Linkage of Aromatic Ring Structures in Saturates, Aromatics, Resins and Asphaltenes Fractions of Vacuum Residues Determined by Collision-Induced Dissociation Technology

The linkage of aromatic ring structures in vacuum residues was important for the refining process. The Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS) combined with collision-induced dissociation(CID) is a powerful method to characterize the molecular structure of petroleum fractions. In this work, model compounds with different aromatic ring structures were measured by CID FT-ICR MS. The cracking of the parent ions and the generated fragment ions were able to distinguish different linkage of the model compounds. Then, vacuum residues were separated into saturates, aromatics, resins and asphaltenes fractions(SARA), and each fraction was characterized by CID technology. According to the experimental results, the aromatic rings in saturates and aromatics fractions were mainly of the island-type structures, while the aromatic rings in resins and asphaltenes fractions had a significant amount of archipelago-type structures.

Collision-induced Rotational Energy Transfer in an Atom-Diatom System

As a further theoretical study of the collision-induced quantum interference on rotational energy transfer in an atom-diatom system, based on the first-Born approximation of time-dependent perturbation theory, taking into account the anisotropic Lennard-Jones interaction potential and the long-range interaction potential, the differential interference angles in singlet-triplet mixed states of CO A^1Π（v=9）-e3∑-（v=1） system in collision with He, Ne, Ar, and other partners were calculated theoretically. The relationships of differential interference angle versus impact parameters, including collision parameter b and velocity, are obtained.

Collision-induced absorption in the V2 fundamental band of ^12CH4

The integrated intensities of the collision-induced absorption of the V2 band of ^12CH4 perturbed by Ar have been calculated theoretically using the ab initio calculations, and the value of the quadrupole transition moment we obtained is （0/Q/V2） = 5.226ea^2.. The corresponding experimental value obtained from ^12 CH4-Ar spectra is /〈0/Q/V2）/ = 4.931ea^2. Ignoring vibration-rotation interaction and Coriolis interaction, and considering both the theoretical approximations and experimental uncertainties, the agreement can be regarded as good, thus confirming that the enhancement is due to the quadrupole collision-induced mechanism.

Appropriate choice of collision-induced dissociation energy for qualitative analysis of notoginsenosides based on liquid chromatography hybrid ion trap time-of-flight mass spectrometry

Liquid chromatography hybrid ion trap/time-of-flight mass spectrometry possesses both the MS^n ability of ion trap and the excellent resolution of a time-of-flight and has been widely used to identify drug metabolites and determine trace multi-components in natural products. Collision energy, one of the most important factors in acquiring MS^n information, could be set freely in the range of 10%–400%. Herein, notoginsenosides were chosen as model compounds to build a novel methodology for the collision energy optimization. Firstly, the fragmental patterns of the representatives for the authentic standards of protopanaxadiol-type and protopanaxatriol-type notoginsenosides were obtained based on accurate MS^2 and MS^3 measurements via liquid chromatography hybrid ion trap/time-of-flight mass spectrometry. The extracted ion chromatograms of characteristic product ions of notoginsenosides in Panax Notoginseng Extract were produced under a series of collision energies and compared to screen the optimum collision energies values for MS^2 and MS^3. The results demonstrated that the qualitative capability of liquid chromatography hybrid ion trap/time-of-flight mass spectrometry was greatly influenced by collision energies, and 50% of MS^2 collision energy was found to produce the highest collision-induced dissociation efficiency for notoginsenosides. Addtionally, the highest collision-induced dissociation efficiency appeared when the collision energy was set at 75% in the MS^3 stage.

Collisional Line Assignments and Hyperfine Structure Interpretation in Cs22^3△1g State

Accurately known energy level structure of the A＇∑u＋b3 IIu complex of states from a recent global de-perturbation of these states has enabled additional assignments of 140 perturbation facilitated infrared-infrared double resonance （PFIIDR） transitions to the 2^3△1g state from collisionally populated intermediate 1 ＋ A Eu levels. Together with the 221 previously observed 2^3△1g←A1∑u＋←X1∑g＋ Eu X Eg double resonance lines [J. Chem. Phys. 128, 204313 （2008）], molecular constants and the Rydberg-Klein-Rees potential energy curve of the 23△1g state have been recalculated （excluding 54 perturbed levels）. The centrifugal distortion constant has been determined and agrees well with the value calculated based on standard empirical formulas. The hyperfine structure of the 23△1g state, which has not resolved in our sub-Doppler excitation spectra of the 23△1g state, has been interpreted with a preliminary simulation.

Quadrupole-Linear Ion Trap Tandem Mass Spectrometry System for Clinical Biomarker Analysis

The accurate and efficient measurement of small molecule disease markers for clinical diagnosis is of great importance.In this study,a quadrupole-linear ion trap(Q-LIT)tandem mass spectrometer was designed and built in our laboratory.Target precursor ions were first selected in the quadrupole,and then injected,trapped,and fragmented simultaneously in the linear ion trap(LIT)to reduce the space charge effect,enrich the target product ions,and promote sensitivity.The targeted analytes were measured with selected reaction monitoring using a positive scan mode with electrospray ionization(ESI).Ions with a mass-to-charge ratio(m/z)ranging from 195 to 2022 were demonstrated.When scanning at 1218amu.s^(-1),unit resolution and an accuracy of higher than m/z 0.28 was obtained for m/z up to 2000.The dimensionless Mathieu parameter(q)value used in this study was 0.40 for collision-induced dissociation(CID),which was activated by resonance excitation.And an overall CID efficiency of 64%was achieved(activation time,50 ms).Guanidinoacetic acid(GAA)and creatine(CRE)were used as model compounds for small molecule clinical biomarkers.The limits of quantification were 1.0 and 0.2 nmol.L^(-1)for GAA and CRE,respectively.A total of 77 actual samples were successfully analyzed by the home-built ESI-Q-LIT tandem mass spectrometry system.The developed method can reduce matrix interference,minimize space charge effects,and avoid the chromatographic separation of complex samples to simplify the pretreatment process.This novel Q-LIT system is expected to be a good candidate for the determination of biomarkers in clinical diagnosis and therapeutics.

Fragmentation Reactions of Adduct Ions [M+CH_3CO]^+ of Isomeric Phenylenediamines

The dissociation routes of the adduct ions [M+CH3CO]+ formed by ion-moleculereaction of isomeric phenylenediamines with acetyl ion from acetone under chemical ionizationcondition were investigated by using collision-induced dissociation (CID) technique performed ation kinetic energies of 40eV. The adduct ions are intermediate ion-neutral complexes.

Structural Characterization of Petroleum Molecules by CID FT-ICR MS with Narrow Isolation Window

High resolution tandem mass spectrometry has been applied to obtain the structure information of petroleumsamples. Here, we report a mefflod for structural characterization of crude oil molecules by the collision-induced dissocia-tion （CID） technology coupled wiffl the high-field Fourier transform ion cyclotron resonmlce mass spectrometry （FT-ICRMS）. The ion isolation window was narrowed down to 1 Da to distinguish file complex homologues contained in petroleum.Aromatic model compounds and crude oil samples were measured by CID FT-ICR MS at different collision energy levels.The fragmentation of model compounds wiffl alkyl side-chains was found to be related to the size of file aromatic rings. Thefragmentation of model compounds wiffl archipelago structures depended on file lengffl of file bridge alkylene chain. Theprevalent reaction pafflway of model compounds with naphthenic rings was mainly determined by the position of naphfflen-ic rings in file molecules. On file basis of file fragmentation pathways, the structure differences of two crude oils were recog-nized as different content of naphthenic rings by CID technology with 1 Da isolation window. The NMR analysis was alsoapplied to confirm file CID results. This study exhibits the great potential of CID FT-ICR MS wiffl narrow isolation windowin file smlctural characterization of crude oil molecules.

The Fundamental Mechanism for the Collision/Pressure Induced Optic Effect

In this work, the fundamental mechanism regarding the collision and pressure induced optic effect is elucidated. Based on the concept of the collision-relaxation/the pressure-release induced optic effect put forth here, a new laser technology may be developed. Furthermore, our work also makes the understanding the photon involved chemical reaction become much clear and rationalized.

Non-Adiabatic Molecular Dynamics Simulations of Non-Charge-Transfer and Charge-Transfer Scattering in H^++CO2 at ELab=30 eV

The H^++CO2 reaction at high energies is relevant in atmospheric chemistry,astrophysics,and proton cancer therapy research.Therefore,we present herein a complete investigation of H^++CO2 at ELab=30 eV with the simplest-level electron nuclear dynamics(SLEND)method.SLEND describes nuclei via classical mechanics and electrons with a singledeterminantal Thouless wavefunction.The 3402 SLEND conducted simulations from 42 independent CO2 target orientations provide a full description of all the reactive processes and their mechanisms in this system:non-charge-transfer scattering(NCTS),charge-transfer scattering(CTS),and single C=O bond dissociation;all this valuable information about reactivity is not accessible experimentally.Numerous details of the projectile scattering patterns are provided,including the appearance and coalescence of primary and secondary rainbow angles as a function of the target orientation.SLEND NCTS and CTS differential cross sections(DCSs)are evaluated in conjunction with advanced semi-classical techniques.SLEND NCTS DCS agrees well with its experimental counterpart at all the measured scattering angles,whereas SLEND CTS DCS agrees well at high scattering angles but less satisfactorily at lower ones.Remarkably,both NCTS and CTS SLEND DCSs predict the primary rainbow angle signatures in agreement with the experiment.

Studies on Ion-molecule Reaction of Disubstituted Benzene with Ion System of Acetyl Chloride in Gas Phase

The ion-molecule reactions of disubstituted benzenes with the ion system of acetyl chloride under the chemical ionization condition were examined and the fragmentation reactions of the adduct ions formed by the ion-molecule reactions were studied by using collision-induced dissociation technique. It was found that the electron-releasing groups favored the adduct reactions and the electron-withdrawing groups did not. The position and properties of substituting groups had an effect on the relative abundance of the adduct ions. The fragmentation reaction of the adduct ions formed by ortho-benzene diamine with the acetyl ion was similar to the reductive alkylation reaction of amine in condensed phase.

Measurement of the argon-gas-induced broadening and line shifting of the barium Rydberg level 6s24d 1^D2 by two-photon resonant nondegenerate four-wave mixing

We apply two-photon resonant nondegenerate four-wave mixing with a resonant intermediate state to the obser-vation of the broadening and shifting of the barium Rydberg level 6s24d 1^D2 by collision with argon. The collision broadening and shifting cross sections are measured. This technique is purely optical, and can investigate the pressure dependence of the transverse relaxation rate-P21 between the Rydberg state and an intermediate state, as well as the transverse relaxation rate F20 between the Rydberg state and the ground state.

Investigation of the Structures of the Product Ions Produced via self-CI of Acetone

The ion-molecule reactions in acetone were investigated which were induced under the chemical ionization. The structural information of the reaction products were obtained by using collision-induced dissociation (CID) technique performed at ion kinetic energies of 30eV.

Sequence analysis of peptides with biological activities using electrospray-Fourier transform ion cyclotron resonance mass spectrometry

The mass spectra of five peptides with biological activities are reported. All mass spectra were recorded using a 4.7-T Fourier transform ion cyclotron resonance mass spectrometer equipped with an external electrospray source. The accurate molecular weights for the five peptides prepared by solid phase synthesis were measured as 1765.9013, 1063.5420, 1092.5254, 820.3804 and 1078.5193, respectively. All the data were obtained with the external calibration. Differences between observed and theoretical monoisotopic molecular weights were in the (0.2-1.0)×10-6 range. The complete primary sequence for the five polypep-tides were determined using the method of in-source electrospray ionization/collision induced dissociation (ESI/CID). All the intact y series ions and b series ions were obtained from various peptides respectively, thus determining the sequences of the five polypeptides. We found that the meas-ured accurate molecular mass of sample 4 was not in agreement with that expected from the planned

STUDY ON C_2H_6^(2+) DOUBLY CHARGED IONS——EVIDENCE FOR THE EXISTENCE OF C_2H_6^(2+) IN GAS PHASE

Collision-Induced Dissociation (CID) or Collision Activation (CA) of ion involves high kinetic energy colliding with neutral gas molecules. In part of the ions, the translational energy is converted into excitation energy, Which may lead to subsequent ion decomposition. CID has developed into an important technique for elucidating

pepgrep:A Tool for Peptide MS/MS Pattern Matching

Typically, detection of protein sequences in collision-induced dissociation （CID） tandem MS （MS2） dataset is performed by mapping identified peptide ions back to protein sequence by using the protein database search （PDS） engine. Finding a particular peptide sequence of interest in CID MS2 records very often requires manual evaluation of the spectrum, regardless of whether the peptide-associated MS2 scan is identified by PDS algorithm or not. We have developed a com- pact cross-platform database-free command-line utility, pepgrep, which helps to find an MS2 finger- print for a selected peptide sequence by pattern-matching of modelled MS2 data using Peptide-to- MS2 scoring algorithm, pepgrep can incorporate dozens of mass offsets corresponding to a variety of post-translational modifications （PTMs） into the algorithm. Decoy peptide sequences are used with the tested peptide sequence to reduce false-positive results. The engine is capable of screening an MS2 data file at a high rate when using a cluster computing environment. The matched MS2 spectrum can be displayed by using built-in graphical application programming interface （API） or optionally recorded to file. Using this algorithm, we were able to find extra peptide sequences in studied CID spectra that were missed by PDS identification. Also we found pepgrep especially useful for examining a CID of small fractions of peptides resulting from, for example, affinity puri- fication techniques. The peptide sequences in such samples are less likely to be positively identified by using routine protein-centric algorithm implemented in PDS. The software is freely available at http：//bsproteomics.essex.ac.uk：8080/data/download/pepgrep- 1.4.tgz.