Automated peak width measurements for targeted analysis of ion mobility unresolved species

Peak broadening in ion mobility (IM) is a relatively predictable process and abnormally broad peaks can be indicative of the presence of unresolved species. Here, we introduce a new ion mobility peak fitting (IM_FIT) software package for automated and systematic determination of traveling wave ion mobility (TWIM) unresolved species. To identify IM unresolved species, the IM_FIT software generates a trend line by plotting ions' mobility peak widths as a function of their arrival times. Utilizing user-defined thresholds, IM_FIT allows for automated and rapid detection of ions that deviate from the peak width trend line. To demonstrate the advantages of IM_FIT for automated detection of IM unresolved species, IM-mass spectrometry (IM-MS) data from a sample mixture containing polypropylene glycol and multiple peptides were analyzed. A total of 14 out of the 34 observed singly-charged IM peaks above 5% relative abundance (i.e., signal-to-noise ratios above ∼200) were tagged as potentially co-eluting ions by IM_FIT. Subsequently, the 14 IM peaks tagged as potentially unresolved (presumably, peaks corresponding to co-eluting compounds), were further analyzed by automated IM deconvolution (AIMD), liquid chromatography-IM-MS (LC-IM-MS), and/or ultra-high resolution mass spectrometry. Using the aforementioned techniques, more than 85% of the tagged IM peaks (12 out of 14) were confirmed to contain co-eluting ions. As an additional new finding, IM_FIT facilitated the discovery of an unexpected sequence-scrambled y-type fragment ion.     

Global stability for a class of mass action systems allowing for latency in tuberculosis

A very general compartmental model of the spread of an infectious disease with mass action incidence is given. The global stability of this system is completely determined using Lyapunov functions. The general system exhibits the traditional threshold behaviour. The dimension of the system is arbitrary, allowing, in particular, for detailed modelling of the distribution of latency times for tuberculosis.     

闭壳层金掺杂钛氧团簇阴离子解离氢分子研究

Dissociation of molecular hydrogen (H₂) is extensively studied to understand the mechanism of hydrogenation reactions. In this study, H₂ dissociation by Au₁-doped closed-shell titanium oxide cluster anions AuTi₃O₇^- and AuTi₃O₈^- has been identified by mass spectrometry and quantum chemistry calculations. The clusters were generated by laser ablation and massselected to react with H₂ in an ion trap reactor. In the reaction of AuTi₃O₈^- with H₂, the ion pair Au⁺-O₂^2- rather than Au⁺-O^2- is the active site to promote H₂ dissociation. This finding is in contrast with the previous result that the lattice oxygen is usually the reactive oxygen species in H₂ dissociation. The higher reactivity of the peroxide species is further supported by frontier molecular orbital analysis. This study provides new insights into gold catalysis involving H₂ activation and dissociation.     

2-甲基-2-丙烯-1-醇的光电离解离研究

利用可调谐真空紫外同步辐射和分子束实验装置在8.0～15.5 eV的光子能量范围内,研究2-甲基-2-内烯-1-醇的光电离解离.测出母体离子和碎片离子:C_4H_8O~+、C_4H_7O~+、C_3H_5O~+、C_4H_7~+、C_4H_6~+、C_4H_5~+、C_2H_4O~+、C_2H_3O~+、C_3H_6~+、C_3H_5~+、C_3H_3~+、CH_3O~+和CHO~+的光电离效率曲线,并获得母体分子的电离能和碎片离子的实验出现势.在B3LYP/6-31+G(d,p)理论水平上,计算光电离过程中母体分子、过渡态和中间体的稳定结构.采用CCSD(T)/cc-pVTZ耦合簇方法计算零点能,得到母体电离能和碎片离子的出现势.通过实验和理论研究,提出2-甲基-2-丙烯-1-醇的光解离路径,分子内氢转移是其中大部分解离途径中的主要过程.     

Determination of Endogenous Neurotoxin 1-Acetyl-6,7-Dihydroxyl-1,2,3,4-Tetrahydroisoquinoline in Rat Substantia Nigra by High Performance Liquid Chromatography-Electrospray Ionization-Tandem Mass Spectrometry

The endogenous neurotoxin, 1-acetyl-6,7-dihydroxyl-1,2,3,4 –tetrahydro isoquinoline (ADTIQ), is acatecholamine isoquinoline, indicating its possible involvement in Parkinson's disease. Moreover, it has been assumed to be a bridge between diabetes and Parkinson's disease because metabolic synthesis resembles glucose metabolism. Therefore, the accurate determination of ADTIQ could play an important role in diagnosis of diabetes and Parkinson's disease. Herein, a sensitive and precise method was established to determine ADTIQ by high performance liquid chromatography-electrospray ionization-tandem mass spectrometry in multiple reaction monitoring mode. The [M+H]⁺ precursor product ions for ADTIQ were 208.1/190.1 and linear range of calibration curve was from 1.0 to 250.0 nM. The limit of detection and limit of quantification of the developed method were 0.2 nM and 1 nM, respectively. The inter-day, intra-day precision, accuracy, and recoveries were acceptable for biological samples. Furthermore, the reported method was used to determine ADTIQ levels in the substantia nigra of rats. The results indicated that the developed method was highly sensitive and accurate for the determination of ADTIQ.     

Determination of triacylglycerol regioisomers using electrospray ionization-quadrupole ion trap mass spectrometry with a kinetic method

The kinetic method was applied to differentiate and quantify mixtures of regioisomeric triacylglycerols (TAGs) by generating and mass selecting alkali ion bound metal dimeric clusters with a TAG chosen as reference (ref) and examining their competitive dissociations in a quadrupole ion trap mass spectrometer. This methodology readily distinguished pairs of regioisomers (AAB/ABA) such as LLO/LOL, OOP/OPO and SSP/SPS and consequently distinguished sn-1/sn-3, sn-2 substituents on the glycerol backbone. The dimeric complex ions [ref, Li, TAG_{(AAB and/or ABA)}]⁺ generated by electrospray ionization mass spectrometry were subjected to collision induced dissociation causing competitive loss of either the neutral TAG reference (ref) leading to [Li(AAB and/or ABA)]⁺ or the neutral TAG molecule (TAG_{(AAB and/or ABA)}) leading to [ref, Li]⁺. The ratio of the two competitive dissociation rates, defined by the product ion branching ratio (R_iso), was related via the kinetic method to the regioisomeric composition of the investigated TAG mixture. In this work, a linear correlation was established between composition of the mixture of each TAG regioisomer and the logarithm of the branching ratio for competitive fragmentation. Depending on the availability of at least one TAG regioisomer as standard, the kinetic method and the standard additions method led to the quantitative analysis of natural TAG mixtures.     

Rapid detection of pesticide residues in Chinese herbal medicines by molecularly imprinted membrane electrospray ionization mass spectrometry

Chinese herbal medicines(CHMs) play an increasingly important role in the field of medicine and affects public health in the world.Although more and more strict has been employed to ensure the quality and safety of CHMs,pesticide residues in CHMs remain a serious issue and are the bottleneck for the global development of CHMs.In this work,we applied molecularly imprinted membrane electrospray mass spectrometry(MIM-ESI MS) for rapid detecting 4 classes of pesticide residues in CHMs,including organophosphorus(OPP),carbamates,pyrethroids and neonicotinoids in CHMs.Compared with our previous ambient ionization method MESI,MIM-ESI is capable of achieving a ～50-fold increase in the detection limit of conventional analytical methods owing to the specificity recognition and unique enrichment of MIM.The optimal experimental conditions were determined,and the method was further validated for its sensitivity and specificity.Our data showed that MIM-ESI MS is applicable for the direct quantitation of pesticide residues in CHMs.This detection technology may help to ensure the quality of CHMs in the future.     

Identification and Characterization of 4-Hydroxy-2H-1,2-benzothiazine-3-carboxylic Acid 1,1-Dioxide Derivatives by Mass Spectroscopy

Electron impact mass spectral fragmentation of certain esters and amides derived from 4-hydroxy-2H-1,2-benzothiazine-3-carboxylic acid 1,1-dioxide is described. Common ions to both series may be observed, as well as others allowing them to be differentiated. The method is promissory for identification and analysis of these compounds.     

辉光放电质谱分析中质谱干扰及其校正方法的现状

详细地介绍了辉光放电质谱分析中的质谱干扰如同量异位素、多原子离子和多电荷离子干扰。从同位素选择、高分辨率仪器、碰撞诱导解离、离子源冷却、数学方法校正、放电气体更换和放电气体纯度提高等方面对辉光放电质谱的质谱干扰校正方法的现状进行了评述(引用文献共68篇)。