Publications de Oleg Boyarkine

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The noncovalent binding of proteins to glycans is amazingly selective to the isoforms of carbohydrates, including alpha/beta anomers that coexist in solution. We isolate in the gas phase and study at the atomic level the simplest model system: noncovalent ...

A laser spectroscopic study on the structure and dynamics of cold host–guest inclusion complexes of crown ethers (CEs) with various neutral and ionic species in the gas phase is presented. The complexes with neutral guest species are formed by using supers ...

We present herein the design of a nano-electrospray ion source capable of reliable generation of large quantities of microsolvated ions. The source is based on a triple molecular skimmer scheme and can be quickly tuned to generate bare ions or their ionic ...

Dimethylaminonitrene complexes of IMesM+ (IMes = 1,3-bis(2,4,6-trimethylphenyl)- imidazol-2-ylidene; M = Cu, Ag, Au) were prepared in the gas phase and structurally characterized by high-resolution infrared spectroscopy of the cold species, ion-molecule re ...

The tremendous structural and isomeric diversity of lipids enables a wide range of their functions in nature but makes the identification of these biomolecules challenging. We distinguish and quantify isomeric lipids using cold ion UV fragmentation spectro ...

Linking the intrinsic tertiary structures of biomolecules to their native geometries is a central prerequisite for making gas-phase studies directly relevant to biology. The isolation of molecules in the gas phase eliminates hydrophilic interactions with s ...

We describe here experiments that combine differential ion mobility, which separates conformational isomers of biomolecular ions, with electronic spectroscopy in a cold, radio-frequency ion trap. Although the low temperature attainable in a cold ion trap g ...

State-selected spectra of the OH stretch overtones of methanol in the range of upsilon(1) = 3-8 reveal spectral splittings and broadenings that result from vibrational couplings within the molecule. We employ a two-color excitation technique in which an infrared pulse promotes jet-cooled methanol molecules to a single rotational state in upsilon(1) = 1 or 2 and a second visible or near-infrared laser pulse is scanned to record a vibrational overtone spectrum. The final vibrationally excited species are dete

We present here the design of a linear octupole ion trap, suitable for collisional cryogenic cooling and spectroscopy of large ions. The performance of this trap has been assessed using ultraviolet (UV) photofragmentation spectroscopy of protonated dipeptides. At the trap temperature of 6.1 K, the vibrational temperature of the ions reaches 9.1 K, although their estimated translational temperature is similar to 150 K. This observation suggests that, despite the significant translational heating by radio-fre

We have applied conformer-selective IR-UV double-resonance photofragment spectroscopy at low temperatures in an ion trap mass spectrometer for the spectroscopic characterization of peptide fragment ions. We investigate b- and a-type ions formed by collisio ...

Characterization of native structures of proteins in the gas phase remains challenging due to the unpredictable conformational changes the molecules undergo during desolvation and ionization. We spectroscopically studied cryogenically cooled protonated pro ...

Biological functionality of isomeric carbohydrates may differ drastically, making their identifications indispensable in many applications of life science. Because of the large number of isoforms, structural assignment of saccharides is challenging and oft ...

Identification of isomeric amino acid residues in peptides and proteins is challenging but often highly desired in proteomics. One of the practically important cases that require isomeric assignments is that associated with single-nucleotide polymorphism s ...

The tremendous isomeric diversity of carbohydrates enables a wide range of their biological functions but makes the identification and study of these molecules difficult. We investigated the ability of intermolecular interactions to communicate structural ...

To better understand the complex photophysics of the amino acid tryptophan, which is widely used as a probe of protein structure and dynamics, we have measured electronic spectra of protonated, gas-phase tryptophan solvated with a controlled number of wate ...

Double-resonance vibrational overtone excitation spectra of small molecules, in combination with laser-induced fluorescence product detection, provide information on both their energetics and intramolecular energy redistribution dynamics. Application of this approach to measure OH stretch overtone spectra of HOOH and NH2OH near their dissociation threshold provides estimates of the O-O and N-O bond energies of 17051.8 +/- 4 cm(-1) and 21 620 +/- 20 cm(-1) respectively. In symmetrical molecules, such as HOOH

Identification of isomeric biomolecules remains a challenging analytical problem. A recently developed spectroscopic method that combines UV photofragmentation and mass spectrometry for fingerprinting of cold ions (2D UV-MS), has already demonstrated its h ...

We report here infrared spectra of protonated and lithiated valine with varying degrees of hydration in the gas phase and interpret them with the help of DFT calculations at the B3LYP/6-31++G** level. In both the protonated and lithiated species, our resul ...

We have measured a vibrationally-resolved UV spectrum of doubly-protonated gramicidin S (GS) in the gas phase and, subsequently, a highly-resolved, conformer-specific infrared spectra in the 6 μm fingerprint region, using a cold ion trap in combination wit ...

Files related to publications under FNS grant 200020_204072:

(1) Zviagin, A.; Kopysov, V.; Kozlovskii, V.; Chernyshev, D.; Makarov, A.; Boyarkin, O. V. Identification of Isomeric Metabolites Using Cold Ion Spectroscopy Add-on to Orbitrap-Based Mass Spectrometer, Anal Chem 2025, 97, 14097-14102.
(2) Zviagin, A.; Boyarkin, O. V. Ion Spectroscopy Reveals Structural Difference for Proteins Microhydrated by Retention and Condensation of Water, J Phys Chem A 2024, 128, 2317-2322.
(3) Kopysov, V.; Yamaletdi

Oleg Boyarkine

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Revealing Single-Bond Anomeric Selectivity in Carbohydrate-Protein Interactions

Laser Spectroscopic Study of Cold Host–Guest Complexes of Crown Ethers in the Gas Phase

Gentle nano-electrospray ion source for reliable and efficient generation of microsolvated ions

Structure and Bonding of Isoleptic Coinage Metal (Cu, Ag, Au) Dimethylaminonitrenes in the Gas Phase

Identification of Isomeric Lipids by UV Spectroscopy of Noncovalent Complexes with Aromatic Molecules

Exploring the relevance of gas-phase structures to biology: cold ion spectroscopy of the decapeptide neurokinin A

Spectroscopy of mobility-selected biomolecular ions

Intramolecular energy transfer in highly vibrationally excited methanol. II. Multiple time scales of energy redistribution

Cryogenically cooled octupole ion trap for spectroscopy of biomolecular ions

Conformation-Specific Spectroscopy of Peptide Fragment Ions in a low-Temperature Ion Trap

Tracking local and global structural changes in a protein by cold ion spectroscopy

Identification and Quantification of Any Isoforms of Carbohydrates by 2D UV-MS Fingerprinting of Cold Ions

Method for Identification of Threonine Isoforms in Peptides by Ultraviolet Photofragmentation of Cold Ions

Interplay of H-Bonds with Aromatics in Isolated Complexes Identifies Isomeric Carbohydrates

Microsolvation effects on the excited state dynamics of protonated tryptophan

State-to-state studies of intramolecular dynamics and unimolecular reactions

Accelerating photofragmentation UV Spectroscopy–Mass spectrometry fingerprinting for quantification of isomeric peptides

Infrared spectroscopy of hydrated amino acids in the gas phase: protonated and lithiated valine

Highly-resolved Spectra of Gas-phase Gramicidin S: A Benchmark for Peptide Structure Calculations

FNS 200020_204072: Cold ion spectroscopy – mass spectroscopy for structural determinations and identifications odf biomolecules