Offline two-dimensional liquid chromatography coupled with ion mobility-quadrupole time-of-flight mass spectrometry enabling fourdimensional separation and characterization of the multicomponents from white ginseng and red ginseng

Inherent complexity of plant metabolites necessitates the use of multi-dimensional information to accomplish comprehensive profiling and confirmative identification.A dimension-enhanced strategy,by offline two-dimensional liquid chromatography/ion mobility-quadrupole time-of-flight mass spectrometry(2 D-LC/IM-QTOF-MS)enabling four-dimensional separations(2 D-LC,IM,and MS),is proposed.In combination with in-house database-driven automated peak annotation,this strategy was utilized to characterize ginsenosides simultaneously from white ginseng(WG)and red ginseng(RG).An offline 2 DLC system configuring an Xbridge Amide column and an HSS T3 column showed orthogonality 0.76 in the resolution of ginsenosides.Ginsenoside analysis was performed by data-independent high-definition MSE(HDMSE)in the negative ESI mode on a Vion?IMS-QTOF hybrid high-resolution mass spectrometer,which could better resolve ginsenosides than MSEand directly give the CCS information.An in-house ginsenoside database recording 504 known ginsenosides and 58 reference compounds,was established to assist the identification of ginsenosides.Streamlined workflows,by applying UNIFI?to automatedly annotate the HDMSEdata,were proposed.We could separate and characterize 323 ginsenosides(including 286 from WG and 306 from RG),and 125 thereof may have not been isolated from the Panax genus.The established 2 D-LC/IM-QTOF-HDMSEapproach could also act as a magnifier to probe differentiated components between WG and RG.Compared with conventional approaches,this dimensionenhanced strategy could better resolve coeluting herbal components and more efficiently,more reliably identify the multicomponents,which,we believe,offers more possibilities for the systematic exposure and confirmative identification of plant metabolites.

Analyzing crude oils from the Junggar Basin(NW China) using comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry(GC×GC-TOFMS)

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.

Dimension-Enhanced Ultra-High Performance Liquid Chromatography/Ion Mobility-Quadrupole Time-of-Flight Mass Spectrometry Combined with Intelligent Peak Annotation for the Rapid Characterization of the Multiple Components from Seeds of Descurainia sophia

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.

Spectrum-effect relationship between HPLC fingerprints and bioactive components of Radix Hedysari on increasing the peak bone mass of rat

The traditional Chinese medicine of Radix Hedysari plays an important role in invigorating gas for ascending, benefiting blood for promoting production of fluid, and promoting circulation for removing obstruction in collaterals, which is consistent with the principle of treatment for osteoporosis. This study is designed to investigate the bioactive components on increasing peak bone mass (PBM) by exploring the spectrum-effect relationship between chromatography fingerprints and effect. Multiple indicators are selected to evaluate the pharmacological activity. In fingerprints, 21 common peaks are obtained, five of which are identified. Furthermore, gray relational analysis (GRA) is a quantitative method of gray system theory and is used to describe the correlation degree of common peaks and pharmacological activities with relational value. 21 components are then divided into three different regions, of which ononin and calycosin play an extremely significant role in increasing PBM. In addition, factor analysis and hierarchical cluster analysis (HCA) are used to screen the optimal producing area for Radix Hedysari. This provides a comprehensive and efficient method to improve the quality evaluation of Radix Hedysari, confirming the bioactive components for PBM-enhancement and further develop its medicinal value.

Dependence of Decamethylcyclopentasiloxane (DMCPS) Dissociation on Ionized Energy by Using Quadrupole Mass Spectrum

Dependence of decamethylcyclopentasiloxane （DMCPS） organosilicon dissociation on ionized energy in the energy range of 25 eV to 70 eV is investigated by using a quadrupole mass spectrometry. At the ionized energy below 55 eV, the dissociation of DMCPS is dominant. As the ionized energy is above 55 eV, the DMCPS dissociation achieves the maximum cross section, while the fragments from the DMCPS dissociation can further dissociate, which leads to a different ingredient of fragments. At the lower ionized energy of 25 eV, the main fragments are SiOC2H＋, SiCH＋, Si＋, O＋ and CH＋ ions, which shows an important effect on the SiCOH low-k film deposition.

Towards the understanding of 1^1 p1 meson mass spectrum

Based on the meson-meson mixing and Regge trajectory, this paper establishes the mass relations which can describe the mass spectrum of 1^1 P1 meson state. Using these mass relations, it obtains the mass of K1B, hi （1380） and hc（1P） to be 1358.5MeV, 1468 MeV and 3543.9 MeV, respectively. The results are compared with other theoretical results and should be tested by experiments in the future.

Studies on Fragmentation Regularity of 5-Methoxycarbonyl- 4-substituted-6-methyl-3,4-dihydropyrimidin-2(1H)-ones by Time-of-flight Mass Spectrometry

The electron impact time-of-flight(TOF) mass spectra of the title compounds were studied to establish their fragmentation processes. With the high resolution of the TOF instrument, the exact mass for each fragment was determined. These data were used to infer the molecular formulas and the elemental compositions for all the molecular ions and fragments through software interpretation. By further applying the fragmentation regularity, the majority of ions were fully assigned. The main fragmentation pathways of the title compounds include the formation of molecular ions by the loss of R 1 groups in the 4-position and the ester groups in the 5-position. The formed ion can be further fragmented by the elimination of MeOH.

Temporal and spatial study of differently charged ions emitted by ns-laser-produced tungsten plasmas using time-of-flight mass spectroscopy

Tungsten(W)is an important material in tokamak walls and divertors.The W ion charge state distribution and the dynamic behavior of ions play important roles in the investigation of plasma–wall interactions using laser-ablation-based diagnostics such as laser-induced breakdown spectroscopy and laser-induced ablation spectroscopy.In this work,we investigate the temporal and spatial evolutions of differently charged ions in a nanosecond-laser-produced W plasma in vacuum using time-of-flight mass spectroscopy.Ions with different charge states from 1 to 7(W+to W7+)are all observed.The temporal evolutions of the differently charged ions show that ions with higher charge states have higher velocities,indicating that space separation occurs between the differently charged ion groups.Spatially-resolved mass spectroscopy measurements further demonstrate the separation phenomenon.The temporal profile can be accurately fitted by a shifted Maxwell–Boltzmann distribution,and the velocities of the differently charged ions are also obtained from the fittings.It is found that the ion velocities increase continuously from the measured position of 0.75 cm to 2.25 cm away from the target surface,which indicates that the acceleration process lasts through the period of plasma expansion.The acceleration and space separation of the differently charged ions confirm that there is a dynamic plasma sheath in the laser-produced plasma,which provides essential information for the theoretical laser-ablation model with plasma formation and expansion.

The Development of Time-of-flight Mass Spectrometry( TOF-MS) and Its Applications in Screening Food Hazard Factors

The time-of-flight mass spectrometry(TOF-MS),one of the mass spectrometry techniques,has been widely applied in the field of rapid screening of food hazard factors as a superior analysis technique because of its wide mass range,high resolution and mass measurement accuracy,high sensitivity and high analysis speed.In this paper,research progresses of TOF-MS on the detection of food additives,food contaminants and residues,illegal additives,pesticide residues,veterinary drug residues and mycotoxin were reviewed,and its probable approaching applications were prospected.

MicrobMatcher: a microbial comparison software based on matrix-assisted laser desorption/ionization with time-of-flight mass spectrometry

Matrix-assisted Laser Desorption/Ionization with Time-of-flight Mass Spectrometry (MALDI-TOFMS) was investigated as a method for the rapid identifica-tion of species. Current demand in microbial identi-fication is how to compare unknown strains to the known one quickly, semi-automatically and accurately. In this paper, we present a software tool that allows flexibly microbial matching in a user-friendly way, by letting the users to customize comparison parameters including: in vitro transcription enzyme, mass tolerance,minimum fragment length, intensity threshold and corresponding weights. We provide three spectral scoring functions to compute the affin-ity between the species. Therefore, the precision of microbial comparison increases. To test and verify this tool, we employed experimental spectral data based on MALDI-TOFMS and the gene sequences of E.coli and Salmonella. This software is written in Java for cross-platform intention.

Vector Boson Mass Spectrum from Extra Dimension

Based on the mechanism for mass creation in the space-time with extradimensions proposed in our previous work, (arXiv: 1301.1405 [hep-th] 2013) we consider now the mass spectrum of vector bosons in extradimensions. It is shown that this spectrum is completely determined by some function of compactification length and closely related to the metric of extradimensions.

Mass Spectrum of Dirac Equation with Local Parabolic Potential

In this paper, we solve the eigen solutions to the Dirac equation with local parabolic potential which is approximately equal to the short distance potential generated by spinor itself. The energy spectrum is quite different from that with Coulomb potential. The mass spectrum of some bary-ons is similar to this one. The angular momentum-mass relation is quite similar to the Regge trajectories. The parabolic potential has a structure of asymptotic freedom near the center and confinement at a large distance. So, the results imply that, the local parabolic potential may be more suitable for describing the nuclear potential. The procedure of solving can also be used for some other cases of Dirac equation with complicated potential.

Application of Liquid Chromatography-High Resolution Time-of-flight Mass Spectrometry in the Detection of Raw Milk and Dairy Products

Milk and dairy products are more and more popular with consumers due to their various nutrients, and their quality and safety issues have always been concerned. Therefore, the development of rapid, accurate and simple screening techniques is of great significance. Liquid chromatography-high resolution time-of-flight mass spectrometry has high-resolution and high-throughput detection functions, and has gradually begun to be applied in the detection of milk and dairy products. This paper summarized the application of milk and dairy products in liquid chromatography-high resolution time-of-flight mass spectrometry, laying a foundation for the development of new methods.

5-22 Design and Optimization of a Multi-re Time-of-flight Mass Analyzer for LPT

Multi-reflection time-of-flight mass spectrometer (MR-TOF-MS) is one of the new experimental devices developed in recent years. As the flight path extended several orders of magnitude as the analyzer is traversed many times by the ions, it allows achieving higher mass resolving power than the conventional time-of-flight mass spectrometry.

Time-of-Flight Mass Spectrometer with Transaxial Ion Reflector

Two variants of application of a transaxial mirror with stigmatic spatial time-of-flight focusing in the time-of-flight mass spectrometer have been considered. In the first variant, the transaxial mirror is used as an ion reflector in the ordinary scheme of the time-of-flight mass reflectron. In the second variant, the transaxial mirror simultaneously fulfills the function of the ion reflector and corrector of aberrations caused by the energy spread of ions in the package, formed by the ion source of the mass reflectron. The expressions defining the conditions of stigmatic spatial time-of-flight focusing in the transaxial mirror and the combined system consisting of an ion source and a mirror have been derived. The relationships between geometrical and electrical parameters of three- and four-electrode transaxial mirrors realizing these conditions have been obtained by numerical calculations.

茉莉酸调控马铃薯离体块茎发育的主要代谢物变化

【目的】茉莉酸(jasmonic acid,JA)是马铃薯块茎发育过程中重要调控激素之一,研究JA调控块茎发育机理将为块茎产量及品质性状形成提供重要理论基础。【方法】采用马铃薯离体匍匐茎作为供试材料,外源添加JA(0、0.5、5和50μmol·L^(-1))处理,分析JA诱导离体块茎表型形态、组织显微结构、碳水化合物积累及蛋白质组变化。【结果】随JA处理浓度升高,单个匍匐茎形成块茎数目、块茎直径及干鲜重、环髓区细胞面积、淀粉及可溶性糖含量在0.5和5μmol·L^(-1)JA处理后逐渐增加(P<0.05),而50μmol·L^(-1)JA处理后块茎直径及干鲜重、淀粉含量显著减少(P<0.05);脂氧合酶活性随JA浓度升高逐渐降低(P<0.05)。采用双向凝胶电泳(2-DE)和MALDI-TOF/TOF-MS质谱技术鉴定到JA调控块茎发育密切相关的35个差异表达蛋白质(P<0.05且差异表达倍数≥2.5倍),主要涉及生物能量与代谢(28.6%)、细胞防御(28.6%)、蛋白质生物合成与贮藏(11.4%)、信号转导(8.6%)、转录(8.6%)、未知功能(8.6%)和混杂(5.6%)。通过聚类分析将这些蛋白质差异表达模式聚为三类:第一类包括17个蛋白质,在0.5μmol·L^(-1)JA处理后下调表达,而在5μmol·L^(-1)JA处理后上调表达,主要参与生物能量与代谢、蛋白质生物合成与贮藏、信号转导、转录;第二类包括10个蛋白质,随JA浓度升高上调表达,主要参与细胞防御、生物能量与代谢、转录;第三类包括8个蛋白质,JA处理后均下调表达,主要参与生物能量与代谢、细胞防御、蛋白质生物合成与贮藏。【结论】低浓度JA(0.5和5μmol·L^(-1))主要通过诱导块茎环髓区细胞膨大、细胞内蔗糖及多糖积累、细胞防御能力来促进块茎形态建成,而高浓度JA(50μmol·L^(-1))则表现为抑制作用。

六种常用农药成分在茄子中残留降解动态

本研究旨在探索啶虫脒、噻虫胺、噻虫嗪、哒螨灵、联苯菊酯和高效氟氯氰菊酯在茄子中的残留降解动态,以支持食品安全和生态环境保护。通过气相色谱—三重四极杆质谱法和液相色谱—三重四极杆质谱法,检测了这些农药在茄子中的降解情况,并采用一级动力学模型拟合了降解曲线,得到了农药组分的半衰期。结果表明,农药残留降解受到农药种类、环境条件和作物种类等多重因素的影响,不同农药在茄子中的残留期有所差异。部分农药的降解需结合二级动力学模型进行深入分析,从而得到了新的拟合降解方程。本研究为茄子种植中农药的合理施用及减少农药残留提供了科学指导。

基于MassARRAY平台的人血小板抗原基因分型的质谱检测方法

目的:建立基于MassARRAY质谱iPLEX分析技术的人血小板抗原(human platelet antigen,HPA)基因分型方法。方法:通过文献检索HPA1-29W系统的单核苷酸多态性突变或缺失位点的信息,确定35个目的基因突变位点,按MassARRAY突变位点标示方法、引物设计固定格式和引物设计软件在线设计90条引物(正、反向扩增引物和延伸引物各30条),以12个插入HPA1-29W野生型和突变型序列的合成质粒以及50例已知HPA分型的献血者样本进行扩增和质谱检测,分析灵敏度、特异度和重复性,随机抽取15例样本的一代测序和质谱分型结果进行对比验证,建立检测方法。结果:基于MassARRAY平台的HPA基因分型的质谱检测方法与测序法检测结果相符合,灵敏度为100%,特异度为100%,重复性为100%。结论:成功建立基于MassARRAY平台的HPA1-29W系统的质谱分型方法,适合中国人群HPA分型,具有临床应用前景。

改进的高压气枪震源气泡物理模型及其应用

基于可压缩气泡动力学理论,建立改进的高压气枪震源气泡物理模型,其中考虑气枪气泡系统之间的物质输运效应、气液热传导等多种影响因素.改进模型的计算结果与实验数据吻合良好,且优于传统模型.在此基础上,本文分别探究了特征参数对单枪和双枪气泡动力学特性及流场压力波的影响规律.研究表明气枪开口方式是模拟压力波首脉冲的关键因素,但是对于后续的气泡溃灭脉动压力影响较小;气枪平移运动对气泡的影响可忽略不计;气枪非同步激发可在保证压力波低频段能量不降低的前提下,在一定程度上削弱高频段能量.本研究旨在为深海资源勘探新型气枪的设计提供参考.