The Laboratory of Photochemical Radical Reactions, led by Dr. Phys.-Math. Sci. A. V. Yurkovskaya, studies the mechanisms of reactions, structure, reactivity, and dynamic behavior of short-lived radical intermediates in biologically important molecular systems and photoprocesses. To investigate these processes, powerful pulsed lasers are used for optical initiation of chemical reactions in NMR spectrometers, along with modern pulsed nuclear magnetic resonance (NMR) methods to detect spin-polarized reaction products with microsecond time resolution. The creation of nonequilibrium spin systems is based on the key role of magnetic interactions in chemistry, particularly the influence of electron and nuclear spins on the rate and yield of chemical and biological reactions. The Chemically Induced Dynamic Nuclear Polarization (CIDNP) method, with its high spectral sensitivity and selectivity, is applied to study radical intermediates of biomolecules under near-physiological conditions, as well as to investigate dynamic processes involving proteins and nucleic acids.
Nuclear spin hyperpolarization, induced by para-hydrogen and ortho-deuterium, is generated using a high-pressure automated setup developed by Dr. Chem. Sci. A. S. Kiryutin in 2016. The PHIP, ODIP, and SABRE (Parahydrogen Induced Polarization, Ortho-deuterium Induced Polarization, Signal Amplification By Reversible Exchange) methods are employed to create nuclear spin hyperpolarization in hydrogenation reactions or polarization transfer via substrate interaction with spin isomers of molecular hydrogen. Collaborative research with the Theoretical Chemistry Group (led by Dr. Phys.-Math. Sci. N. N. Lukzen) focuses on studying hyperpolarization mechanisms, developing efficient pulse sequences, and optimizing magnetic field strength to generate hyperpolarized substrates and preserve this polarization in long-lived spin states. These studies enhance the sensitivity of NMR spectroscopy and imaging.
In 2017, Dr. Chem. Sci. A. S. Kiryutin and Dr. Phys.-Math. Sci. Yu. A. Grishin (Institute of Chemical Kinetics and Combustion, SB RAS) developed a unique experimental setup at the International Tomography Center (ITC SB RAS) based on a 400 MHz spectrometer. This system enables experiments with fast magnetic field switching by positioning the sample along the axis of a 9.4 T cryomagnet, as well as measurements in ultra-weak fields (several orders of magnitude below Earth's magnetic field). The NMR spectra retain high resolution (~1 Hz), crucial for studying CIDNP, PHIP, DNP, and investigating relaxation dispersion for any magnetic nuclei across an exceptionally wide field range (10 nT to 9.4 T) with atomic-level spectral resolution.
Research is conducted by Dr. Chem. Sci. O. B. Morozova, Dr. Chem. Sci. N. N. Fishman, Dr. Chem. Sci. A. S. Kiryutin, Dr. Phys.-Math. Sci. I. V. Zhukov, and graduate students D. A. Markelov and M. G. Geniman using NMR spectrometers with proton operating frequencies of 200, 300, 400, and 700 MHz.
