Comparative study of ion kinetic energy,chemical ionisation and field desorption spectra

A comparison of the fragmentation processes operating in the first field free region was made with the fragmentation in the ion source under electron ionisation, chemical ionisation and field desorption conditions for some selected compounds which undergo retro-DielsI-Alder fragmentation in the ion source under electron ionisationconditions. The fragmentation processes which com-ete with retro-Diels-Alder fragmentation under chemical ionisation and field desorption conditions are discussed. The complementary nature of these techniques are illustrated.     

A study of the collisional fragmentation problem using the Gamma distribution approximation

The nonlinear fragmentation population balance formulation has been elevated in recent years from a prototype for studying nonlinear integro-differential equations to a vehicle for analyzing and understanding several physicochemical processes of technological interest. The so-called pure collisional fragmentation, which is the particular mode of nonlinear fragmentation induced by collisions between particles, is studied here. It is shown that the corresponding population balance equation admits large time asymptotic (self-similarity) solutions for homogeneous fragmentation and collision functions (kernels). The self-similar solutions are given in closed form for some simple kernels. Based on the shape of the self-similar solutions the method of moments with Gamma distribution approximation is employed for transient solution (from initial state to establishment of the asymptotic shape) of the collisional fragmentation equation. These solutions are presented for several sets of parameters and their behavior is discussed rather extensively. The present study is similar to the one has already been performed for the case of the much simpler linear fragmentation equation [G. Madras, B.J. McCoy, AIChE J. 44 (1998) 647].     

Identification of fragmentation channels of dinucleotides using deuterium labeling

The fragmentation of the totally deuterated dinucleotide dAT⁻ in labile positions (heteroatom-bound hydrogens) was compared for different MS/MS methods: CID, IRMPD, and EID. These experiments allowed us to affirm the coexistence of several fragmentation channels. They can be classified according to the involvement of nonlabile or labile protons in the fragmentation process. Moreover, double resonance experiments were performed in IRMPD and EID. They demonstrated the existence of consecutive fragmentation processes. The probability with which each channel is taken depends on the fragmentation technique used, i. e., the energy and the time scale of the method. The fragmentation channels that involve labile protons requiring peculiar three-dimensional structures are entropically unfavorable and enthalpically favorable. They are more observed in IRMPD and EID. The involvement of labile and, therefore, exchangeable protons in the fragmentation mechanism casts doubt on the use of tandem mass spectrometry to localize incorporated deuteriums in oligonucleotides.     

Photoionization of small sodium-doped acetic acid clusters

The uptake of sodium and the fragmentation before and after "soft" photoionization with ultraviolet light are investigated for small acetic acid clusters. The acetic acid clusters are generated in a supersonic expansion and ionized with ultraviolet light after doping with sodium in a pick-up chamber. The composition of the bare acetic acid clusters in the molecular beam is determined independently from complementary photoionization experiments using extreme ultraviolet light. The experimental results are analyzed with the help of density functional calculations for energetics and statistical adiabatic channel calculations for fragmentation kinetics. The study demonstrates that the detected ions originate from fragmentation in the neutral as well as in the ionic state, and in particular that the fragmentation pathway strongly depends on the cluster size.     

Studies on morphine alkaloids—IX. The mass spectra of indolinocodeine and its derivatives

The mass spectra of indolinocodeine and its derivatives have been determined. Some of the fragmentation pathways are discussed on the basis of high-resolution mass spectrometry and deuterium labelling. Although basic fragmentation patterns for this series of compounds are similar to each other, the substituents in B- and/or C-ring were found to determine the course of the fragmentation.     

Fragmentation-based QM/MM simulations: length dependence of chain dynamics and hydrogen bonding of polyethylene oxide and polyethylene in aqueous solutions

Molecular fragmentation quantum mechanics (QM) calculations have been combined with molecular mechanics (MM) to construct the fragmentation QM/MM method for simulations of dilute solutions of macromolecules. We adopt the electrostatics embedding QM/MM model, where the low-cost generalized energy-based fragmentation calculations are employed for the QM part. Conformation energy calculations, geometry optimizations, and Born-Oppenheimer molecular dynamics simulations of poly(ethylene oxide), PEO(n) (n = 6-20), and polyethylene, PE(n) ( n = 9-30), in aqueous solution have been performed within the framework of both fragmentation and conventional QM/MM methods. The intermolecular hydrogen bonding and chain configurations obtained from the fragmentation QM/MM simulations are consistent with the conventional QM/MM method. The length dependence of chain conformations and dynamics of PEO and PE oligomers in aqueous solutions is also investigated through the fragmentation QM/MM molecular dynamics simulations.     

Collision-induced dissociation pathways of anabolic steroids by electrospray ionization tandem mass spectrometry

Anabolic steroids are structurally similar compounds, and their product-ion spectra obtained by tandem mass spectrometry under electrospray ionization conditions are quite difficult to interpret because of poly-ring structures and lack of a charge-retaining center in their chemical structures. In the present study, the fragmentation of nine anabolic steroids of interest to the racing industry was investigated by using triple quadrupole mass spectrometer, Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer, and a linear ion trap instrument. With the aid of an expert system software (Mass Frontier version 3.0), accurate mass measurements, and multiple stage tandem mass spectrometric (MS(n)) experiments, fragmentation pathways were elucidated for boldenone, methandrostenolone, tetrahydrogestrinone (THG), trenbolone, normethandrolone and mibolerone. Small differences in the chemical structures of the steroids, such as an additional double-bond or a methyl group, result in significantly different fragmentation pathways. The fragmentation pathways proposed in this paper allow interpretation of major product ions of other anabolic steroids reported by other researchers in a recent publication. The proposed fragmentation pathways are helpful for characterization of new steroids. The approach used in this study for elucidation of the fragmentation pathways is helpful in interpretation of complicated product-ion spectra of other compounds, drugs and their metabolites.     

A study of the electrospray ionisation and ion trap fragmentation of hemiterpenoid and dimeric coumarin derivatives

The electrospray ionisation (ESI) of selected hemiterpenoid and dimeric coumarin derivatives and their subsequent fragmentation using an ion trap mass spectrometer are reported and discussed. Sequential product ion fragmentation experiments (MS(n)) were performed in order to elucidate the degradation pathways for these compounds. The results illustrate that the observed characteristic fragmentation patterns are of considerable utility in the application of ESI mass spectrometry to the characterisation of this class of compounds.     

流化床条件下煤的一次爆裂特性的实验研究

流化床锅炉中煤的爆裂特性对锅炉运行的炉内传热、碳转化率和细微颗粒的排放等许多方面有重要影响。本文在一台小型常压流化床反应器中研究了了种烟煤的一次爆裂烟煤的。对此烟煤不同宏观煤岩类型（亮煤和暗煤）的一次爆裂特性进行了比较研究。实验发现颗粒的一次爆裂率和爆裂程度很大程度上取决于颗粒粒径以及煤颗粒的组成,亮煤具有与暗煤不同的一次爆裂特性,同一粒径的煤颗粒爆裂后形成具有一定特点的粒径分布。针对不同煤岩类型     

FRAGMENTIERUNGSDIA GRAMME ZUR AUFKLÄRUNG DER ABBAUREAKTIONEN ORGANISCHER VERBINDUNGEN II–PPOLYMETHYL- UND CHILORBENZOLE

Complete fragmentation patterns are used for the investigation of the fragmentation properties of polymethylbenzenes and chlorobenzenes. The increased resonance effect of the methyl group bound to the ionised aromatic carbon septet determines the fragmentation of the polymethyl-benzenes under investigation. The structure of the different consecutive fragment ions from compounds with many methyl groups changes several times between a carbon sextet and a carbon septet in the fragmentation pathway. The fragmentation of chlorobenzenes can be understood as a consequence of an increased resonance effect. The C? Cl-bond of the chlorotropylium ion appears to be strengthened.     

Constituents of cannabis sativa L. XII—mass spectral fragmentation patterns for some. Cannabinoid acid as their TMS derivatives

Fragmentation schemes for a number of TMS derivatized cannabinoid acids are described. Specific fragmentation pathways and rearrangement mechanisms were determined based on the ion composition of deuterium labeled derivatives. Significant differences in the mode of fragmentation of the two isomeric Δ⁹-tetrahydrocannabinolic acids are described. These results are based on information obtained from deuterium labeling and high resolution data or by the extension of previously reported mechanisms for neutral cannabinoids. Comparisons of the fragmentation schemes between the neutral and acidic cannabinoids are used to confirm many of the fragmentation mechanisms.     

On the fragmentation modes in PMO analyses

The molecular species 1,1- and 1,2-disubstituted alkenes have been used as model systems for a comparative discussion of the results obtained with quantitative orbital analyses using different fragmentation modes. It is shown that when indices of the overall energy effects are used, the results of a quantitative orbital analysis are independent of the chosen fragmentation mode. On the other hand, the results of such analysis can depend on the fragmentation mode when indices of partial energy effects are used.     

Spectres de masse des composés organiques. 5e communication. Perte de méthane et d'éthylène à partir des ions butyle

The loss of methane and ethylene in the mass-spectrometric fragmentation of different isomeric butyl ions which originate from butyl halides has been studied. The different carbon atoms in n-butyl are already equivalent after 10^?7 s, whereas the statistical distribution of the hydrogen atoms within the molecule can only be observed for the metastable peaks. A protonated cyclobutane structure is proposed as an intermediate product in the fragmentation of the n-butyl ion. The fragmentation of this model has been simulated by a computer. This allows prediction as to the time-scale of fragmentation. The comparison of this model fragmentation with that of isomeric butyl ions shows that, even in the decay of the tertiary butyl ion, the formation of the proposed rearranged cyclic structure competes favorably with the direct fragmentation.     

Disintegration mechanisms of charged aqueous nanodroplets studied by simulations and analytical models

The mechanism of fragmentation processes in aqueous nanodroplets charged with ions is studied by molecular dynamics (MD) simulations. By using constant-temperature MD, the evaporation of the water is naturally taken into account and sequences of ion fragmentation events are observed. The size of the critical radius of the charged droplet just before the fragmentation and the distribution of the sizes of the fragments are estimated. Comparison of the Rayleigh critical radius for fragmentation and simulation data is within 0.23 nm. This seemingly small difference arises from a large difference in the number of water molecules that makes fragmentation an activated process as in the ion evaporation mechanism (IEM). This finding is in agreement with the predictions of Labowsky et al. [Anal. Chim. Acta 2000, 406, 105-118] for charged aqueous drops. The size of the daughter droplets is larger than the prediction of Born's theory by 0.1 to 0.15 nm. The nature and the dynamics of the intermediate states of the fragmentation process characterized by a bridge formed between the mother droplet and the evaporating ion or thorned structures where the ion sits on the tip are important for the outcome of the size-distribution of the fragments, while they are is missing in Born's theory.     

Ultraviolet photodissociation of protonated pharmaceuticals in a pressurized linear quadrupole ion trap

Ultraviolet photodissociation (UVPD) was evaluated as a technique for generating ion fragmentation information that is alternative and/or complementary to the information obtained by collision‐induced dissociation (CID). Ions trapped in a pressurized linear ion trap were dissociated using a 355 nm or a 266 nm pulsed laser. Comparisons of UVPD and CID spectra using a set of aromatic chromophore‐containing compounds (desmethyl bosentan, haloperidol, nelfinavir) demonstrated distinct characteristic fragmentation patterns resulting from photodissociation. The wavelength of light and the pressure of the buffer gas in the UVPD cell are important parameters that control fragmentation pathways. The wavelength effect is related to the absorption cross section, location of the chromophore and the energy carried by one photon. Thus, UV irradiation wavelength affects fragmentation pathways as well as the fragmentation rate. The pressure effect can be explained by collisional quenching of ‘slow’ fragmentation pathways. We observed that higher pressure of the buffer gas during UVPD experiments highlights unique fragment ions by suppressing slow fragmentation pathways responsible for CID‐like fragmentation patterns. Copyright © 2010 John Wiley & Sons, Ltd.     

Chemical ionization mass spectra of amino acids and derivatives. Occurrence and fragmentation of ion-molecule reaction products

The Chemical ionization mass spectra of free amino acids, their amides, methyl esters and Na-acetyl derivatgives, using methane as reagent gas, are presented, The occurrence and fragmentation of ion-molecules reaction products are discussed. A preference for a head to tail, configuration of the association complex [2M + 1]⁺ is postulated to esplain promienent fragmentation pathways of this complex. Interesting fragmentation pathways have been found with onithine, arginine and citrulline.     

Unimolecular and collision-induced fragmentation of protonated nitroarenes

The unimolecular fragmentation reactions of 28 protonated nitroarenes, occurring on the metastable ion time-scale, are reported. In addition, the collision-induced fragmentation of the same species have been studied at 10 eV and at 50 eV collision energy. When an OH, COOH or NH₂ substituent is ortho to the nitro function, the dominant fragmentation involves loss of H₂O, for both unimolecular and collision-induced reactions. When there is an electron-releasing substituent ortho or para to the litro group, loss of OH is the dominant fragmentation reaction both on the metastable ion time-scale and for ions activated by collision. When the electron-releasing substituent is meta to the nitro group, loss of NO₂ is the dominant low-energy unimolecular fragmentation reaction while loss of HNO₂ is the most important fragmentation for ions activated by 50 eV collisions. Elimination of NO from [MH]⁺ occurs to a significant extent in the unimolecular fragmentation of protonated nitrobenzene and those protenated nitrobenzenes containing electron- attracting substituents. In the collision-induced dissociation of these species loss of HNO₂ occurs at the expense of loss of NO. The results are consistent with protonation predominantly at the nitro group. The results are discussed in terms of the use of neutral loss scans in tandem mass spectrometry to monitor complex mixtures for nitroarenes.     

PDMS-chemistry of angiotensin II and insulin in glucose glass thin films

A plasma desorption mass spectrometry study was made on the properties of glucose and glucose/glucuronic acid thin films as matrices for amino acids, small and large peptides and insulin. Amino acids and small peptides are distributed throughout the film as it is formed from aqueous solutions and the mass spectra are similar to what is observed for nitrocellulose matrices. AngiotensinII (angII), insulin, and reduced insulin containing the separated A- and B-chains concentrate at the surface of the film due to the hydrophobic interaction. Extensive positive and negative fragmentation patterns are observed for angII using the glucose glass film. The fragment ions appear to be formed from layers just below the surface of the film. The co-matrix of glucuronic acid/glucose produces a higher molecular ion yield. The spectrum of insulin in glucuronic acid/glucose consists mainly of positive ions with a fragmentation pattern from the B-chain. The spectrum of reduced insulin using a nitrocellulose matrix gives B-chain ions but glucose/glucuronic acid gives A-chain ions in both the positive and negative ion spectra. The fragmentation patterns of the A-chain and B-chain ions are sensitive to the nature of the matrix. An extensive negative ion A-chain fragmentation pattern was observed with glutamate ions serving as the charge centers. The reasons for the behavior of the A- and B-chain fragmentation patterns in these matrices is not clear.     

Fragmentation studies of monensin A and B in negative electrospray and nanospray tandem mass spectrometry

This paper reports the first comparative study of the gas-phase fragmentation chemistry of monensin in negative ion mode electrospray and nanoelectrospray tandem mass spectrometry. The fragmentation was observed to occur at lower energies in nanoelectrospray than electrospray. The major product ions are proposed to be formed via an initial neutral elimination of methanol followed be subsequent fragmentation. The low-mass product ions were observed at the same m/z for both monensin A and B.     

Fragmentation Pathways of Singly- and Doubly-charged Ions in the Mass Spectra of Si-, N- and C-Substituted 1,3-Dioxa-6-aza-2-silacyclooctanes

The fragmentation pathways of singly- and doubly-charged ions in the mass spectra of Si-, N-, and C-substituted 1,3-dioxa-6-aza-2-silacyclooctanes upon electron impact have been studied. The directions for the fragmentation of the singly- and doubly-charged molecular ions differ markedly. All the doubly-charged fragmentation ions are formed by the loss of neutral molecules from M⁺⁺ and contain nitrogen and silicon atoms.