuously developed to gain actionable insights from complex samples.This review presents the recent advancements in the application of multidimensional chromatography for the quality evaluation of TCMs,encompassing 2D-gas chromatography(GC),2D-liquid chromatography(LC),as well as emerging three-dimensional(3D)-GC,3D-LC,and their associated data-processing approaches.These studies highlight the promising potential of multidimensional chromatographic separation for future phytochemical analysis.Nevertheless,the increased separation capability has resulted in higher-order data sets and greater demands for data-processing tools.Considering that multidimensional chromatography is still a relatively nascent research field,further hardware enhancements and the implementation of chemometric methods are necessary to foster its robust development.
文摘Genetic algorithm and partial least square(GA-PLS),kernel PLS(KPLS) and Levenberg-Marquardt artificial neural network(L-M ANN) techniques were used to investigate the correlation between retention time(RT) and descriptors for 15 nanoparticle compounds obtained by the comprehensive two-dimensional gas chromatography system(GC × GC).Application of the dodecanethiol monolayer-protected gold nanoparticle(MPN) column was for a high-speed separation as the second column of GC × GC.The L-M ANN model with the final optimum network architecture of [13-5-1] gave a significantly better performance than the other models.This is the first research on the quantitative structure-retention relationship(QSRR) of nanoparticle compounds using the GA-PLS,GA-KPLS and L-M ANN.
基金funded by the National Natural Science Foundation of China(Grant No.41172126)the State Key Laboratory of Petroleum Resources and Prospecting(PRP/indep-2-1402)
文摘Heavy biodegraded crude oils have larger numbers of coeluting compounds than nonbiodegraded oils, and they are typically not resolved with conventional gas chromatography(GC). This unresolved complex mixture(UCM) has been investigated using comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry(GC×GC-To FMS) within a set of biodegraded petroleums derived from distinct sedimentary basins, including northwestern Sichuan(Neoproterozoic, marine), Tarim(Early Paleozoic, marine), Bohai Bay(Eocene, saline/brackish) and Pearl River Mouth(Eocene, freshwater). In general, the hydrocarbons that constitute the UCM in petroleum saturate fractions can be classified into three catalogues based on the distributions of resolved compounds on two dimensional chromatograms. Group 1 is composed mainly of normal and branched alkanes, isoprenoid alkanes and monocyclic alkanes; Group 2 comprises primarily terpanes ranging from two to five rings, and Group 3 is dominated by monoaromatic hydrocarbons such as tetralins and monoaromatic steranes. In addition, the UCM is source dependent and varies between oil populations. i.e., the UCM of petroleum derived from Precambrian and Early Paleozoic marine, Eocene saline/brackish and freshwater source rocks is specifically rich in higher homologues of A-norsteranes, series of 1,1,3-trimethyl-2-alkylcyclohexanes(carotenoid-derived alkanes), and tetralin and indane compounds, respectively.
文摘The cause of black-streak defects on food-container screw caps is analyzed by two-dimensional gas chromatography time-of-flight mass spectrometry,morphological analysis,and energy-dispersive X-ray spectroscopy.An immersion experiment was conducted with the cap immersed in different concentrations of acetic acid to simulate the growth of black streaks.The experimental results show that the acetic acid concentration in food is closely related to the appearance of the black-streak defects.Acetic acid is speculated to permeate into the gaps of the cap,followed by the formation of ferric acetate(light brown solid).The ferric acetate then breaks through the paint surface and its color coincides with that of the paint,which leads to the formation of the black-streak defects.