Exhaled ammonia(NH_(3))is an essential noninvasive biomarker for disease diagnosis.In this study,an acetone-modifier positive photoionization ion mobility spectrometry(AM-PIMS)method was developed for accurate qualita...Exhaled ammonia(NH_(3))is an essential noninvasive biomarker for disease diagnosis.In this study,an acetone-modifier positive photoionization ion mobility spectrometry(AM-PIMS)method was developed for accurate qualitative and quantitative analysis of exhaled NH_(3)with high selectivity and sensitivity.Acetone was introduced into the drift tube along with the drift gas as a modifier,and the characteristic NH_(3)product ion peak of(C_(3)H_(6)O)_(4)NH_(4)^(+)(K_(0)=1.45 cm^(2)/V·s)was obtained through the ion-molecule reaction with acetone reactant ions(C_(3)H_(6)O)_(2)H^(+)(K_(0)=1.87 cm^(2)/V·s),which significantly increased the peak-to-peak resolution and improved the accuracy of exhaled NH_(3)qualitative identification.Moreover,the interference of high humidity and the memory effect of NH_(3)molecules were significantly reduced via online dilution and purging sampling,thus realizing breath-by-breath measurement.As a result,a wide quantitative range of 5.87-140.92μmol/L with a response time of 40 ms was achieved,and the exhaled NH_(3)profile could be synchronized with the concentration curve of exhaled CO_(2).Finally,the analytical capacity of AM-PIMS was demonstrated by measuring the exhaled NH_(3)of healthy subjects,demonstrating its great potential for clinical disease diagnosis.展开更多
Ion mobility spectrometry (IMS) is a very fast, highly sensitive, and inexpensive technique, it permits efficient monitoring of volatile organic compounds like alcohols. In this article, positive ion mobility spectr...Ion mobility spectrometry (IMS) is a very fast, highly sensitive, and inexpensive technique, it permits efficient monitoring of volatile organic compounds like alcohols. In this article, positive ion mobility spectra for six alcohol organic compounds have been systematically studied for the first time using a high-resolution IMS apparatus equipped with a discharge ionization source. Utilizing protonated water cluster ions (H2O)nH^+ as the reactant ions and clean air as the drift gas, alcohol organic compounds, ethanol, 1- propanol, 2-propanol, 1-butanol, 1-pentanol and 2-octanol, all exhibit product ion characteristic peaks in their respective ion mobility spectrometry, that is a result of proton transfer reactions between the alcohols and reaction ions (H2O)nH^+. The mixture of these alcohols, including two isomers, has been detected, and the results showed that they could be distinguished effectively in the ion mobility spectrum. The reduced mobility values have been determined, which are in very well agreement with the traditional ^63Ni-IMS experimental values. The exponential dilution method was used to calibrate the alcohol concentrations, and a detection limit available for the alcohols is in order of magnitude of a few ng/L.展开更多
To ensure authenticity of sesame oil,an authentication technology was proposed using ion mobility spectrometry(IMS)and chemometrics.One-class classification(OCC)methods including one-class partial least squares(OCPLS)...To ensure authenticity of sesame oil,an authentication technology was proposed using ion mobility spectrometry(IMS)and chemometrics.One-class classification(OCC)methods including one-class partial least squares(OCPLS)and one-class support vector machine(OCSVM)were employed to build authentication models for sesame oil.Subsequently,an independent test set was used to validate the constructed models.Validation set of 45 adulterated oils indicated that prediction correction rate of OCPLS model reached 95.6%(43 out of 45).Moreover,the complete set of sesame oils adulterated by sesame oil essence could be identified as counterfeit.Compared with previous studies,OCPLS model could work to identify untargeted adulteration.In conclusion,OCC method could effectively detect adulterated sesame oils containing as little as 10%other vegetable oils.This study provided a rapid screening method for adulterated sesame oil in market surveillance and a reference for developing authentication methods of other edible oils.展开更多
Cancer cell spheroids(CCS) are a valuable three-dimensional cell model in cancer studies because they could replicate numerous characteristics of solid tumors. Increasing researches have used matrix-assisted laser des...Cancer cell spheroids(CCS) are a valuable three-dimensional cell model in cancer studies because they could replicate numerous characteristics of solid tumors. Increasing researches have used matrix-assisted laser desorption/ionization mass spectrometry imaging(MALDI-MSI) to investigate the spatial distribution of endogenous compounds(e.g., lipids) in CCS. However, only limited lipid species can be detected owing to a low ion yield by using MALDI. Besides, it is still challenging to fully characterize the structural diversity of lipids due to the existence of isomeric/isobaric species. Here, we carried out the initial application of MALDI coupled with laser-postionization(MALDI-2) and trapped ion mobility spectrometry(TIMS) imaging in HCT116 colon CCS to address these challenges. We demonstrated that MALDI-2 is capable of detecting more number and classes of lipids in HCT116 colon CCS with higher signal intensities than MALDI. TIMS could successfully separate numerous isobaric/isomeric species of lipids in CCS. Interestingly, we found that some isomeric/isobaric species have totally different spatial distributions in colon CCS. Further MS/MS imaging analysis was employed to determine the compositions of fatty acid chains for isomeric species by examining disparities in signal intensities and spatial distributions of product ions. This work stresses the robust ability of TIMS and MALDI-2 imaging in analyzing endogenous lipids in CCS, which could potentially become powerful tools for future cancer studies.展开更多
The complex composition of herbal metabolites necessitates the development of powerful analytical techniques aimed to identify the bioactive components.The seeds of Descurainia sophia(SDS)are utilized in China as a co...The complex composition of herbal metabolites necessitates the development of powerful analytical techniques aimed to identify the bioactive components.The seeds of Descurainia sophia(SDS)are utilized in China as a cough and asthma relieving agent.Herein,a dimension-enhanced integral approach,by combining ultra-high performance liquid chromatography/ion mobility-quadrupole time-of-flight mass spectrometry(UHPLC/IMQTOF-MS)and intelligent peak annotation,was developed to rapidly characterize the multicomponents from SDS.Good chromatographic separation was achieved within 38 min on a UPLC CSH C18(2.1×100 mm,1.7μm)column which was eluted by 0.1%formic acid in water(water phase)and acetonitrile(organic phase).Collision-induced dissociation-MS^(2)data were acquired by the data-independent high-definition MS^(E)(HDMS^(E))in both the negative and positive electrospray ionization modes.A major components knockout strategy was applied to improve the characterization of those minor ingredients by enhancing the injection volume.Moreover,a self-built chemistry library was established,which could be matched by the UNIFI software enabling automatic peak annotation of the obtained HDMS^(E)data.As a result of applying the intelligent peak annotation workflows and further confirmation process,a total of 53 compounds were identified or tentatively characterized from the SDS,including 29 flavonoids,one uridine derivative,four glucosides,one lignin,one phenolic compound,and 17 others.Notably,four-dimensional information related to the structure(e.g.,retention time,collision cross section,MS^(1)and MS^(2)data)was obtained for each component by the developed integral approach,and the results would greatly benefit the quality control of SDS.展开更多
Based on two-dimensional topological structures, a novel molecular electronegativity interaction vector with hybridization (MEHIV) was developed to describe atomic hybridization state in different molecular environm...Based on two-dimensional topological structures, a novel molecular electronegativity interaction vector with hybridization (MEHIV) was developed to describe atomic hybridization state in different molecular environments. Five quantitative models by MEHIV characterization and multiple linear regression modeling were successfully established to predict reduced ion mobility constants (Ko) of alkanes, aromatic hydrocarbons, fatty alcohols, fatty aldehydes and ketones and carboxylic esters. The correlation coefficients Roy by leave-one-out cross-validation are 0.792, 0.787, 0,949, 0.972 and 0.981, respectively, and the standard deviations SDcv are 0.067, 0.086, 0.064, 0.043 and 0.042, respectively. These results suggested that MEHIV is an excellent topological index descriptor with many advantages such as straightforward physicochemical meaning, high characterization competence, convenient expansibility and easy manipulation.展开更多
Herbal components characterization represents a challenging task because of the co-existing of multiple classes of naturally occurring compounds with wide spans of polarity,molecular mass,and the ubiquitous isomerism....Herbal components characterization represents a challenging task because of the co-existing of multiple classes of naturally occurring compounds with wide spans of polarity,molecular mass,and the ubiquitous isomerism.The root and rhizome of Salvia miltiorrhiza have been utilized as a reputable traditional Chinese medicine Salviae Miltiorrhizae Radix et Rhizoma(Dan-Shen)in the treatment of cardiovascular disease.Herein,a dimensionenhanced ultra-high performance liquid chromatography/ion mobility/quadrupole time-of-flight mass spectrometry approach in combination with intelligent peak annotation workflows was established aimed to rapidly characterize the multicomponents from S.miltiorrhiza.Due to the sufficient optimization,satisfactory chromatography separation was enabled on an HSS T3 column within 33 min using 0.1%formic acid in water(A)and acetonitrile(B)as the mobile phase,while the data-independent HDMS^(E) in both the negative and positive electrospray ionization modes was utilized for the high-coverage MS^(2) data acquisition.Streamlined automatic peak annotation by searching an in-house library(recording 198 known compounds)followed by the subsequent confirming steps(e.g.,comparison with the reference compounds,fragmentation pathways analysis,and retention behavior comparison,etc.),allowed us to identify or tentatively characterize a total of 86 components(including 50 terpenoids,21 phenolic acids,and 15 others)from S.miltiorrhiza.Importantly,three-dimensional structure information,such as the retention time,MS^(1) and MS^(2) data,and collision cross section(CCS),was provided,which can facilitate the more reliable characterization of herbal components.展开更多
Objective:Quality control of traditional Chinese medicine(TCM)begins with the chemical basis elucidation.The root of Stephania tetrandra has long been utilized as an antirheumatic,analgesic,and diuretic TCM,Stephaniae...Objective:Quality control of traditional Chinese medicine(TCM)begins with the chemical basis elucidation.The root of Stephania tetrandra has long been utilized as an antirheumatic,analgesic,and diuretic TCM,Stephaniae Tetrandrae Radix(STR;Fang-Ji).Powerful analytical strategies enabling its multicomponent characterization is still rare.Methods:A rapid,reliable,and enhanced profiling approach,by ultra-high performance liquid chromatography coupled with ion mobility/quadrupole time-of-flight mass spectrometry(UHPLC/IM-QTOF-MS)and automatic peak annotation facilitated by computational matching of in-house library,was established and utilized to characterize the multicomponents from STR.A knockout strategy was utilized by automated valve switching to overcome the interference of predominant peaks.Results:Good chromatographic separation was achieved within 17 min on a reversed-phase BEH C18 column eluted with acetonitrile/0.1%ammonium hydroxide in water,while data-independent high-definition MS^(E)(HDMS^(E))in positive mode was applied to acquire the MS^(2)data by using a Vion TM IM-QTOF instrument,which in theory,could cover all the profiled precursor ions.An in-house library of 163 compounds was established and incorporated into the UNIFITM platform.By feat of these efforts,we were able to identify or tentatively characterize 76 alkaloids from the methanolic extract of STR,including 14 aporphine-type,four morphine-type,48 bisbenzylisoquinoline-type,seven tetrahydroprotoberberine-type,one protopine-type,one benzylisoquinoline-type,and one other.Four-dimensional information,such as the retention time,collision cross section(CCS),high-accuracy MS1 and MS2 data,for each component was provided.Conclusions:The systematic multicomponent characterization of STR was accomplished with high coverage,high degree of automation,and high reliability.展开更多
基金This work was supported by the National Natural Science Foundation of China(Grant Nos.:22027804,21974141,and 21904125)Natural Science Foundation of Liaoning Province(Grant Nos.:2022-MS-019 and 2022-MS-016)+2 种基金Science and Technology Innovation Foundation of Dalian(Grant No.:2022JJ13SN096)Dalian Institute of Chemical Physics(Grant Nos.:DICP I202141 and DICP I202144)1+X Program for Large Cohort Study-Clinical Research Incubation Project,The Second Hospital of Dalian Medical University(Project No.:2022DXDL01).
文摘Exhaled ammonia(NH_(3))is an essential noninvasive biomarker for disease diagnosis.In this study,an acetone-modifier positive photoionization ion mobility spectrometry(AM-PIMS)method was developed for accurate qualitative and quantitative analysis of exhaled NH_(3)with high selectivity and sensitivity.Acetone was introduced into the drift tube along with the drift gas as a modifier,and the characteristic NH_(3)product ion peak of(C_(3)H_(6)O)_(4)NH_(4)^(+)(K_(0)=1.45 cm^(2)/V·s)was obtained through the ion-molecule reaction with acetone reactant ions(C_(3)H_(6)O)_(2)H^(+)(K_(0)=1.87 cm^(2)/V·s),which significantly increased the peak-to-peak resolution and improved the accuracy of exhaled NH_(3)qualitative identification.Moreover,the interference of high humidity and the memory effect of NH_(3)molecules were significantly reduced via online dilution and purging sampling,thus realizing breath-by-breath measurement.As a result,a wide quantitative range of 5.87-140.92μmol/L with a response time of 40 ms was achieved,and the exhaled NH_(3)profile could be synchronized with the concentration curve of exhaled CO_(2).Finally,the analytical capacity of AM-PIMS was demonstrated by measuring the exhaled NH_(3)of healthy subjects,demonstrating its great potential for clinical disease diagnosis.
基金Project supported by the National Natural Science Foundation of China(No.20577049)the Excellent Youth Foundation of Anhui Province Scientific Committee(No.06045098)the Hefei Institues of Physical Science,Chinese Academy of Sciences.
文摘Ion mobility spectrometry (IMS) is a very fast, highly sensitive, and inexpensive technique, it permits efficient monitoring of volatile organic compounds like alcohols. In this article, positive ion mobility spectra for six alcohol organic compounds have been systematically studied for the first time using a high-resolution IMS apparatus equipped with a discharge ionization source. Utilizing protonated water cluster ions (H2O)nH^+ as the reactant ions and clean air as the drift gas, alcohol organic compounds, ethanol, 1- propanol, 2-propanol, 1-butanol, 1-pentanol and 2-octanol, all exhibit product ion characteristic peaks in their respective ion mobility spectrometry, that is a result of proton transfer reactions between the alcohols and reaction ions (H2O)nH^+. The mixture of these alcohols, including two isomers, has been detected, and the results showed that they could be distinguished effectively in the ion mobility spectrum. The reduced mobility values have been determined, which are in very well agreement with the traditional ^63Ni-IMS experimental values. The exponential dilution method was used to calibrate the alcohol concentrations, and a detection limit available for the alcohols is in order of magnitude of a few ng/L.
基金This work was supported by the National Science and Technology Major Project of China(2017YFC1601700)the National Nature Foundation Committee of P.R.China(31871886)+2 种基金the National Major Project for Agro-product Quality&Safety Risk Assessment(GJFP2019003)the earmarked fund for China Agricultural Research System(CARS-12)the Fundamental Research Funds for Central Non-profit Scientific Institution(1610172018002 and 1610172018012).
文摘To ensure authenticity of sesame oil,an authentication technology was proposed using ion mobility spectrometry(IMS)and chemometrics.One-class classification(OCC)methods including one-class partial least squares(OCPLS)and one-class support vector machine(OCSVM)were employed to build authentication models for sesame oil.Subsequently,an independent test set was used to validate the constructed models.Validation set of 45 adulterated oils indicated that prediction correction rate of OCPLS model reached 95.6%(43 out of 45).Moreover,the complete set of sesame oils adulterated by sesame oil essence could be identified as counterfeit.Compared with previous studies,OCPLS model could work to identify untargeted adulteration.In conclusion,OCC method could effectively detect adulterated sesame oils containing as little as 10%other vegetable oils.This study provided a rapid screening method for adulterated sesame oil in market surveillance and a reference for developing authentication methods of other edible oils.
基金supported by the National Natural Science Foundation of China (Nos.22036001, 22276034 and 22106130)。
文摘Cancer cell spheroids(CCS) are a valuable three-dimensional cell model in cancer studies because they could replicate numerous characteristics of solid tumors. Increasing researches have used matrix-assisted laser desorption/ionization mass spectrometry imaging(MALDI-MSI) to investigate the spatial distribution of endogenous compounds(e.g., lipids) in CCS. However, only limited lipid species can be detected owing to a low ion yield by using MALDI. Besides, it is still challenging to fully characterize the structural diversity of lipids due to the existence of isomeric/isobaric species. Here, we carried out the initial application of MALDI coupled with laser-postionization(MALDI-2) and trapped ion mobility spectrometry(TIMS) imaging in HCT116 colon CCS to address these challenges. We demonstrated that MALDI-2 is capable of detecting more number and classes of lipids in HCT116 colon CCS with higher signal intensities than MALDI. TIMS could successfully separate numerous isobaric/isomeric species of lipids in CCS. Interestingly, we found that some isomeric/isobaric species have totally different spatial distributions in colon CCS. Further MS/MS imaging analysis was employed to determine the compositions of fatty acid chains for isomeric species by examining disparities in signal intensities and spatial distributions of product ions. This work stresses the robust ability of TIMS and MALDI-2 imaging in analyzing endogenous lipids in CCS, which could potentially become powerful tools for future cancer studies.
基金This work was financially supported by the National Key Research and Development Program of China(Grant No.2018YFC1704500)Tianjin Committee of Science and Technology of China(Grant No.21ZYJDJC00080)National Natural Science Foundation of China(Grant No.81872996).
文摘The complex composition of herbal metabolites necessitates the development of powerful analytical techniques aimed to identify the bioactive components.The seeds of Descurainia sophia(SDS)are utilized in China as a cough and asthma relieving agent.Herein,a dimension-enhanced integral approach,by combining ultra-high performance liquid chromatography/ion mobility-quadrupole time-of-flight mass spectrometry(UHPLC/IMQTOF-MS)and intelligent peak annotation,was developed to rapidly characterize the multicomponents from SDS.Good chromatographic separation was achieved within 38 min on a UPLC CSH C18(2.1×100 mm,1.7μm)column which was eluted by 0.1%formic acid in water(water phase)and acetonitrile(organic phase).Collision-induced dissociation-MS^(2)data were acquired by the data-independent high-definition MS^(E)(HDMS^(E))in both the negative and positive electrospray ionization modes.A major components knockout strategy was applied to improve the characterization of those minor ingredients by enhancing the injection volume.Moreover,a self-built chemistry library was established,which could be matched by the UNIFI software enabling automatic peak annotation of the obtained HDMS^(E)data.As a result of applying the intelligent peak annotation workflows and further confirmation process,a total of 53 compounds were identified or tentatively characterized from the SDS,including 29 flavonoids,one uridine derivative,four glucosides,one lignin,one phenolic compound,and 17 others.Notably,four-dimensional information related to the structure(e.g.,retention time,collision cross section,MS^(1)and MS^(2)data)was obtained for each component by the developed integral approach,and the results would greatly benefit the quality control of SDS.
基金the State Key Laboratory of Chemo/Biosensing and Chemometrics Foundation(No.05-12-1)
文摘Based on two-dimensional topological structures, a novel molecular electronegativity interaction vector with hybridization (MEHIV) was developed to describe atomic hybridization state in different molecular environments. Five quantitative models by MEHIV characterization and multiple linear regression modeling were successfully established to predict reduced ion mobility constants (Ko) of alkanes, aromatic hydrocarbons, fatty alcohols, fatty aldehydes and ketones and carboxylic esters. The correlation coefficients Roy by leave-one-out cross-validation are 0.792, 0.787, 0,949, 0.972 and 0.981, respectively, and the standard deviations SDcv are 0.067, 0.086, 0.064, 0.043 and 0.042, respectively. These results suggested that MEHIV is an excellent topological index descriptor with many advantages such as straightforward physicochemical meaning, high characterization competence, convenient expansibility and easy manipulation.
基金This work was financially supported by the National Key Research and Development Program of China(Grant No.2018YFC1704500)Tianjin Committee of Science and Technology of China(Grant No.21ZYJDJC00080)National Natural Science Foundation of China(Grant No.81872996)。
文摘Herbal components characterization represents a challenging task because of the co-existing of multiple classes of naturally occurring compounds with wide spans of polarity,molecular mass,and the ubiquitous isomerism.The root and rhizome of Salvia miltiorrhiza have been utilized as a reputable traditional Chinese medicine Salviae Miltiorrhizae Radix et Rhizoma(Dan-Shen)in the treatment of cardiovascular disease.Herein,a dimensionenhanced ultra-high performance liquid chromatography/ion mobility/quadrupole time-of-flight mass spectrometry approach in combination with intelligent peak annotation workflows was established aimed to rapidly characterize the multicomponents from S.miltiorrhiza.Due to the sufficient optimization,satisfactory chromatography separation was enabled on an HSS T3 column within 33 min using 0.1%formic acid in water(A)and acetonitrile(B)as the mobile phase,while the data-independent HDMS^(E) in both the negative and positive electrospray ionization modes was utilized for the high-coverage MS^(2) data acquisition.Streamlined automatic peak annotation by searching an in-house library(recording 198 known compounds)followed by the subsequent confirming steps(e.g.,comparison with the reference compounds,fragmentation pathways analysis,and retention behavior comparison,etc.),allowed us to identify or tentatively characterize a total of 86 components(including 50 terpenoids,21 phenolic acids,and 15 others)from S.miltiorrhiza.Importantly,three-dimensional structure information,such as the retention time,MS^(1) and MS^(2) data,and collision cross section(CCS),was provided,which can facilitate the more reliable characterization of herbal components.
基金supported by the National Key Research and Development Program of China(Grant No.2018YFC1704500)the National Natural Science Foundation of China(Grant No.81872996)。
文摘Objective:Quality control of traditional Chinese medicine(TCM)begins with the chemical basis elucidation.The root of Stephania tetrandra has long been utilized as an antirheumatic,analgesic,and diuretic TCM,Stephaniae Tetrandrae Radix(STR;Fang-Ji).Powerful analytical strategies enabling its multicomponent characterization is still rare.Methods:A rapid,reliable,and enhanced profiling approach,by ultra-high performance liquid chromatography coupled with ion mobility/quadrupole time-of-flight mass spectrometry(UHPLC/IM-QTOF-MS)and automatic peak annotation facilitated by computational matching of in-house library,was established and utilized to characterize the multicomponents from STR.A knockout strategy was utilized by automated valve switching to overcome the interference of predominant peaks.Results:Good chromatographic separation was achieved within 17 min on a reversed-phase BEH C18 column eluted with acetonitrile/0.1%ammonium hydroxide in water,while data-independent high-definition MS^(E)(HDMS^(E))in positive mode was applied to acquire the MS^(2)data by using a Vion TM IM-QTOF instrument,which in theory,could cover all the profiled precursor ions.An in-house library of 163 compounds was established and incorporated into the UNIFITM platform.By feat of these efforts,we were able to identify or tentatively characterize 76 alkaloids from the methanolic extract of STR,including 14 aporphine-type,four morphine-type,48 bisbenzylisoquinoline-type,seven tetrahydroprotoberberine-type,one protopine-type,one benzylisoquinoline-type,and one other.Four-dimensional information,such as the retention time,collision cross section(CCS),high-accuracy MS1 and MS2 data,for each component was provided.Conclusions:The systematic multicomponent characterization of STR was accomplished with high coverage,high degree of automation,and high reliability.