Features of the first and second order electrospray ionization mass spectra of salt-like products derived from mono and diols with the aid of combined reagents on the basis of ω-bromoacyl chlorides and nitrogen bases

T14N2

V.V. Ilyushenkova, L.N.Kulikova, R.S. Borisov, V.G. Zaikin

The paper describes the results of application of derivatization by composite reagents on the basis of ω-bromoacyl chlorides [ClCO(CH2)nBr (n=1-4)] and pyridine for the investigation of aliphatic and alicyclic alcohols and diols by ordinary and tandem electrospray/ionization (ESI) mass spectrometry. The applied derivatization involves the simultaneous acylation of hydroxyl groups by acyl chloride part of a reagent and quaternization of pyridine by bromoalkyl end group. Under the ESI conditions, quaternary salts produce corresponding mono and diammonium cations that appear in first order mass spectra. Collision induced dissociation (CID) of primary cations generated from monool derivatives gives rise to ammonium cations of corresponding acids HOOC(CH2)n-N+(C5H5). CID of primary dications gives rise to the same cations which are also eliminated from dications to form mono-charged fragments.

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Gas-phase fragmentation studies of biotinylated, hexaethylene glycol-spacered oligosaccharides — molecular probes — using electrospray mass spectrometry on hybrid high-resolution mass spectrometer

T13N3

A.O. Chizhov, D.A. Argunov, M.L. Gening, E.V. Sukhova, E.A. Khatuntseva, A.A. Karelin,
B.S. Komarova, M.V. Orekhova, V.B. Krylov, D.V. Yasunskii, Yu.E. Tsvetkov, N.E. Nifantiev

Electrospray ionization high-resolution mass spectra of biotinylated, hexaethylene glycol spacered molecular probes bearing biologically relevant carbohydrate moieties in positive and negative modes were recorded and interpret. Collisionally-induced decay mass spectra (positive mode) reveal different patterns depending on the charge of the parent ion, attached cations (or ions), the composition, and the sequence of carbohydrate fragment. The most intense peaks (two series) originate from the sequential cleavage of glycoside bonds resulting in charge location on the “reducing” end (Y series, observed for all compounds studied) or “non-reducing” end (B series). Fragmentation of the hexaethylene glycol chain giving rise to the cleavage of the C—O bond remoted from the biotin moiety is observed. Other fragment ions lighter than the mentioned above on the difference of (C2H4O)n were absent or much smaller. Similar fragmentation was found for all of the non-sulfated, biotinylated glycosides with the hexaethylene glycol spacer thus demonstrating that this type of fragmentation was characteristic for such molecular probes. Similar cleavages along with decay of biotin moiety via elimination of H2S and H2CS were observed for negative ions in collisionally-induced decay mass spectra of sulfated and neutral molecular probes.

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A comparison of electrospray tandem mass spectra of some derivatives of sialic acid: ion trap and high resolution QqToF mass spectrometers

T13N2

A.O. Chizhov, A.M. Spirt1, N.Y. Savel’eva, L.O. Kononov

Using O-acetyl-N-acyl derivatives of O-methyl sialoside methyl esters it was shown that an ion trap and a hybrid analyzer (linear quadrupole — time-of-flight analyzer, reflectron) give comparable, though not identical secondary order mass spectra for the [M+Na]+ and [M+K]+ ions. A parallel use of an ion trap and a hybrid QqToF instrument makes possible to get information on fragmentation pathways of ions of sialic acid derivatives under collisional activation. In this case, a sequence of fragmentation may be established using an ion trap, whereas a QqToF instrument gives a possibility to reveal elemental composition of fragment ions quickly and unequivocally.

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Study of the dependence of peptide collision cross section on the ion bunch drift velocity in nitrogen

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T12N1

Study of the dependence of peptide collision cross section
on the ion bunch drift velocity in nitrogen

A.V. Chudinov, Yu.G. Martynovich, I.V. Sulimenkov, V.S. Brusov, V.V. Filatov,
A.R. Pikhtelev, V.I. Kozlovskiy

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Высокоэффективный анализ и идентификация пептидов и белков

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Количественный анализ простагландинов и полиненасыщенных жирных кислот

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Тандемная масс-спектрометрия с ионизацией электрораспылением бензоатов

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Тандемная масс-спектрометрия с ионизацией

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Letter to the Editor Selected statistics of the use of mass spectral libraries

T11N2

B.L. Milman1, I.K. Zhurkovich2

1 Institute of Experimental Medicine,
Akad. Pavlov str., 12, 197376, Saint-Petersburg, Russia,
E-mail: bmilman@mail.rcom.ru; bormilman@yandex.ru
2Institute of Toxicology,
Bekhterev str., 1, 192019, Saint-Petersburg, Russia,
E-mail: zhurkovich@toxicology.ru

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Mass spectrometric study and computer modeling of noncovalent interactions of cytosine with polyethylene glycol oligomers

T11N2

V.G. Zobnina, V.V. Chagovets, О.А. Boryak, M.V. Kosevich

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