Pavlo Bielytskyi

Martin Luther University Halle-Wittenberg | MLU · Institute of Biochemistry and Biotechnology

Several parameters in NMR depend on the magnetic field strength. Field-cycling NMR is an elegant way to explore the field dependence of these properties. The technique is well developed for solution state and in relaxometry. Here, a shuttle system with magic-angle spinning (MAS) detection is presented to allow for field-dependent studies on solids....

In the present study, we exploit the light-induced hyperpolarization occurring on 13C nuclei due to the solid-state photochemically induced dynamic nuclear polarization (photo-CIDNP) effect to boost the NMR signal intensity of selected protons via inverse cross-polarization. Such hyperpolarization transfer is implemented into 1H-detected two-dimens...

Joo et al. have recently reported a crystal structure of a polyethylene terephthalate (PET) hydrolyzing enzyme (IsPETase) from Ideonella sakaiensis which has been described able to metabolize PET at 30 °C. They proposed a PET degradation mechanism solely based on covalent computational docking of an oligomeric substrate—2-hydroxyethyl-(monohydroxye...

The biocatalytic degradation of polyethylene terephthalate (PET) emerged recently as a promising alternative plastic recycling method. However, limited activity of previously known enzymes against post-consumer PET materials still prevents the application on an industrial scale. In this study, the influence of ultraviolet (UV) irradiation as a pote...

The human ATPase p97, also known as valosin containing protein or Cdc48, is a highly abundant AAA+ engine that fuels diverse energy-consuming processes in the human cell. p97 represents a potential target for cancer therapy and its malfunction causes a degenerative disease. Here, we monitor the enzymatic activity of p97 in real time via an NMR-base...

We all will remember Shimon Vega (1942–2021) as wonderful human and scientist. Paramount examples of his scientific work are quoted in this special issue dedicated to his memory. This article is dedicated to remember Shimon Vega as a fantastic teacher. To introduce to the world of product operators, Shimon created a simple scheme that we now call t...

The hepatitis B virus (HBV) is the leading cause of persistent liver infections. Its DNA-based genome is synthesized through reverse transcription of an RNA template inside the assembled capsid shell. In addition to the structured assembly domain, the capsid protein harbors a C-terminal extension that mediates both the enclosure of RNA during capsi...

Cyanobacteriochromes (CBCRs) are phytochrome-related photosensory proteins that play an essential role in regulating phototaxis, chromatic acclimation, and cell aggregation in cyanobacteria. Here, we apply solid-state NMR spectroscopy to the red/green GAF2 domain of the CBCR AnPixJ assembled in vitro with a uniformly ¹³C- and ¹⁵N-labeled bilin chro...

Unlike canonical phytochromes, the GAF domain of cyanobacteriochromes (CBCRs) can bind bilins autonomously and is sufficient for functional photocycles. Despite the astonishing spectral diversity of CBCRs, the GAF1 domain of the three-GAF-domain photoreceptor all2699 from the cyanobacterium Nostoc 7120 is the only CBCR-GAF known that converts from...

nido‐Carboranes are valuable backbones for the development of phosphorus‐based ligands. The cover, designed by Dr. Christoph Selg (Leipzig University), shows a highlight of the present study: Cu2I2 units bridged by the first nido‐carborane‐substituted diphosphetane, as symbolised by the crabs, forming a one‐dimensional coordination polymer. The dip...

Deboronation of a carborane‐substituted diphosphetane 2 in toluene yielded the first nido‐carboranyldiphosphetane 1. The P−P bond in 1 can be broken via dismutation reactions with diaryl dichalcogenides yielding nido‐carboranyl bis‐phosphanes which were not accessible via established synthetic protocols. Additionally, transition metal complexes of...

Recently, we have demonstrated the possibility to transfer the light-induced hyperpolarization occurring on select 13C nuclei of photosynthetic cofactors due to the solid-state photochemically induced dynamic nuclear polarization (photo-CIDNP) effect into the proton pool via inverse 13C–1H cross-polarization Bielytskyi et al. (J Magn Reson 293: 82–...

The magnetic field dependence of Chemically Induced Dynamic Nuclear Polarization (CIDNP) in solid-state systems is analyzed theoretically with the aim to explain the puzzling sign change of polarization found at low fields [D. Gräsing et al., Sci. Rep. 7, 12111 (2017)]. We exploit the analysis of polarization in terms of level crossings and level a...

The solid-state photo-CIDNP (photochemically induced dynamic nuclear polarization) effect allows for increase of signal and sensitivity in magic-angle spinning (MAS) NMR experiments. The effect occurs in photosynthetic reaction centers (RC) proteins upon illumination and induction of cyclic electron transfer. Here we show that the strength of the e...

Modified versions of through-bond heteronuclear correlation (HETCOR) experiments are presented to take advantage of the light-induced hyperpolarization that occurs on 13C nuclei due to the solid-state photochemically induced dynamic nuclear polarization (photo-CIDNP) effect. Such 13C – 1H photo-CIDNP MAS-J-HMQC and photo-CIDNP MAS-J-HSQC experiment...

For the first time, a ¹H solid-state photo-CIDNP effect is reported. The effect is observed in frozen solution of cyclohexanone in 1,4-dioxane-d8 under magic-angle spinning and continuous irradiation by the full spectrum of a xenon arc lamp. The spectral features show close similarity with those observed by ¹H liquid-state photo-CIDNP NMR.

We demonstrate a technique which can change the pH inside an NMR tube in steps of ≤0.01 pH unit, during a solution-state NMR experiment. We use a photo-acid co-solute with the actual specimen, and photo-excite the solution by direct fibre-mediated light delivery to the NMR tube. The photo-excitation and NMR measurements can be performed simultaneou...

Supplementary Data including: the picture of photosynthetic reaction center of R. sphaeroides WT; calculation of the 1H chemical shift scaling factor; 13C-1H correlation MAS NMR spectra of U-13Clabeled L-alanine; Photo-CIDNP 13-C1H HETCOR MAS NMR spectra of 5-ALA R. sphaeroides WT with tentative assignment of certain correlation peaks