RAPID COMMUNICATIONS IN MASS SPECTROMETRY
·
2017
·Vol. 32
·期 3
·262-268
·
IF 1.998
Xiafen Xu,Xinhui Li,Xianrui Liang
Rationale Metabolites of isoflavones have attracted much attention in recent years due to their potential bioactivities. However, the complex constituents of the metabolic system and the low level of metabolites make them difficult to analyze. A mass spectrometry (MS) method was applied in our identification of metabolites and study of their fragmentation pathways due to the advantages of rapidity, sensitivity, and low level of sample consumption. Methods Three isoflavone glycosides and their metabolites were identified using ultra-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry (UPLC/QTOF-MS). These metabolites were obtained by anaerobically incubating three isoflavone glycosides with human intestinal flora. The characteristic fragments of isoflavone glycosides and their metabolites were used for the identification work. Results Two metabolites from ononin, three metabolites from irilone-4′- O -β-D-glucoside, and five metabolites from sissotrin were identified respectively by the retention time (RT), accurate mass, and mass spectral fragmentation patterns. The losses of the glucosyl group, CO from the [M+H] + ion were observed for all the three isoflavone glycosides. The characteristic retro-Diels-Alder (RDA) fragmentation patterns were used to differentiate the compounds. The metabolic pathways of the three isoflavone glycosides were proposed according to the identified chemical structures of the metabolites. Conclusions A selective, sensitive and rapid method was established for detecting and identifying three isoflavone glycosides and their metabolites using UPLC/QTOF-MS. The established method can be used for further rapid structural identification studies of metabolites and natural products. Furthermore, the proposed metabolic pathways will be helpful for understanding the in vivo metabolic process of isoflavone.
研究领域:
分析化学
·
药理学
·
营养学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
TALANTA
·
2025
·
IF 6.1
Keke Yi,Wei Wan,Ziyu Qu,Di Zhang,Zihong Ye,Xinhua Dai,Jie Xie,You Jiang,Xiang Fang
A determination method using a home-built quadrupole-linear ion trap tandem mass spectrometry (Q-LIT) multistage fragmentation function to accurate measure ultra-trace steroid hormones in human serum was established. The capability of ion trap for multistage fragmentation (MS 3 ) overcomes the limitation of triple quadrupole systems restricted to MS 2 , enabling deeper structural characterization. Multistage fragmentation (MS3) enables the accurate detection of steroid hormones in serum samples without requiring extensive derivatization or time-consuming sample preparation and improves sensitivity by effectively reducing noise. Hydrocortisone, 4-androstenedione, 11-deoxycortisol, 21-deoxycortisol, and 17α-hydroxyprogesterone were quantified by MS 3 transitions m/z 363.2 → 327.2→309.2, m/z 287.2 → 97.0→79.0, m/z 347.1 → 311.2→293.2, m/z 347.0 → 311.1→293.1, and m/z 331.2 → 313.3→295.2, respectively. Multistage fragmentation mass spectrometry effectively prevents matrix interference, and the quantitative results of MS 3 are less affected by matrix effect than those of MS 2 . The established multistage fragmentation quantitative method showed good linearity (R 2 ≥ 0.99), and the limits of detection and quantification of 5 steroid hormones were lower than 0.06 and 0.20 ng/mL, respectively. The recovery was 86.56 %–123.14 %, with an RSD of ≤13.57 %. A total of 22 real serum samples were accurately and sensitively measured using the Q-LIT multistage fragmentation method. Therefore, Q-LIT based multistage fragmentation has great potential for applications, such as detecting steroid hormones with severe matrix effects and distinguishing among related isomers in complex biological samples.
研究领域:
分析化学
·
内分泌学
·
临床医学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF MATERIALS SCIENCE
·
2021
·Vol. 56
·期 19
·11426-11435
·
IF 4.22
Yan Dong,Peng Zhen,Wang Wei,Zeng Peng,Huang Yiyin
Abstract Carbon-based metal-free catalysts exhibit great applications in electrochemical CO 2 reduction (ECR), while most studies merely focus on large-sized carbons with limited ratio of surface atoms for engineering to create surface active centers. Here, we report a joint treatment of C60 by heating and plasma to induce a dramatic performance promotion during ECR. The electrochemical measurements indicate the Faraday efficiency for ECR toward CO production kept at high level over 80% in a wide potential region from − 0.4 to − 0.7 V versus RHE, with the highest value reaching 96.8%. The physical characterization reveals that fragmentation of C60 occurs together with N/O doping, both of which could induce change in electron structure, causing the formation of *COOH intermediate and ultimately leading to the optimized activity and selectivity for CO production. This treatment route was further revealed to be applicative for other carbon materials, e.g., single-walled carbon nanotube, to promote its ECR activity and selectivity. Graphical Abstract
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MASS SPECTROMETRY
·
2020
·Vol. 55
·期 9
·e4528
·
IF 1.671
Feng-Jie Liu,Yan Jiang,Ping Li,Yang-Dan Liu,Gui-Zhong Xin,Zhong-Ping Yao,Hui-Jun Li
Fully understanding the chemicals in an herbal medicine remains a challenging task. Molecular networking (MN) allows to organize tandem mass spectrometry (MS/MS) data in complex samples by mass spectral similarity, which yet suffers from low coverage and accuracy of compound annotation due to the size limitation of available databases and differentiation obstacle of similar chemical scaffolds. In this work, an enhanced MN-based strategy named diagnostic fragmentation-assisted molecular networking coupled with in silico dereplication (DFMN-ISD) was introduced to overcome these obstacles: the rule-based fragmentation patterns provide insights into similar chemical scaffolds, the generated in silico candidates based on metabolic reactions expand the available natural product databases, and the in silico annotation method facilitates the further dereplication of candidates by computing their fragmentation trees. As a case, this approach was applied to globally profile the steroidal alkaloids in Fritillariae bulbus, a commonly used antitussive and expectorant herbal medicine. Consequently, a total of 325 steroidal alkaloids were discovered, including 106 cis -D/E-cevanines, 142 trans -D/E-cevanines, 29 jervines, 23 veratramines, and 25 verazines. And 10 of them were confirmed by available reference standards. Approximately 70% of the putative steroidal alkaloids have never been reported in previous publications, demonstrating the benefit of DFMN-ISD approach for the comprehensive characterization of chemicals in a complex plant organism.
研究领域:
中药化学
·
代谢组学
·
药用植物研究
✓ 已验证
产品关联
DOI
PubMed
高影响因子
COMPOSITES PART B-ENGINEERING
·
2024
·
IF 12.7
Wenli An,Yan Zhang,Junyan Li,Shun Zhang,Chengfeng Shen,Xuehui Liu,Zhishan Su,Shimei Xu,Yu-Zhong Wang
As the most productive thermosetting polymer, unsaturated polyester resin (UPR) and its composies were difficult to be chemcycled due to the mass transfer barrier in dense network structure. High temperature/pressure and mechanical crushing were usually applied to improve the mass transfer during chemcycling processes, but at the sacrifice of reaction selectivity and fiber integrity. Here, a unique fragmentation effect of aprotic solvents was observed in UPR, which is a non-reactive solvation that has the potential to replace mechanical fragmentation and improve the recyclability of UPR and its composite materials. The solvation was found to be based on the hydrogen bond between the solvent and ester group of UPR through Hansen solubility parameters and molecular dynamics simulation. It was the intermolecular force between the polyester clusters of UPR that was destroyed, leading to the fragmentation of UPR into micron-sized powder. The fragmentation effect is also applicable to other ester-containing polymers and provides a simple, facile, and energy-efficient method for the chemcycling of thermosetting resins, as well as direct exfoliation of reinforced fillers.
研究领域:
材料科学
·
化学工程
✓ 已验证
DOI
高影响因子
MICROCHEMICAL JOURNAL
·
2021
·
IF 4.821
Guo-Sheng Li,Min-Hua Wang,Xing Fan,Xueming Dong,Xian-Yong Wei,Bo Chen,Jiao-Fei Wang
To provide basic knowledge for coal conversion, twenty one coal-related model compounds (MCs) were analyzed using a tandem Orbitrap mass spectrometer (MS). Higher-energy collisional dissociation (HCD), a method of Orbitrap MS, unraveled the detailed fragmentation pathways and de-alkylation behaviors of the ionized MCs under collision energies from 10 to 80 eV. Chemical bond breaking, hydrogen loss, rearrangement reaction, and elimination of neutral fragments were discussed to elucidate clear fragmentation pathways. For arenes without alkyl chains, a higher energy threshold of fragmentation was observed with the increasing of aromatic ring due to a higher conjugate effect of condensed aromatic structure. The existence of alkyl chains decreased the threshold of fragmentation because of the electron-donating effect of alkyl chains. Heteroatom-containing aromatic compounds, a series of important species in coal, showed a diversified fragmentation patterns due to a low bond dissociation energy and a weak conjugate effect compared with arenes. Fragmentation pathways and de-alkylation behaviors of coal-related MCs will contribute to building monitoring methods for coal and its derivatives conversions in chemical industry.
研究领域:
化学
·
能源科学
·
分析化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CHROMATOGRAPHY B-ANALYTICAL TECHNOLOGIES IN THE BIOMEDICAL AND LIFE SCIENCES
·
2018
·
IF 2.441
Hao Wang,Honglei Chen,Jie Geng,Yi Zheng,Zhongyu Zhang,Lin Sun,Guihua Tai,Yifa Zhou
Dextran is a biocompatible glucose-based polymer that is widely used clinically as a plasma volume expander , anti-thrombotic agent, macromolecular carrier, peripheral blood flow enhancer, and artificial tears promoter. Because dextran has polydisperse molecular weights and tends to produce innumerable multi-charged precursor ions in the ion source, it is difficult to analysis this polymer using conventional liquid chromatography mass spectrometry . In this assay, all ion fragmentation strategy is used to solve this problem by allowing all dextran precursor ions generated in the ion source to enter the collision cell. Then serial dextran-specific fragments can be effectively generated from all precursor ions by higher energy collision dissociation and scanned by Orbitrap detector. These high resolution fragment ions provide high specificity and sensitivity for the quantitation of dextran in rat plasma. Here, we report a new quantitative method using size exclusion chromatography combined with Q Exactive mass spectrometry based on an all ion fragmentation strategy. Assay validation showed that this method is linear over the concentration range from 3 to 300 μg/mL. Our approach has been successfully applied to a pharmacokinetic study of dextran in rat and will promote the development of studies with other polysaccharides .
研究领域:
生物化学
·
药理学
·
分析化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Water
·
2024
·Vol. 16
·期 11
·1529
·
IF 3
Luhan Su,Zhongwen Liu,Jia He,Yan Wu,Qingguo Wang
The aging behavior of microplastics (MPs) in the environment has garnered significant attention, yet the exact aging process undergone by microplastics during advanced oxidation still remains unclear. This study emphasized elucidating the oxidation and dechlorination mechanisms of polyvinyl chloride microplastics (PVC MPs) within the UV-activated sodium percarbonate system (UV/SPC). After 35 h of UV/SPC (0.05 M) treatment, it exhibited effective dechlorination with a Cl−release of 100.62 ± 13.17 mg/L. And this treatment resulted in the fragmentation and release of fragments from the PVC MPs, thereby contributing to their further aging and dechlorination. In addition, an increase in oxygen-containing functional groups was identified. Quenching experiments confirm that·OHand·CO3−are the primary active species present in the system. In summary, the aging of PVC MPs results in a process of fragmentation, releasing fragments that are more fragile and susceptible to mineralization compared to the original PVC MPs. The release of chloride ions originates from the mineralization of these fragments released from PVC MPs by·OHand·CO3−. This study has provided valuable insights into the aging mechanisms of MPs in practical wastewater treatment.
研究领域:
环境科学
·
化学工程
·
废水处理
✓ 已验证
产品关联
DOI
高影响因子
TALANTA
·
2019
·
IF 4.916
Yue Lin,Xiu Huang,Qian Liu,Zhenyu Lin,Guibin Jiang
As an emerging field of study, microplastics have drawn tremendous attention, but until now little is known about their fate and impacts in the environment. A critical bottleneck is lack of reliable techniques to identify and quantify microplastics in complex media. Here we present a simple, rapid, and effective method for identification and quantification of micro/nanoplastics (MNPs) based on thermal fragmentation and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) with polystyrene (PS) particles as a model MNP. The PS MNPs are identified by fingerprint peaks in both low-mass ( m/z 90, 104, 128, 130, and 312–318) and high-mass regions (repeated peaks with Δ m/z 104 in the m/z range 350–5000), and the quantification is carried out with m/z 315.3. The different ionization behaviors enable the differentiation of MNPs with different molecular weights . Notably, we find that a simple thermal pretreatment at 380 °C can facilitate the fragmentation of PS and significantly enhances the intensities of fingerprint peaks in low-mass regions, yielding a detection limit of 25 ng for PS MNPs. The applicability of the method in different sample matrices and for other types of MNPs such as polyethylene terephthalate (PET) is also validated. Considering the current shortcomings in MNP analysis, this work provides a powerful tool to advance the MNPs research.
研究领域:
环境科学
·
分析化学
✓ 已验证
DOI
高影响因子
JOURNAL OF MASS SPECTROMETRY
·
2023
·Vol. 58
·期 11
·e4979
·
IF 2.3
Qi-Qi Zhang,Yang Liu,Shu-Ping Tan,Yan Chen,Jie Gao,Xin-Yue Liang,Wei-Qun Shi,Yong-Gang Zhao
Electrospray Ionization Mass Spectrometry (ESI-MS) technique and density functional theory (DFT) calculations were combined to study the formation of the complexes of lanthanides (Ln = La, Ce, Nd, Sm, Eu, Yb) and actinides (UO 2 2+ , Th 4+ ) with CyMe 4 -BTBP (6,6′-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-benzo-[1,2,4-]triazin-3-yl)-[2,2′]bipyridine) to understand the mechanisms during the extraction process. Mass spectrometry titrations showed the formation of the complexation in acetonitrile. For lanthanides, only 1:2 complexes ([Ln(L) 2 ] 3+ , [Ln(L) 2 (CH 3 CN)] 3+ ), [Ln(L) 2 (NO 3 )] 2+ ) were found at low [Ln]/[L] concentration ratios, whereas the 1:1 complexes ([Ln(L)(NO 3 ) 2 ] + ) were observed when the [Ln]/[L] concentration ratio reached 1.0. For uranyl complexes, 1:1 complex ([UO 2 L(NO 3 )] + ) was the only species within the measuring range. Th 4+ complexes had two compositions: 1:1 and 1:2, in which 1:2 species was the dominant complex. Collision-induced dissociation (CID) was employed to characterize the fragmentation process. The fragmentation process was unfolded sequentially on both sides of CyMe 4 -BTBP ligand with the loss of alkyl groups and cleavage of triazinyl rings. The CID results of CyMe 4 -BTBP complexes revealed a slight difference depending on the metal center. The DFT calculations showed that the stable complexes formed in acetonitrile solution were consistent with the ESI-MS results.
研究领域:
无机化学
·
分析化学
·
计算化学
✓ 已验证
DOI
PubMed
高影响因子
EUROPEAN JOURNAL OF MASS SPECTROMETRY
·
2018
·
IF 1
Shanshan Wang,Yuanyuan Cheng,Mengmeng Chen,Kezhi Jiang
Differentiation of the isomeric haloanilines still remains a challenging and necessary analytic task due to their identical retention time in chromatography and similar mass spectra. In this work, p-tosylation of haloanilines by reaction of haloanilines with p-toluenesulfonyl chloride resulted in the corresponding N-tosyl haloanilines. Fragmentation of protonated N-tosyl haloanilines in electrospray ionization tandem mass spectrometry (ESI-MS/MS) mainly resulted in tosyl cation, haloaniline radical cation, and halohydroxyaniline radical cation. The MS/MS of the three group isomeric derivatives showed significant difference in abundance distribution of these product ions, respectively. Theoretical calculations showed that the stability of the ion-neutral complex (INC) is a key factor influencing the relative intensity of the product ions. The three group isomeric derivatives were also separated by high performance liquid chromatograph (HPLC) at conventional conditions. p-Tosylation combined tandem MS (or HPLC) technique were carried out to realize the differentiation of isomeric haloanilines.
研究领域:
分析化学
·
质谱学
·
有机化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Cartilage
·
2021
·
IF 4.634
Yunliang Lei,Jiabin Peng,Zhu Dai,Ying Liao,Quanhui Liu,Jian Li,Yonghui Jiang
ObjectiveThis study was undertaken to elucidate the mechanism of improved chondrocyte migration after juvenile articular cartilage fragmentation.DesignIn vitro organ culture with rabbit cartilage fragments and cell culture with rabbit chondrocytes were performed. In part A, minced juvenile cartilage fragments (~0.5 × 0.5 × 0.5 mm) from rabbits, planted in gelatin sponge and fibrin glue, were cultured for 2, 4, or 6 weeks in vitro and compared with the cartilage chunks (~4 × 4 × 1 mm) and membrane type 1 matrix metalloprotease (MT1-MMP) inhibitor groups. Chondrocyte outgrowth was evaluated on histology and confocal laser scanning microscopy. MT1-MMP expression was compared between the cartilage fragment group and the cartilage chunks group. In part B, articular chondrocytes were harvested from juvenile rabbits, MT1-MMP was transfected into the cells, and cell migration was evaluated using the Transwell and wound healing tests.ResultsThe histology and confocal microscopy results revealed that cell accumulation occurred at the edge of cartilage fragments, and outgrowth was better in the cartilage fragment group than those in the cartilage chunks group. Similar results were observed for MT1-MMP expression. After MT1-MMP inhibition, cells did not accumulate at the edge of the cartilage fragments, and chondrocyte outgrowth did not occur. Furthermore, overexpression of MT1-MMP enhanced the migration of articular chondrocytes.ConclusionsJuvenile articular cartilage fragmentation improved chondrocyte migration by upregulating MT1-MMP.
研究领域:
骨科
·
细胞生物学
·
组织工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）