Q-band Electron Paramagnetic Resonance Research Articles

Retrospective EPR dosimetry in glass and tooth enamel – The methodology and results of MUG group in RENEB 2021 inter-laboratory comparison

Electron Paramagnetic Resonance (EPR) is recognized method in retrospective dosimetry, based on detection of stable paramagnetic centres induced by radiation in biological materials, like enamel, bones, nails, or artificial materials, like glasses and other. EPR dosimetry in glass and enamel were included, in addition to several biological dosimetry tests, in the recent intercomparison project RENEB ILC 2021 as one of the physical dosimetry methods potentially applicable for dose assessment in radiation accidents. EPR group from Medical University of Gdansk (MUG) was one of participants in this intercomparison. The participants reconstructed doses in three blinded samples of watch glass, Gorilla Glass from phone screens and in enamel irradiated with 0 Gy, 1.2 Gy and 3.5 Gy (these doses were revealed after reporting the final results by all participants). For reconstruction of doses in the glass samples the respective calibration samples were provided by organizers of the ILC project. For dosimetry in enamel the participants used their own calibration data. The doses reconstructed by us in the blinded samples (in terms of kerma in air) were: in watch glass: −0.05 Gy, 1.03 Gy, 3.16 Gy, in Gorilla Glass: −0.03 Gy, 1.20 Gy, 3.44 Gy, in enamel: 0.1 Gy, 1.3 Gy, 3.1 Gy. The differences between the reconstructed and the nominal doses were small and the accuracy was sufficient for triage of irradiated people at the level of 1–2 Gy. The small sample mass of the enamel, suitable rather to Q-band EPR dosimetry and potentially available without whole tooth extraction, allowed to obtain satisfactory accuracy of EPR dosimetry also in the X-band measurements.

Full optimization of dynamic nuclear polarization on a 1 tesla benchtop polarizer with hyperpolarizing solids.

Hyperpolarization by dissolution dynamic nuclear polarization (dDNP) provides the opportunity to dramatically increase the weak nuclear magnetic resonance (NMR) signal of liquid molecular targets using the high polarization of electron radicals. Unfortunately, the solution-state hyperpolarization can only be accessed once since freezing and melting of the hyperpolarized sample happen in an irreversible fashion. A way to expand the application horizon of dDNP can therefore be to find a recyclable DNP alternative. To pursue this ambitious goal, we recently introduced the concept of recyclable hyperpolarized flow (HypFlow) DNP where hyperpolarization happens in porous hyperpolarizing solids placed in a compact benchtop DNP polarizer at a magnetic field of 1 T and a temperature of 77 K. Here we aim to optimize the radical concentrations immobilized in hyperpolarizing solids with the objective of generating as much polarization as possible in a timeframe (<1 s) compatible with future recyclable DNP applications. To do so, the solid-state DNP enhancement factors, build-up rates and DNP spectra of different hyperpolarizing solids containing various nitroxide radical loadings (20-74 μmol cm-3) are compared against the DNP performance of varying nitroxide concentrations (10-100 mM) solvated in a glassy frozen solution. We demonstrate that in <1 s, polarization enhancement goes up to 56 and 102 with surface-bound and solvated radicals, respectively, under the optimized conditions. For the range of nitroxide concentrations used cross effect DNP seems to be the dominant mechanism under benchtop conditions. This was deduced from the electron paramagnetic resonance (EPR) lineshape of TEMPOL investigated using Q-band EPR measurements.

In One Fell Sweep: Modeling Exchange, Hyperfine and Dipolar Interactions from EPR Spectra of Copper(II) Spin Triangles

The weak intramolecular magnetic interactions within a series of CuII3 complexes based on the trinucleating 2,4,6-tris(di-2-pyridylamino)-1,3,5-triazine (dipyatriz) ligand were investigated via Electron Paramagnetic Resonance (EPR) spectroscopy. X- and Q-band EPR spectroscopy in powders and frozen solutions were recorded and the Q-band spectra were interpreted by a multispin Hamiltonian model comprising exchange, dipolar and hyperfine interactions. The described methodology is suitable for the elucidation of weak intramolecular interactions which are not amenable to analysis via magnetic susceptibility studies.

Molecular Structure Related to an S = 5/2 High-Spin S2 State Manganese Cluster of Photosystem II Investigated by Q-Band Pulse EPR Spectroscopy.

The high-spin S2 state of the photosynthetic oxygen-evolving cluster Mn4CaO5, corresponding to the g = 4.1 signal for X-band electron paramagnetic resonance (EPR), was investigated using Q-band pulsed EPR, which detected a main peak at g = 3.10 and satellite peaks at 5.25, 4.55, and 2.80. We evaluated the spin state as the zero-field splitting of D = 0.465 cm-1 and E/D = 0.245 with S = 5/2. The temperature dependence of the T1 relaxation time revealed that the excited-state energy was 28.7 cm-1 higher than that of the S = 5/2 ground state. By comparing present quantum mechanical (QM) calculation models, a closed-cubane structure with the protonation state of two oxygens, W1 (= OH-) and W2 (= H2O), was the most probable structure for the S = 5/2 state. The three-pulse electron spin-echo envelope modulation (ESEEM) detected the nuclear signal, which was assigned to nitrogen as His332 ligated to the Mn1 ion. The obtained hyperfine constant for the nitrogen signal was significantly reduced from that in the S = 1/2 low-spin state. These results indicate that the S = 5/2 spin state arises from the closed-cubane structure.

Cleavage of an Aromatic C–C Bond in Ferrocene by Insertion of an Iridium Nitrido Nitrogen Atom

The intermolecular cleavage of C-C bonds is a rare event. Herein, we report on a late transition-metal terminal nitrido complex, which upon oxidation undergoes insertion of the nitrido nitrogen atom into the aromatic C-C bond of ferrocene. This reaction path was confirmed through 15N and deuterium isotope labeling experiments of the nitrido complex and ferrocenium, respectively. Cyclic voltammetry and UV/vis spectroscopy monitoring of the reaction revealed that oxidation is the initial step, yielding the tentative radical cationic nitrido complex, which is experimentally supported by extended X and Q-band electron paramagnetic resonance (EPR) and ENDOR, UV/vis, vT 1H NMR, and vibrational spectroscopic data. Density functional theory (DFT) and multireference calculations of this highly reactive intermediate revealed an S = 1/2 ground state. The high reactivity can be traced to the increased electrophilicity in the oxidized complex. Based on high-level PNO-UCCSD(T) calculations and UV/vis kinetic measurements, it is proposed that the reaction proceeds by initial electrophilic exo attack of the nitrido nitrogen atom at the cyclopentadienyl ring and consecutive ring expansion to a pyridine ring.

Dual-radical-based molecular anisotropy and synergy effect of semi-conductivity and valence tautomerization in a photoswitchable coordination polymer.

Organic radicals are widely used as linkers or ligands to synthesize molecular magnetic materials. However, studies regarding the molecular anisotropies of radical-based magnetic materials and their multifunctionalities are rare. Herein, a photoisomerizable diarylethene ligand was used to form {[CoIII(3,5-DTSQ·-)(3,5-DTCat2-)]2(6F-DAE-py2)}·3CH3CN·H2O (o-1·3CH3CN·H2O, 6F-DAE-py2=1,2-bis(2-methyl-5-(4-pyridyl)-3-thienyl)perfluorocyclopentene), a valence-tautomeric (VT) coordination polymer. We directly observed dual radicals for a single crystal using high-field/-frequency (∼13.3 T and ∼360GHz) electron paramagnetic resonance (EPR) spectroscopy along the c-axis, which was further confirmed by angle-dependent Q-band EPR spectroscopy. Moreover, a conductive anomaly close to the VT transition temperature was observed only when probes were attached at the ab plane of the single crystal, indicative of synergy between valence tautomerism and conductivity. Structural anisotropy studies and density functional theory (DFT) calculations revealed that this synergy is due to electron transfer associated with valence tautomerism. This study presents the first example of dual-radical-based molecular anisotropy and charge-transfer-induced conductive anisotropy in a photoswitchable coordination polymer.

High-field EPR of copper(II)-nitroxide compound exhibiting three-step phase transition: structural insights from the field-induced sample orientation.

Copper(II)-nitroxide based Cu(hfac)2LR compounds exhibit unusual magnetic behavior that can be induced by various stimuli. In many aspects, the magnetic phenomena observed in Cu(hfac)2LR are similar to classical spin-crossover behavior. However, these phenomena originate from polynuclear exchange-coupled spin clusters Cu2+-O˙-N< or >N-˙O-Cu2+-O˙-N<. Such peculiarities may result in additional multifunctionality of Cu(hfac)2LR compounds, making them promising materials for spintronic applications. Herein, we investigate the Cu(hfac)2LMeMe material, which demonstrates a three-step temperature-induced magnetostructural transition between high-temperature, low-temperature, and intermediate states, as revealed by magnetometry. Two main steps were resolved using variable-temperature Fourier-transform infrared and Q-band electron paramagnetic resonance (EPR) spectroscopies. The intermediate-temperature states (∼40-90 K) are characterized by the coexistence of two types of copper(II)-nitroxide clusters, corresponding to the low-temperature and high-temperature phases. High-field EPR experiments revealed the effect of partial alignment of Cu(hfac)2LMeMe microcrystals in a strong (>20 T) magnetic field. This effect was used to unveil the structural features of the low-temperature phase of Cu(hfac)2LMeMe, which were inaccessible using single-crystal X-ray diffraction (XRD) technique. In particular, high-field EPR allowed us to determine the relative direction of the Jahn-Teller axes in CuO6 and CuO4N2 units.

A rare diiodo-L-tyrosine copper(II) complexes – Crystal and molecular structure of materials stabilized by weak interactions

The problem in formation of 3,5-diiodo-L-tyrosinato (L-I2Tyr) various metal ion complexes as a crystals is generated by the low solubility of iodo-L-tyrosinato derivatives (as ligands) in pure aqueous solution. However, two inorganic–organic hybrid l-I2Tyr copper(II) complexes i.e. [CuCl(L-I2TyrOH)(phen)]∙2H2O (1) and [Cu(l-I2TyrOH)(H2O)(phen)](NO3) (2) with l-I2TyrOH were isolated in acid aqueous/methanol medium. In crystals 1 and 2, the monomeric distorted square planar pyramidal copper(II) coordination is stabilized by weak intramolecular π···π stacking, copper(II)···π and π···I non-covalent interactions. The connection of adjacent 2D layers into 3D supramolecular network is realised by weak π···π contacts in 1, while in 2 the 3D architecture is stabilized by weak CH···π interaction as well as π···π contacts. The complexes are also characterized by infrared and Raman spectroscopies (FT-IR, FT-Raman), X- and Q-band electron paramagnetic resonance spectroscopy (EPR), electronic spectroscopy (NIR-Vis-UV), magnetic method, and theoretical calculation.

Mechanism of Reduction of an Aminyl Radical Intermediate in the Radical SAM GTP 3',8-Cyclase MoaA.

The diversity of the reactions catalyzed by radical S-adenosyl-l-methionine (SAM) enzymes is achieved at least in part through the variety of mechanisms to quench their radical intermediates. In the SPASM-twitch family, the largest family of radical SAM enzymes, the radical quenching step is thought to involve an electron transfer to or from an auxiliary 4Fe-4S cluster in or adjacent to the active site. However, experimental demonstration of such functions remains limited. As a representative member of this family, MoaA has one radical SAM cluster ([4Fe-4S]RS) and one auxiliary cluster ([4Fe-4S]AUX), and catalyzes a unique 3',8-cyclization of GTP into 3',8-cyclo-7,8-dihydro-GTP (3',8-cH2GTP) in the molybdenum cofactor (Moco) biosynthesis. Here, we report a mechanistic investigation of the radical quenching step in MoaA, a chemically challenging reduction of 3',8-cyclo-GTP-N7 aminyl radical. We first determined the reduction potentials of [4Fe-4S]RS and [4Fe-4S]AUX as -510 mV and -455 mV, respectively, using a combination of protein film voltammogram (PFV) and electron paramagnetic resonance (EPR) spectroscopy. Subsequent Q-band EPR characterization of 5'-deoxyadenosine C4' radical (5'-dA-C4'•) trapped in the active site revealed isotropic exchange interaction (∼260 MHz) between 5'-dA-C4'• and [4Fe-4S]AUX1+, suggesting that [4Fe-4S]AUX is in the reduced (1+) state during the catalysis. Together with density functional theory (DFT) calculation, we propose that the aminyl radical reduction proceeds through a proton-coupled electron transfer (PCET), where [4Fe-4S]AUX serves as an electron donor and R17 residue acts as a proton donor. These results provide detailed mechanistic insights into the radical quenching step of radical SAM enzyme catalysis.

Chromium Environment within Cr-Doped Silico-Aluminophosphate Molecular Sieves from Spin Density Studies.

X-/Q-band electron paramagnetic resonance (EPR) and hyperfine sublevel correlation (HYSCORE) spectroscopies have been employed, in conjunction with density functional theory (DFT) modeling, to determine the location of Cr5+ions in SAPO-5 zeotype materials. The interaction of the unpaired electron of the paramagnetic Cr5+ species with 27Al could be resolved, allowing for the first detailed structural analysis of Cr5+ paramagnetic ions in SAPO materials. The interpretation of the experimental results is corroborated by DFT modeling, which affords a microscopic description of the system investigated. The EPR-active species is found to be consistent with isolated Cr5+ species isomorphously substituted in the framework at P5+ sites.

On the incorporation of nickel into hexagonal barium titanate: magnetic properties and electron paramagnetic resonance (EPR)

Systematic measurements of the magnetic moment of hexagonal 6H-BaTiO3 + 0.04 BaO + x NiO (0.005 ≤ x ≤ 0.02) ceramics were performed to study the influence of Ni ions on the magnetic properties. By temperature-dependent measurements of the paramagnetic susceptibility at 90 kOe, the Ni2+ ion was identified as the majority defect in air-sintered Ni-doped hexagonal barium titanate. Q-band EPR investigations of a 2.0 mol% Ni-doped single crystal revealed three different Ni centers located at Ti sites: first, Ni3+ ions at Ti sites in intact oxygen octahedra, second, Ni3+ associated with an oxygen vacancy and third, the presence of Ni2+ centers leading to a forbidden transition. The Ni3+—VO associate characterized by a vacancy in the face-sharing oxygen plane of the oxygen octahedra can be ruled out. The crystal field parameters of the Ni2+ defect were estimated by a combined fitting of the paramagnetic susceptibility and the EPR fine structure parameter D to B_{0}^{4} ≈ −17,300 cm−1, left| {B_{0}^{2} } right| ≈ 2500 cm−1 and B_{3}^{4} ≈ 19,000 cm−1.

Correlation of native point defects and photocatalytic activity of annealed ZnO nanoparticle studied by electron spin resonance and photoluminescence emission

In this paper, we investigate the origin of point defects revealed by electron spin resonance (ESR) and photoluminescence (PL) emission in correlation with the photocatalytic activity of ZnO nanocrystals subjected to thermal annealing at various temperatures. Two ESR signals at g ∼ 1.96 and ∼2.003 were consistently observed in all annealed ZnO samples. However, their relative intensities have changed, indicating that the point defect densities were influenced by the annealing temperature. Interestingly, when doping nanoZnO with Cr3+, the Q-band ESR measurements at T = 100 K did show that the g ∼ 1.96 signal was completely passivated, suggesting that the origin of the signal lies in the electrons located near the conduction band, i.e. at a shallow-donor level. The intensity of the g ∼ 2.003 signal decreased by rising the annealing temperature, and this is attributed to the depopulation of zinc interstitials through the thermally induced migration process and/or recombination with the zinc vacancies. The green PL emission line at ∼520 nm, which is dominant in the 700 °C annealed ZnO sample, shows a correlation with the ESR signal at g ∼ 1.96, whose origin is attributed to the radiative transition of the electron from the shallow donor level to the singly ionized zinc vacancy. Furthermore, the high density of the shallow donor electron states was found to be primarily responsible for the high photocatalytic activity in the degradation of methylene blue.

On the incorporation of iron into hexagonal barium titanate: II. Magnetic moment, electron paramagnetic resonance (EPR) and optical transmission

Systematic measurements of the magnetic moment in dependence on temperature and magnetic field of hexagonal 6H-BaTiO3 + 0.04 BaO + x/2 Fe2O3 (0.005 ⩽ x ⩽ 0.05) ceramics were performed to study the influence of Fe ions on the magnetic properties. While the samples show Curie–Weiss paramagnetism for Fe concentrations ⩽1.0 mol%, antiferromagnetic interactions become manifest for 2.0 and 5.0 mol% iron. With increasing Fe content the antiferromagnetic interaction, which is assumed to be caused by a superexchange mechanism , becomes stronger. At external magnetic fields smaller than 1 T a further, ferromagnetic interaction between Fe3+ ions is detected below 200 K. The interactions between Fe3+ ions in the samples with 2.0 and 5.0 mol% iron are also manifest in the EPR spectra by numerous lines with low intensity. Q-band EPR investigations of 5.0 mol% Fe doped single crystals confirm the existence of only one type of Fe3+–VO associates in the samples.

Electron Spin Relaxation of Photoexcited Porphyrin in Water-Glycerol Glass.

Recently, the photoexcited triplet state of porphyrin was proposed as a promising spin-label for pulsed dipolar electron paramagnetic resonance (EPR). Herein, we report the factors that determine the electron spin echo dephasing of the photoexcited porphyrin in a water–glycerol matrix. The electron spin relaxation of a water-soluble porphyrin was measured by Q-band EPR, and the temperature dependence and the effect of solvent deuteration on the relaxation times were studied. The phase memory relaxation rate (1/Tm) is noticeably affected by solvent nuclei and is substantially faster in protonated solvents than in deuterated solvents. The Tm is as large as 13–17 μs in deuterated solvent, potentially expanding the range of distances available for measurement by dipole spectroscopy with photoexcited porphyrin. The 1/Tm depends linearly on the degree of solvent deuteration and can be used to probe the environment of a porphyrin in or near a biopolymer, including the solvent accessibility of porphyrins used in photodynamic therapy. We characterized the noncovalent binding of porphyrin to human serum albumin (HSA) from 1/Tm and electron spin echo envelope modulation (ESEEM) and found that porphyrin is quite exposed to solvent on the surface of HSA. The 1/Tm and ESEEM are equally effective and provide complementary methods to determine the solvent accessibility of a porphyrin bound to protein or to determine the location of the porphyrin.

Presence and distribution of impurity defects in crystalline cubic boron nitride. A spectroscopic study

The results of the present Q-band electron spin resonance (ESR) investigation on amber colored cubic boron nitride (cBN) crystalline superabrasive powder (BORAZON CBN400) offer further support to the hypothesis that impurity ions with high natural abundant zero nuclear spin isotopes, distributed non-uniformly, are involved in the structure of the observed paramagnetic centers. One could thus explain the absence of any hyperfine structure in the multifrequency electron spin resonance spectra of both presently and previously investigated cBN crystalline powders and single crystals. The scanning electron microscopy, cathodoluminescence and photoluminescence studies performed on single crystallites selected from the same cBN400 batch further confirm the presence of electro- and photo-luminescent active impurity related centers, non-uniformly distributed in the cBN crystallite host lattice. The observation of an intense and reproducible thermoluminescence spectrum, up to high radiation doses, attributed to several trapping centers involving impurities, is also reported here.

On the Use of Q-Band Double Electron-Electron Resonance To Resolve the Relative Orientations of Two Double Histidine-Bound Cu2+ Ions in a Protein.

In this work, we explore the potential of a rigid Cu2+ spin-labeling technique, the double histidine (dHis) motif, along with Q-band electron paramagnetic resonance to report on the relative orientations of the spin labels. We show that the precision of the dHis motif, coupled with the sensitivity and resolution of Q-band frequencies, may allow for the straightforward determination of the relative orientation of the dHis-Cu2+ labels using double electron-electron resonance (DEER). We performed Q-band DEER measurements at different magnetic fields on a protein containing two dHis Cu2+ sites. These measurements exhibited orientational selectivity such that each discrete magnetic field yielded a unique DEER signal. We determined the relative orientation of the two metal centers by simulating the orientationally selective DEER data. These relative orientations were validated by visual analysis of the protein crystal structure modified with dHis sites. The simple visual analysis was shown to agree well with the angular values determined via simulation of the experimental data. The combination of the dHis-Cu2+ motif along with the advantages of the Q-band can aid in the accurate measurement of protein structural and conformational dynamics.

Pulse EPR of Triarylmethyl Probes: A New Approach for the Investigation of Molecular Motions in Soft Matter.

Triarylmethyl (TAM) radicals have become widely used free radicals in the past few years. Their electron spins have long relaxation times and narrow electron paramagnetic resonance (EPR) lines, which make them an important class of probes and tags in biological applications and materials science. In this work, we propose a new approach to characterize librations by means of TAM radicals. The temperature dependence of motional parameter ⟨α2⟩τc, where ⟨α2⟩ is the mean-squared amplitude of librations and τc is their characteristic time, is obtained by comparison of the 1/ Tm phase-relaxation rates at X- and Q-band EPR frequencies. We study three soft matrixes, viz., glassy trehalose and two ionic liquids, using TAMs with optimized relaxation properties OX063D and a dodeca- n-butyl homologue of Finland trityl (DBT). The motional parameters ⟨α2⟩τc obtained using TAMs are in excellent agreement with those obtained by means of nitroxide radicals. At the same time, the new TAM-based approach has (1) greater sensitivity due to the narrower EPR spectrum and (2) greater measuring accuracy and broader temperature range due to longer relaxation times. The developed approach may be fruitfully implemented to probe low-temperature molecular motions of TAM-labeled biopolymers, membrane systems, polymers, molecules in glassy media, and ionic liquids.

In Situ X- and Q-Band EPR Investigation of Ethylene Polymerization on Cr/SiO2 Phillips Catalyst

We present an X- and Q-band electron paramagnetic resonance (EPR) investigation of a 0.5 wt % Cr/SiO2 Phillips catalyst, aimed at establishing the Cr oxidation and spin state under different ethyle...

Spectroscopic Characterization of Natural Melanin from a Streptomyces cyaneofuscatus Strain and Comparison with Melanin Enzymatically Synthesized by Tyrosinase and Laccase.

An actinobacteria strain was isolated from Algerian Sahara soil and assigned to Streptomyces cyaneofuscatus Pridham et al. 1958 species. This strain was selected for its ability to produce melanin exopigments in liquid and solid media. Melanin synthesis was associated with tyrosinase activity and the enzyme from this strain was isolated and biochemically characterized. Synthetic melanin was then enzymatically produced using the S. cyaneofuscatus Pridham et al. 1958 tyrosinase. As this enzyme showed a higher diphenolase activity, a synthetic melanin from the enzymic oxidation of 3,4-dihydroxyphenylalanine (dopa) was obtained by the use of a Trametes versicolor (L.) Lloyd laccase for comparison. The natural and synthetic pigments were physico-chemically characterized by the use of ultraviolet (UV)-Visible, and Fourier transform infrared (FT-IR) and multifrequency electron paramagnetic resonance (EPR) spectroscopies. All the melanin samples displayed a stable free radical when analyzed by X-band EPR spectroscopy. Once the samples were recorded at Q-band EPR, a copolymer derived from a mixture of different constituents was evident in the natural melanin. All radical species were analyzed and discussed. The use of water-soluble melanin naturally produced by S. cyaneofuscatus Pridham et al. 1958 represents a new biotechnological alternative to commercial insoluble pigments.

Interplay between Dopant Species and a Spin-Crossover Host Lattice during Light-Induced Excited-Spin-State Trapping Probed by Electron Paramagnetic Resonance Spectroscopy.

Q-band electron paramagnetic resonance (EPR) data conclusively demonstrate that the iron and cobalt centers in the solid solution [Fe(bpp)2]0.97[Co(terpy)2]0.03[BF4]2 (bpp = 2,6-dipyrazol-1-ylpyridine) undergo allosteric spin-state switching during light-induced excited-spin-state trapping (LIESST) at 20 K and thermal relaxation around 80 K. EPR of [Cu(terpy)2]2+ and [Cu(bpp)2]2+, doped into the same host lattice, also indicates expansion of the copper coordination sphere during LIESST excitation.