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Yinlong Guo

Publications and source records attributed to Yinlong Guo.

11 recordsLinked to original sources

Study of methylation of nitrogen-containing compounds in the gas phase.

The methyl migration between the protonated N,N-dimethylisopropylamine and other neutral aliphatic amines in the gas phase has been investigated by a hybrid external chemical ionization source ion trap mass spectrometer. Similar reactions have been found in the aqueous solution by Callahan and Wolfenden (J. Am. Chem. Soc. 2003; 125: 310). At the same time, density functional theory (DFT) calculations show that in contrast with the neutral N,N-dimethylisopropylamine, protonated N,N-dimethylisopropylamine is a better methyl donor. These results indicate that protonation promotes the methyl migration between aliphatic amines both in the gas phase and in the aqueous solution. In addition, methyl transfer also exists between the protonated N,N-dimethylisopropylamine and some other nitrogen-containing compounds.

Gases↗

Studies of gas-phase fragmentation reactions of [Pd(PPh3)2(OCOR)]+ by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry.

Gas-phase fragmentation reactions of [Pd(PPh3)2(OCOR)]+ (R = H, CH3, CD3, C2H5, n-C3H7, n-C6H13 and C6H5) were studied by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS). In sustained off-resonance irradiation collision-activated dissociation (SORI-CAD) experiments, the complexes all dissociated to yield the same product ion at m/z 629.1. We propose that the fragmentation pathway occurs through the elimination of RCOOH and a palladium(IV) hydride intermediate. Semi-empirical (PM3) calculations shed light on the mechanism for the fragmentation reactions of these compounds. The results of deuterium-labeling experiments indicate that the protons of RCOOH lost from [Pd(PPh3)2(OCR)]+ originate from the phenyl in the triphenylphosphine ligand. [Pd(PPh3)2(OCOH)]+ undergoes two competitive pathways in SORI-CAD experiments, one of which is similar to that of [Pd(PPh3)2(OCOR)]+ (R = CH3, CD3, C2H5, n-C3H7, n-C6H13 and C6H5), and the other involves decarboxylation. The present study demonstrates that MS could play an important role in studying the gas-phase chemistry of palladium hydrides.

Journal Article↗

Interception of the radicals produced in electrophilic fluorination with radical traps (Tempo, Dmpo) studied by electrospray ionization mass spectrometry.

The interaction of the nitroxide radical traps (Tempo and Dmpo) and radicals produced in the electrophilic fluorination of olefins (styrene and alpha-methylstyrene) and Selectfluor (1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octanebis(tetrafluoroborate) (F-TEDA-BF(4)) (1)) was investigated by electrospray ionization mass spectrometry (ESI-MS). Tempo succeeded in intercepting the radical cationic intermediates and the radical adduct ions were detected at m/z 260 (for styrene) and m/z 274 (for alpha-methylstyrene). Dmpo could also intercept the fluorine radical and radical adduct ions were detected at m/z 131, 132 and 152. The interception of the radical cationic intermediates and fluorine radical is good evidence for the presence of a single-electron transfer mechanism in the electrophilic fluorination.

Fluorine↗

Investigation of radical cation in electrophilic fluorination by ESI-MS.

Reaction solutions of selectfluor (1) with triphenylethylene (4a) and tetraphenylethylene (4b) were monitored by ESI-MS and ESI-MS/MS. Detection and characterization of the key radical cationic intermediates 5a.+ and 5b.+) fully supports the SET mechanism in electrophilic fluorination as depicted above. [reaction: see text]

Journal Article↗

Identification of volatile basic components in tobacco by headspace liquid-phase microextraction coupled to matrix-assisted laser desorption/ionization with Fourier transform mass spectrometry.

A method incorporating headspace liquid-phase microextraction (HS-LPME) coupled to matrix-assisted laser desorption/ionization (MALDI) with Fourier transform mass spectrometry (FTMS) was established to analyze volatile basic components in tobacco. The sample preparation volume for MALDI-MS was compatible with the volume of the solvent microdrop in the HS-LPME procedure. The pH and the polarity of the solvent for HS-LPME were adjusted by choice of the MALDI matrix and matrix additive. Based on the elemental composition and tandem mass spectrometry information, 25 volatile nitrogenous compounds in tobacco were detected and identified. The approach is fast and sensitive, and has the potential for automation for high-throughput analysis. This approach offers an alternative method for analysis of trace volatile organic compounds in complex samples.

Gas Chromatography-Mass Spectrometry↗

Porous anodic alumina membrane as a sample support for MALDI-TOF MS analysis of salt-containing proteins.

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometric (MALDI-TOF MS) analysis of proteins in salt-containing solution was performed for the first time using porous anodic alumina (PAA) membrane as sample support. The resulting spectral quality of proteins under standard sample preparation conditions was superior to that of normal metal sample stages. Analysis of phosphate-doped protein solutions indicated that porous anodic alumina membranes as a target yielded better results than a metallic target for salt-containing solutions. Because of the biocompatibility of the PAA, proteins can be adsorbed on the PAA and thus a washing process can be introduced to remove the salts from the PAA target before MS analysis. This desalting step significantly enhanced spectral quality, and better signal-to-noise ratios were obtained. The present technique is promising for proteomics research.

Adsorption↗

Using amino acids for probing structural information of cytochrome c by electrospray ionization mass spectrometry.

By using electrospray ionization mass spectrometry (ESI-MS), protein complexes of cytochrome c with amino acids were studied. Different amino acids were investigated to explore these complexes. Using these amino acids, a strategy for probing the structure of cytochrome c was established. It was found that L-Arg and L-Glu could bind with cytochrome c to form noncovalent complexes. At low pH solution, complexes between the cytochrome c molecule with several L-Arg molecules (multiple L-Arg adducts) were formed, and the number of binding ligands depended on the charge state of cytochrome c. While in neutral solution, the cytochrome c molecule complexed with only one L-Arg molecule (single L-Arg adducts). As for L-Glu, only single L-Glu adducts were formed in both acidic and neutral solutions.

Amino Acids↗

High accuracy mass measurement of peptides with internal calibration using a dual electrospray ionization sprayer system for protein identification.

A dual-ESI-sprayer system was constructed and applied to achieve high accuracy of peptide mass measurement for protein identification by means of peptide mapping. Sample was introduced in one sprayer, and reference in the other, thus making internal calibration possible greatly enhancing the mass accuracy. Several samples were utilized to evaluate the reliability of this dual-ESI-sprayer system. The range of mass errors was 0.16-5.37 ppm. The peptide masses of tryptic digests of myoglobin (horse) were measured by the HPLC/dual-ESI-MS system, with mass deviations ranging from 0.01-7.67 ppm, and about 75% mass deviations below 5 ppm with 40% below 1[?]ppm. These peptide masses were utilized to perform database searching for protein identification, and compared to results obtained by external calibration. This comparison showed that the internal calibration provides a more reliable method of protein identification, with a much smaller number of required peptides for matching, and with less CPU time consumed for database searching.

Animals↗