During the analysis of benziamidazole-class irreversible proton pump inhibitors,an unusual mass spectral response with the mass-to-charge ratio at[Mt10]t intrigued us,as it couldn't be assigned to any literature k...During the analysis of benziamidazole-class irreversible proton pump inhibitors,an unusual mass spectral response with the mass-to-charge ratio at[Mt10]t intrigued us,as it couldn't be assigned to any literature known relevant structure,intermediate or adduct ion.Moreover,this mysterious mass pattern of[Mt10]t has been gradually observed by series of marketed proton pump inhibitors,viz.omeprazole,pantoprazole,lansoprazole and rabeprazole.All the previous attempts to isolate the corresponding component were unsuccessful.The investigation of present work addresses this kind of signal to a pyridinium thiocyanate mass spectral intermediate(10),which is the common fragment ion of series of labile aggregates.The origin of such aggregates can be traced to the reactive intermediates formed by acid-promoted degradation.These reactive intermediates tend to react with each other and give raise series of complicated aggregates systematically in a water/acetonitrile solution by electrospray ionization.The structure of the corresponding pyridinium thiocyanate species of omeprazole(10a)has been eventually characterized with the help of synthetic specimen(10a′).Our structural proposal as well as its origin was supported by in situ nuclear magnetic resonance,chemical derivatization and colorimetric experiments.展开更多
The positive and negative ESI-MS/MS spectra of N-ethoxy（phenyl） phosphoryl amino acids（EPP-AA） were investigated by electrospray ionization（ESI） ion trap mass spectrometry. The fragmentation pathways of [ M ＋ N...The positive and negative ESI-MS/MS spectra of N-ethoxy（phenyl） phosphoryl amino acids（EPP-AA） were investigated by electrospray ionization（ESI） ion trap mass spectrometry. The fragmentation pathways of [ M ＋ Na]^＋ and [ M - H]^- ions are proposed and rationalized. The observation may have some potential applications in the interpretation of the MS/MS spectra of novel N-phosphoryl compounds. The complexity of MS/MS spectra of EPP-AA [ M ＋ Na]^＋ ions is decreased compared with that of N-dialkyloxyphosphoryl amino acid. Therefore, the new phosphonamidate method may be considered one of the superior methods that can be used in sequencing peptides and proteins extensively.展开更多
The sequence analysis of peptides was performed by nano-electrospray ionization Fourier transform ion cyclotron resonance tandem mass spectrometry（Nano-ESI-FT-ICR-MSn） and several peptides were chosen as examples. W...The sequence analysis of peptides was performed by nano-electrospray ionization Fourier transform ion cyclotron resonance tandem mass spectrometry（Nano-ESI-FT-ICR-MSn） and several peptides were chosen as examples. With the aid of the collision induced dissociation（CID）, FT-ICR provides not only precise mass/charge ratio, but also structure information of the selected peptides. The fragment ions were identified according to the observed molecular weights and peptide sequence was determined successfully. So Nano-ESI-FT-ICR-MSn is a useful tool for identification of the amino acid sequence of peptides with high confidence. Besides, a pathway for the dehydration of y ions without amino acids containing carboxylic acid under sustained off-resonance irradiation collision-induced dissociation（SORI-CID） condition was proposed.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
Dating techniques including gypsum dissolution in water, iron hydroxide co-precipitation with uranium and thorium and mass spectrometric determination have been investigated in this note. The ages of the gypsum sample...Dating techniques including gypsum dissolution in water, iron hydroxide co-precipitation with uranium and thorium and mass spectrometric determination have been investigated in this note. The ages of the gypsum samples in a CK core from Luobubo lacustrine sediments are in the range of (12.85±0.21) kaBP (4 m distance from the top core) to (153.2 ± 7.2) kaBP (49 m distance from the top core) with the relative errors of ( 1.6%-±4.7%. It indicates that the sedimental environment of the CK core was situated in the middle-late Pleistocene and Holocene periods, corresponding to 1-6 stages of oxygen isotopes in the abyssal sediments and included much information from last inter-glacial to Holocene warm periods.展开更多
A high precision thermal ionization mass spectrometric (HP-TIMS) technique is used to determine 238U,234U,232Th,230Th concentrations and their ratios in whole rocks and minerals separated from Ouaternary Maanshan, Day...A high precision thermal ionization mass spectrometric (HP-TIMS) technique is used to determine 238U,234U,232Th,230Th concentrations and their ratios in whole rocks and minerals separated from Ouaternary Maanshan, Dayingshan and Heikongshan volcanic rocks of Tengchong volcanic field .Yunnan Province, China. The 238U-230Th isochrons are given, yielding four age values (227 ? 20) ka (D-1, Dayingshan), (79.6 ±5.5) ka (D-7, Dayingshan), (21.9 ± 3.0) ka (h-1, Heikongshan), and (7.5 ± 1.0) ka (M-1, Maanshan). The result is not only consistent with but also preciser than those measured by the K-Ar method and the alpha spectrometry U-series method, indicating that the HP-TIMS method is reliable and has high precision. Besides, a procedure of HP-TIMS analysis of young volcanic rocks in China is set up preliminarily.展开更多
I. INTRODUCTION Lithium as a nucleal material has been applied in nucleal industry extensively, The geologists are very interested in lithium isotopic compositions which are an important method for studying cosmology....I. INTRODUCTION Lithium as a nucleal material has been applied in nucleal industry extensively, The geologists are very interested in lithium isotopic compositions which are an important method for studying cosmology. Thus, it is essential to determine precisely and accurately the isotopic ratio of lithium. The large relative mass difference between the展开更多
Two national stalagmite standard （GBW04412, GBW04413） and one international coral standard （RKM4） have been determined by using thermal ionization mass spectrometry （TIMS） method. The values of （ 234 U/ 238 U）...Two national stalagmite standard （GBW04412, GBW04413） and one international coral standard （RKM4） have been determined by using thermal ionization mass spectrometry （TIMS） method. The values of （ 234 U/ 238 U） act , （ 230 Th/ 234 U） act and age are all consistent in error range with the standard values obtained by using α spectrometry.展开更多
Salinity tolerance of ambient electric arc ionization(AEAI)was evaluated by comparing electrospray ionization for various samples at NaCl concentrations from 0 to 1000 mmol/L.AEAI-mass spectrometry(AEAI-MS)exhibited a...Salinity tolerance of ambient electric arc ionization(AEAI)was evaluated by comparing electrospray ionization for various samples at NaCl concentrations from 0 to 1000 mmol/L.AEAI-mass spectrometry(AEAI-MS)exhibited an excellent signal intensity even at NaCl concentrations of 1000 mmol/L,while the ESI-MS had no signal because high salinity has a strong inhibitory effect on analytes.The sodium adduct was verified using LiCl instead of NaCl.AEAI-MS successfully quantified saline samples with an excellent quantitative ability(R^(2)≥0.998).We also achieved some analytical samples in the buffer solution at a very high concentration and even in a saturated salt solution.Overall,AEAI-MS has protonated ions for most target analytes.In addition,the relationship between auxiliary temperature and the distance from the sample to the arc was investigated,and the results indicated that thermal desorption plays an important role in AEAI source.展开更多
The nitrogen-containing compounds in Changqing crude oil, its atmospheric residue(AR), and vacuum reside(VR) were characterized by negative and positive ion electrospray ionization(ESI) Fourier transform ion cyclotron...The nitrogen-containing compounds in Changqing crude oil, its atmospheric residue(AR), and vacuum reside(VR) were characterized by negative and positive ion electrospray ionization(ESI) Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS). The heteroatom compounds(N_1, N_2, N_1O_1, O_1, and O_2 class species) could be identified by the negative ESI analysis, while the positive mode could only detect the N_1, N_2, and N_1O_1 class species. Among them, the N_1 class species were found to be predominant in crude oil, as confirmed by either negative or positive ESI analyses,which were similar in composition to AR and VR. These compounds with higher abundance were characterized by double bond equivalent(DBE) values and carbon numbers. The composition of these compounds in crude oil and its AR as well as VR was correlated with their different boiling range, DBE values and carbon numbers. The negative ESI analysis showed that the abundant N_1 class species in crude oil and AR were centered at a DBE value of 12, and these species were likely benzocarbazoles, while the N_1 class species with the DBE value ranging from 13 to 16 having more complicated molecular structures were dominant in VR. And the positive ESI analysis gave the information of the abundant N_1 class species in crude oil, AR, and VR having the DBE values in the range of 10, 9―11, and 10―16, respectively, which were likely the compounds with the core of quinoline and benzoquinoline. The analysis confirmed that the distillation process in refinery preferentially removed the low DBE value and low molecular N-class species and brought them into the light and medium distillates, while those N-class species having a high molecular condensation in the molecules with large carbon number remained in the residual oil and could continually affect the downstream oil refining process.展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.:82030107 and 81872831)the National Science and Technology Major Projects for significant new drugs creation of the 13th five-year plan(Grant Nos.:2017ZX09101001 and 2018ZX09721002007).
文摘During the analysis of benziamidazole-class irreversible proton pump inhibitors,an unusual mass spectral response with the mass-to-charge ratio at[Mt10]t intrigued us,as it couldn't be assigned to any literature known relevant structure,intermediate or adduct ion.Moreover,this mysterious mass pattern of[Mt10]t has been gradually observed by series of marketed proton pump inhibitors,viz.omeprazole,pantoprazole,lansoprazole and rabeprazole.All the previous attempts to isolate the corresponding component were unsuccessful.The investigation of present work addresses this kind of signal to a pyridinium thiocyanate mass spectral intermediate(10),which is the common fragment ion of series of labile aggregates.The origin of such aggregates can be traced to the reactive intermediates formed by acid-promoted degradation.These reactive intermediates tend to react with each other and give raise series of complicated aggregates systematically in a water/acetonitrile solution by electrospray ionization.The structure of the corresponding pyridinium thiocyanate species of omeprazole(10a)has been eventually characterized with the help of synthetic specimen(10a′).Our structural proposal as well as its origin was supported by in situ nuclear magnetic resonance,chemical derivatization and colorimetric experiments.
基金Supported by the Education Department of Henan Province(No. 200510459015).
文摘The positive and negative ESI-MS/MS spectra of N-ethoxy（phenyl） phosphoryl amino acids（EPP-AA） were investigated by electrospray ionization（ESI） ion trap mass spectrometry. The fragmentation pathways of [ M ＋ Na]^＋ and [ M - H]^- ions are proposed and rationalized. The observation may have some potential applications in the interpretation of the MS/MS spectra of novel N-phosphoryl compounds. The complexity of MS/MS spectra of EPP-AA [ M ＋ Na]^＋ ions is decreased compared with that of N-dialkyloxyphosphoryl amino acid. Therefore, the new phosphonamidate method may be considered one of the superior methods that can be used in sequencing peptides and proteins extensively.
基金Supported by the National Natural Science Foundation of China(No.20675079)
文摘The sequence analysis of peptides was performed by nano-electrospray ionization Fourier transform ion cyclotron resonance tandem mass spectrometry（Nano-ESI-FT-ICR-MSn） and several peptides were chosen as examples. With the aid of the collision induced dissociation（CID）, FT-ICR provides not only precise mass/charge ratio, but also structure information of the selected peptides. The fragment ions were identified according to the observed molecular weights and peptide sequence was determined successfully. So Nano-ESI-FT-ICR-MSn is a useful tool for identification of the amino acid sequence of peptides with high confidence. Besides, a pathway for the dehydration of y ions without amino acids containing carboxylic acid under sustained off-resonance irradiation collision-induced dissociation（SORI-CID） condition was proposed.
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 supported by the National Key Basis Research Project (Grant No. G19990434) the Innovative Project of the Chinese Academy of Sciences (Grant No. KZCX 1-y 05) and the Resources and Environment Basis Project of the University of Science an
文摘Dating techniques including gypsum dissolution in water, iron hydroxide co-precipitation with uranium and thorium and mass spectrometric determination have been investigated in this note. The ages of the gypsum samples in a CK core from Luobubo lacustrine sediments are in the range of (12.85±0.21) kaBP (4 m distance from the top core) to (153.2 ± 7.2) kaBP (49 m distance from the top core) with the relative errors of ( 1.6%-±4.7%. It indicates that the sedimental environment of the CK core was situated in the middle-late Pleistocene and Holocene periods, corresponding to 1-6 stages of oxygen isotopes in the abyssal sediments and included much information from last inter-glacial to Holocene warm periods.
文摘A high precision thermal ionization mass spectrometric (HP-TIMS) technique is used to determine 238U,234U,232Th,230Th concentrations and their ratios in whole rocks and minerals separated from Ouaternary Maanshan, Dayingshan and Heikongshan volcanic rocks of Tengchong volcanic field .Yunnan Province, China. The 238U-230Th isochrons are given, yielding four age values (227 ? 20) ka (D-1, Dayingshan), (79.6 ±5.5) ka (D-7, Dayingshan), (21.9 ± 3.0) ka (h-1, Heikongshan), and (7.5 ± 1.0) ka (M-1, Maanshan). The result is not only consistent with but also preciser than those measured by the K-Ar method and the alpha spectrometry U-series method, indicating that the HP-TIMS method is reliable and has high precision. Besides, a procedure of HP-TIMS analysis of young volcanic rocks in China is set up preliminarily.
文摘I. INTRODUCTION Lithium as a nucleal material has been applied in nucleal industry extensively, The geologists are very interested in lithium isotopic compositions which are an important method for studying cosmology. Thus, it is essential to determine precisely and accurately the isotopic ratio of lithium. The large relative mass difference between the
文摘Two national stalagmite standard （GBW04412, GBW04413） and one international coral standard （RKM4） have been determined by using thermal ionization mass spectrometry （TIMS） method. The values of （ 234 U/ 238 U） act , （ 230 Th/ 234 U） act and age are all consistent in error range with the standard values obtained by using α spectrometry.
基金supported by the China State Key Research Program(No.2016YFF0200503)National Natural Science Founda-tion of China(No.21927810)Sichuan Normal University(Nos.SYJS2020010 and KFSY2020004).
文摘Salinity tolerance of ambient electric arc ionization(AEAI)was evaluated by comparing electrospray ionization for various samples at NaCl concentrations from 0 to 1000 mmol/L.AEAI-mass spectrometry(AEAI-MS)exhibited an excellent signal intensity even at NaCl concentrations of 1000 mmol/L,while the ESI-MS had no signal because high salinity has a strong inhibitory effect on analytes.The sodium adduct was verified using LiCl instead of NaCl.AEAI-MS successfully quantified saline samples with an excellent quantitative ability(R^(2)≥0.998).We also achieved some analytical samples in the buffer solution at a very high concentration and even in a saturated salt solution.Overall,AEAI-MS has protonated ions for most target analytes.In addition,the relationship between auxiliary temperature and the distance from the sample to the arc was investigated,and the results indicated that thermal desorption plays an important role in AEAI source.
基金supported by the Young Talent Fund of University Association for Science and Technoloqy in Shaanxi, China (No. 20160222)The PetroChina Innovation Foundation (No. 2016D-5007-0404)the Natural Science Basic Research Plan in Shaanxi Province of China (No. 2017JQ2034)
文摘The nitrogen-containing compounds in Changqing crude oil, its atmospheric residue(AR), and vacuum reside(VR) were characterized by negative and positive ion electrospray ionization(ESI) Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS). The heteroatom compounds(N_1, N_2, N_1O_1, O_1, and O_2 class species) could be identified by the negative ESI analysis, while the positive mode could only detect the N_1, N_2, and N_1O_1 class species. Among them, the N_1 class species were found to be predominant in crude oil, as confirmed by either negative or positive ESI analyses,which were similar in composition to AR and VR. These compounds with higher abundance were characterized by double bond equivalent(DBE) values and carbon numbers. The composition of these compounds in crude oil and its AR as well as VR was correlated with their different boiling range, DBE values and carbon numbers. The negative ESI analysis showed that the abundant N_1 class species in crude oil and AR were centered at a DBE value of 12, and these species were likely benzocarbazoles, while the N_1 class species with the DBE value ranging from 13 to 16 having more complicated molecular structures were dominant in VR. And the positive ESI analysis gave the information of the abundant N_1 class species in crude oil, AR, and VR having the DBE values in the range of 10, 9―11, and 10―16, respectively, which were likely the compounds with the core of quinoline and benzoquinoline. The analysis confirmed that the distillation process in refinery preferentially removed the low DBE value and low molecular N-class species and brought them into the light and medium distillates, while those N-class species having a high molecular condensation in the molecules with large carbon number remained in the residual oil and could continually affect the downstream oil refining process.
