Exchange interaction in short-lived flavine adenine dinucleotide biradical in aqueous solution revisited by CIDNP (chemically induced dynamic nuclear polarization) and nuclear magnetic relaxation dispersion

Flavin adenine dinucleotide (FAD) is an important cofactor in many light-sensitive enzymes. The role of the adenine moiety of FAD in light-induced electron transfer was obscured, because it involves an adenine radical, which is short-lived with a weak chromophore. However, an intramolecular electron transfer from adenine to flavin was revealed several years ago by Robert Kaptein by using chemically induced dynamic nuclear polarization (CIDNP). The question of whether one or two types of biradicals of FAD in aqueous solution are formed stays unresolved so far. In the present work, we revisited the CIDNP study of FAD using a robust mechanical sample shuttling setup covering a wide magnetic field range with sample illumination by a light-emitting diode. Also, a cost efficient fast field cycling apparatus with high spectral resolution detection up to 16.4 T for nuclear magnetic relaxation dispersion studies was built based on a 700 MHz NMR spectrometer. Site-specific proton relaxation dispersion data for FAD show a strong restriction of the relative motion of its isoalloxazine and adenine rings with coincident correlation times for adenine, flavin, and their ribityl phosphate linker. This finding is consistent with the assumption that the molecular structure of FAD is rigid and compact. The structure with close proximity of the isoalloxazine and purine moieties is favorable for reversible light-induced intramolecular electron transfer from adenine to triplet excited flavin with formation of a transient spin-correlated triplet biradical F⚫−-A⚫+. Spin-selective recombination of the biradical leads to the formation of CIDNP with a common emissive maximum at 4.0 mT detected for adenine and flavin protons. Careful correction of the CIDNP data for relaxation losses during sample shuttling shows that only a single maximum of CIDNP is formed in the magnetic field range from 0.1 mT to 9 T; thus, only one type of FAD biradical is detectable. Modeling of the CIDNP field dependence provides good agreement with the experimental data for a normal distance distribution between the two radical centers around 0.89 nm and an effective electron exchange interaction of −2.0 mT.

The Effect of Hydrogenation on Structure and Superconducting Properties of FeTe0.65Se0.35 Single Crystals

Single crystals of FeTe0.65Se0.35, with the onset of critical temperature (Tc) at 14 K, were hydrogenated for 10–90 hours at various temperatures, ranging from 20 to 250 oC. It is shown that tetragonal matrix becomes unstable and crystal symmetry is reduced for the crystals hydrogenated already at 200 oC despite that molecular impurities do not change matrix symmetry, unless the material is not destroyed under hydrogenation at 250 oC. Bulk Tc, takenat the middle of the transition, equal to about 12–13 K for the as-grown FeTe0.65Se0.35, increases by 1–2 K. The critical current density determined in magnetic field range of 0–70 kOe increases 4–30 times as a result of hydrogenation at 200 oC for 10 h. Electron paramagnetic resonance studies confirmed higher value of the bulk Tc for hydrogenated crystals. Thermal diffusion of hydrogen leads to substantial structural changes, causes degeneration of crystal quality, and significantly affects superconducting properties. A strong correlation was observed between the structural changes and changes in the parameters of the superconducting state for the hydrogenated crystals.

Exchange interaction in short lived flavin adenine dinucleotide biradical in aqueous solution revisited by CIDNP and nuclear magnetic relaxation dispersion

Flavin adenine dinucleotide (FAD) is an important cofactor in many light-sensitive enzymes. The role of the adenine moiety of FAD in light induced electron transfer was obscured because it involves an adenine radical, short-lived with a weak chromophore. However, an intramolecular electron transfer from adenine to flavin was revealed several years ago by R. Kaptein by using chemically induced dynamic nuclear polarization (CIDNP). The question whether one or two types of biradicals of FAD in aqueous solution are formed stays unresolved so far. In the present work, we revisited the CIDNP study of FAD using a robust mechanical sample shuttling setup covering a wide magnetic field range with sample illumination by a light emitting diode. Also, a cost efficient fast field cycling apparatus with high spectral resolution detection up to 16.4 T for nuclear magnetic relaxation dispersion studies was built based on a 700 MHz NMR spectrometer. Site-specific proton relaxation dispersion data for FAD show a strong restriction of the relative motion of its isoalloxazine and adenine rings with coincident correlation times for adenine, flavin and their ribityl-phosphate linker. This finding is consistent with the assumption that the molecular structure of FAD is rigid and compact. The structure with close proximity of the isoalloxazine and purine moieties is favorable for reversible light induced intramolecular electron transfer from adenine to triplet excited flavin with formation of a transient spin-correlated triplet biradical F•−-A•+. Spin selective recombination of the biradical leads to the formation of CIDNP with a common emissive maximum at 4.0 mT detected for adenine and flavin protons. Careful correction of the CIDNP data for relaxation losses during sample shuttling shows that only a single maximum of CIDNP is formed in the magnetic field range from 0.1 mT to 9 T; thus, only one type of FAD biradical is detectable. Modeling of the CIDNP field dependence provides good agreement with the experimental data for a normal distance distribution between the two radical centers around 0.89 nm and an effective electron exchange interaction of −2.0 mT.

Магнитосопротивление и квантовые осцилляции в полуметалле WTe-=SUB=-2-=/SUB=-

The discovery of extreme magnetoresistance (XMR) in non-magnetic materials attracted attention to the WTe2 semimetal. We have carried out studies of magnetoresistance in a tungsten ditelluride single crystal in the magnetic field range up to 14 T. Magnetoresistance increased with increasing field following a near quadratic law without saturation. The Shubnikov-de Haas oscillations were observed. Four fundamental frequencies were found in the oscillations spectrum, which correspond to two electron and two hole pockets caused by strong spin-orbit coupling.

Fitting the magnetoresponses of the OLED using polaron pair model to obtain spin-pair dynamics and local hyperfine fields

Organic light-emitting diode (OLED) displays a sign reversal magnetic field effect (MFE) when the applied magnetic field range is reduced to the sub-milliTesla range and the Polaron Pair Model has been successful in explaining the ultra-small MFE. Here, we obtained high resolution (~ 1 µT) magnetoconductance (MC) and magnetoelectroluminescence (MEL) of a tris-(8-hydroxyquinoline)aluminium-based (Alq3) OLED within the magnetic field range of ± 500 µT with the earth magnetic field components cancelled. A clear “W” shaped MC with a dip position of ± 250 µT and a monotonic MEL were observed. We demonstrate a fitting technique using the polaron pair model to the experimentally obtained MC and MEL. The fitting process extracts physically significant parameters within a working OLED: the local hyperfine fields for electron and hole in Alq3: Bhf1 = (0.63 ± 0.01) mT (electron), Bhf2 = (0.24 ± 0.01) mT (hole); the separation rates for singlet and triplet polaron pairs: kS,s = (44.59 ± 0.01) MHz, kT,s = (43.97 ± 0.01) MHz, and the recombination rate for singlet polaron pair kS,r = (88 ± 6) MHz. The yielded parameters are highly reproducible across different OLEDs and are in broad agreement with density functional theory (DFT) calculations and reported experimental observations. This demonstrates the feasibility of this fitting technique to approach any working OLED for obtaining significant microscopic parameters.

Fiber optic magnetic field sensor using Co doped ZnO nanorods as cladding

A fiber optic magnetic field sensor based on Co doped ZnO nanorods is proposed and demonstrated. The sensor has an operating magnetic field range of 17 mT to 180 mT and shows a maximum sensitivity of ∼18% for 15 at% Co doped ZnO nanorods.

Field-cycling NMR experiments in an ultra-wide magnetic field range: relaxation and coherent polarization transfer

An experimental method is described allowing fast field-cycling Nuclear Magnetic Resonance (NMR) experiments over a wide range of magnetic fields from 5 nT to 10 T.