Pulsed Electron Paramagnetic Resonance Spectroscopy Research Articles

Unveiling Charge Carrier Dynamics at Organic-Inorganic S-Scheme Heterojunction Interfaces: Insights From Advanced EPR.

Understanding charge carrier transfer at heterojunction interfaces is critical for advancing solar energy conversion technologies. This study utilizes continuous wave (CW), pulse, and time-resolved (TR) electron paramagnetic resonance (EPR) spectroscopy to explore the radical species formed at the TAPA (tris(4-aminophenyl)amine)-PDA (Terephthaldicarboxaldehyde)/ZnIn2S4 (TP/ZIS) heterojunction interface. CW and pulse EPR identify stable radical defects localized near the interface, accessible to water molecules. Time-resolved EPR reveals a photoinduced electron transfer from TP to ZIS, leading to the generation of spin-correlated radical pairs under light irradiation, signifying efficient charge carrier separation and spatial transfer within the S-scheme heterojunction. This electron transfer mechanism, confirmed through in situ X-ray photoelectron spectroscopy and femtosecond transient absorption spectroscopy, suppresses undesirable carrier recombination, extending charge carrier lifetimes. These findings provide novel insights into the transport direction of charge carriers at the S-scheme heterojunction interface, offering valuable guidance for designing highly efficient and stable organic-inorganic heterojunction photocatalysts for solar energy applications.

Pulsed EPR Methods in the Angstrom to Nanometre Scale Shed Light on the Conformational Flexibility of a Fluoride Riboswitch.

Riboswitches control gene regulation upon external stimuli such as environmental factors or ligand binding. The fluoride sensing riboswitch from Thermotoga petrophila is a complex regulatory RNA proposed to be involved in resistance to F- cytotoxicity. The details of structure and dynamics underpinning the regulatory mechanism are currently debated. Here we demonstrate that a combination of pulsed electron paramagnetic resonance (ESR/EPR) spectroscopies, detecting distances in the angstrom to nanometre range, can probe distinct regions of conformational flexibility in this riboswitch. PELDOR (pulsed electron-electron double resonance) revealed a similar preorganisation of the sensing domain in three forms, i.e. the free aptamer, the Mg2+-bound apo, and the F--bound holo form. 19F ENDOR (electron-nuclear double resonance) was used to investigate the active site structure of the F--bound holo form. Distance distributions without a priori structural information were compared with in silico modelling of spin label conformations based on the crystal structure. While PELDOR, probing the periphery of the RNA fold, revealed conformational flexibility of the RNA backbone, ENDOR indicated low structural heterogeneity at the ligand binding site. Overall, the combination of PELDOR and ENDOR with sub-angstrom precision gave insight into structural organisation and flexibility of a riboswitch, not easily attainable by other biophysical techniques.

Puls EPR Methoden im Angstöm‐ bis Nanometerbereich geben Aufschluss über die konformationelle Flexibilität eines Fluorid‐Riboschalters

AbstractRiboschalter steuern die Genregulation in Reaktion auf externe Reize wie Umweltfaktoren oder Ligandenbindung. Der fluoriderkennende Riboschalter aus Thermotoga petrophila ist eine komplexe regulatorische RNA, von der angenommen wird, an der Resistenz gegen die zytotoxische Wirkung von Fluorid beteiligt zu sein. Details der Struktur und Dynamik, die dem regulatorischen Mechanismus zugrunde liegen, werden derzeit diskutiert. Hier zeigen wir, dass mit einer Kombination aus Puls Elektronen‐Paramagnetischer‐Resonanz (ESR/EPR) Spektroskopien, die Abstände im Angström‐ bis Nanometerbereich detektiert, spezifische Bereiche konformationeller Flexibilität in diesem Riboschalter untersucht werden können. PELDOR (pulsed electron‐electron double resonance) zeigte eine ähnliche Präorganisation der Sensordomäne in drei Formen: der freien Aptamerform, der Mg2+‐gebundenen apo‐Form und der F−‐gebundenen holo‐Form. 19F ENDOR (electron‐nuclear double resonance) wurde verwendet, um die Struktur des aktiven Zentrums der F−‐gebundenen holo‐Form zu untersuchen. Abstandsverteilungen ohne vorherige strukturelle Informationen wurden mit auf der Kristallstruktur basierenden in silico Modellierungen der Spinmarkerkonformationen verglichen. Während PELDOR, welches die Peripherie der RNA Faltung untersucht, die konformationelle Flexibilität des RNA Rückgrats aufdeckte, zeigte ENDOR eine geringe strukturelle Heterogenität der Ligandenbindungstasche. Die Kombination aus PELDOR und ENDOR lieferte sub‐Angström‐präzise Einblicke in die strukturelle Organisation und Flexibilität eines Riboschalters, die mit anderen biophysikalischen Techniken nur schwer zu erreichen sind.

Proton-Coupled Electron Transfer between a Pendant Thiol and a Ferrous Dioxygen Adduct.

The mechanism of thiol oxidation by O2, as catalyzed by ferrous porphyrins, is investigated by trapping intermediates of the transformation at low temperatures and subsequently characterizing them using continuous wave and pulsed electron paramagnetic resonance and resonance Raman spectroscopy. A Fe(III)-O2•- species is initially formed in an iron porphyrin with a pendant thiol functional group, which undergoes proton-coupled electron transfer (PCET) (not HAT) to form an Fe(III)-OOH species. Following O-O bond homolysis, this forms a Fe(IV)═O species with concomitant oxidation of the thiol to an RSO3H group.

Elucidating Polyphosphate Anion Binding to Lanthanide Complexes Using EXAFS and Pulsed EPR Spectroscopy.

Reversible anion binding to lanthanide complexes in aqueous solution has emerged as an effective method for anion sensing. Through careful design of the organic ligand, luminescent lanthanide complexes capable of binding biologically relevant anions in a bidentate or monodentate manner can be realized. While single-crystal X-ray diffraction analyses and NMR spectroscopy have revealed the structural geometry of several host-guest complexes, the challenge remains in designing preorganized lanthanide receptors with enhanced anion selectivity for broader applications in diagnostics and bioimaging. To address this challenge, innovative and complementary methods to investigate host-anion binding geometry are becoming increasingly important. Herein, we demonstrate the combined use of Eu L3-edge extended X-ray absorption fine structure (EXAFS) and electron paramagnetic resonance (EPR) spectroscopy to elucidate the binding of nucleoside phosphates (ATP, ADP, and AMP) to a cationic lanthanide complex. We establish that ATP unequivocally binds the lanthanide center in a bidentate manner in water, while ADP adopts both bidentate and monodentate modes, and AMP binds in a monodentate manner. This interdisciplinary approach provides deeper insight into lanthanide host-guest chemistry in solution, laying the groundwork for designing emissive probes that undergo specific anion-induced structural changes and elicit desired optical responses upon binding.

High-field pulsed EPR spectroscopy under magic angle spinning.

In this work, we demonstrate the first pulsed electron paramagnetic resonance (EPR) experiments performed under magic angle spinning (MAS) at high magnetic field. Unlike nuclear magnetic resonance (NMR) and dynamic nuclear polarization (DNP), commonly performed at high magnetic fields and under MAS to maximize sensitivity and resolution, EPR is usually measured at low magnetic fields and, with the exception of the Spiess group work in the late 1990s, never under MAS, due to great instrumentational challenges. This hampers the investigation of DNP mechanisms, in which electron spin dynamics play a central role, because no experimental data about the latter under DNP-characteristic conditions are available. We hereby present our dedicated, homebuilt MAS-EPR probehead and show the pulsed MAS-EPR spectra of P1 center diamond defect recorded at 7 tesla. Our results reveal unique effects of MAS on EPR line shape, intensity, and signal dephasing. Time-domain simulations reproduce the observed changes in the line shapes and the trends in the signal intensity.

CaY@C2n: Exploring Molecular Qubits with Ca-Y Metal-Metal Bonds.

Metal-metal bonding is crucial in chemistry for advancing our understanding of the fundamental aspects of chemical bonds. Metal-metal bonds based on alkaline-earth (Ae) elements, especially the heavier Ae elements (Ca, Sr, and Ba), are rarely reported due to their high electropositivity. Herein, we report two heteronuclear di-EMFs CaY@Cs(6)-C82 and CaY@C2v(5)-C80, which contain unprecedented single-electron Ca-Y metal-metal bonds. These compounds were characterized by single-crystal X-ray crystallography, electron paramagnetic resonance (EPR) spectroscopy, and DFT calculations. The crystallographic study of CaY@Cs(6)-C82 shows that Ca and Y are successfully encapsulated into the carbon cage with a Ca-Y distance of 3.691 Å. The CW-EPR study of both CaY@Cs(6)-C82 and CaY@C2v(5)-C80 exhibits a doublet, suggesting the presence of an unpaired electron located between Ca and Y. The combined experimental and theoretical results confirm the presence of a Ca-Y single-electron metal-metal bond with substantial covalent interaction, attributed to significant overlap between the 4s4p orbitals of Ca and the 5s5p4d orbitals of Y. Furthermore, pulse EPR spectroscopy was used to investigate the quantum coherence of the electron spin within this bond. The unpaired electron, characterized by its s orbital nature, is effectively protected by the carbon cage, resulting in efficient suppression of both spin-lattice relaxation and decoherence. CaY@Cs(6)-C82 behaves as an electron spin qubit, displaying a maximum decoherence time of 7.74 μs at 40 K. This study reveals an unprecedented Ae-rare-earth metal-metal bond stabilized by the fullerene cages and elucidates the molecular qubit properties stemming from their unique bonding character, highlighting their potential in quantum information processing applications.

In Situ Generation and High Bioresistance of Trityl-based Semiquinone Methide Radicals Under Anaerobic Conditions in Cellular Systems.

Bioreduction of spin labels and polarizing agents (generally stable radicals) has been an obstacle limiting the in-cell applications of pulsed electron paramagnetic resonance (EPR) spectroscopy and dynamic nuclear polarization (DNP). In this work, we have demonstrated that two semiquinone methide radicals (OXQM⋅ and CTQM⋅) can be easily produced from the trityl-based quinone methides (OXQM and CTQM) via reduction by various reducing agents including biothiols and ascorbate under anaerobic conditions. Both radicals have relatively low pKa's and exhibit EPR single line signals at physiological pH. Moreover, the bioreduction of OXQM in three cell lysates enables quantitative generation of OXQM⋅ which was most likely mediated by flavoenzymes. Importantly, the resulting OXQM⋅ exhibited extremely high stability in the E.coli lysate under anaerobic conditions with 76- and 14.3-fold slower decay kinetics as compared to the trityl OX063 and a gem-diethyl pyrrolidine nitroxide, respectively. Intracellular delivery of OXQM into HeLa cells was also achieved by covalent conjugation with a cell-permeable peptide as evidenced by the stable intracellular EPR signal from the OXQM⋅ moiety. Owing to extremely high resistance of OXQM⋅ towards bioreduction, OXQM and its derivatives show great application potential in in-cell EPR and in-cell DNP studies for various cells which can endure short-term anoxic treatments.

Dielectric microwave resonator with large optical apertures for spin-based quantum devices

We demonstrate a low-loss dielectric microwave resonator with an internal quality factor of 2.30×104 while accommodating optical apertures with a diameter of 8 mm. The two seemingly conflicting requirements, high quality factor and large optical apertures, are satisfied, thanks to the large dielectric constant of rutile (TiO2). The quality factor is limited by radiation loss, and we confirmed by numerical simulation that this radiation loss can be suppressed by extending the enclosure height of the resonator; the resonator can potentially achieve a dielectric loss-limited quality factor, exceeding 106. Using this resonator, we performed both continuous-wave (cw) and pulse electron spin resonance (ESR) spectroscopy on 2,2-diphenyl-1-picrylhydrazyl (DPPH) crystalline powder and P1 centers in a diamond crystal in a dilution refrigerator. The cw ESR spectroscopy demonstrated high-cooperativity and strong spin-resonator coupling with the DPPH and P1 centers, respectively, while the pulse ESR spectroscopy successfully measured longitudinal and transverse relaxation times. This optically accessible low-loss microwave resonator enables the implementation of a spin-based quantum device, such as a microwave-optical photon transducer.

Quantifying the effects of peripheral substituents on the spin-lattice relaxation of a vanadyl molecular quantum bit

Electron spin superpositions represent a critical component of emergent quantum technologies in computation, sensing, encryption, and communication. However, spin relaxation (T1) and decoherence (Tm) represent major obstacles to the implementation of molecular quantum bits (qubits). Synthetic strategies have made substantial progress in enhancing spin coherence times by minimizing contributions from surrounding electron and nuclear spins. For room-temperature operation, however, the lifetime of spin coherence becomes limited by coupling with vibrational modes of the lattice. Using pulse electron paramagnetic resonance (EPR) spectroscopy, we measure the spin-lattice relaxation of a vanadyl tetrapyrazinoporphyrazine complex appended with eight peripheral 2,6-diisopropylphenol groups (VOPyzPz-DIPP) and compare it to the relaxation of the archetypical vanadyl phthalocyanine molecular qubit (VOPc). The added peripheral groups lead to distinctly different spin relaxation behavior. While similar relaxation times are observed at low temperatures and ambient conditions, significant changes are observed for the orientation dependence of T1 at 100 K, as well as the temperature dependence of T1 over the intermediate temperature range spanning [Formula: see text]10–150 K. These results can be tentatively interpreted as arising from loosened spin-phonon coupling selection rules and a greater number of accessible acoustic and optical modes contributing to the spin relaxation behavior of VOPyzPz-DIPP relative to VOPc.

Relativistic Quantum Chemical Investigation of Actinide Covalency Measured by Electron Paramagnetic Resonance Spectroscopy.

We investigate actinide covalency effects in two [AnCptt3] (An = Th, U) complexes recently studied with pulsed electron paramagnetic resonance spectroscopy, using the Hyperion package to obtain relativistic hyperfine coupling constants from relativistic multiconfigurational wave functions. 1H and 13C HYSCORE simulations using the computed parameters show excellent agreement with the experimental data, highlighting the accuracy of modern relativistic ab initio methods. The extent of covalency indicated from the calculations on [ThCptt3] is in agreement with the original report based on traditional spectral fitting methods, while the covalency in [UCptt3] is found to be previously overestimated. The latter is due to the paramagnetic spin-orbit effect that arises naturally in a relativistic theory of hyperfine coupling and yet was not accounted for in the original study, thus highlighting the necessity of relativistic approaches for the interpretation of magnetic resonance data pertaining to actinides.

Conformational Heterogeneity of β-Barrel Membrane Proteins Observed In Situ Using Orthogonal Spin Labels and Pulsed ESR Spectroscopy.

Outer membrane proteins (OMPs) of Gram-negative bacteria are involved in many essential functions of the cell. They are tightly packed in the outer membrane, which is an asymmetric lipid bilayer. Electron spin resonance (ESR) spectroscopic techniques combined with site-directed spin labeling (SDSL) enable observation of structure and conformational dynamics of these proteins directly in their native environments. Here we depict a protocol for site-directed spin labeling of β-barrel membrane proteins in isolated outer membranes and intact E. coli using nitroxide, triarylmethyl (trityl), and Gd3+-based spin tags. Furthermore, subsequent continuous wave (CW) and orthogonal pulsed electron-electron double resonance (PELDOR) measurements are described along with experimental setup at Q-band (34GHz), the data analysis, and interpretation.

Control of excitation selectivity in pulse EPR on spin-correlated radical pairs with shaped pulses.

Spin-correlated radical pairs generated by photoinduced electron transfer are characterised by a distinctive spin polarisation and a unique behaviour in pulse electron paramagnetic resonance (EPR) spectroscopy. Under non-selective excitation, an out-of-phase echo signal modulated by the dipolar and exchange coupling interactions characterising the radical pair is observed and allows extraction of geometric information in the two-pulse out-of-phase electron spin echo envelope modulation (ESEEM) experiment. The investigation of the role of spin-correlated radical pairs in a variety of biological processes and in the fundamental mechanisms underlying device function in optoelectronics, as well as their potential use in quantum information science, relies on the ability to precisely address and manipulate the spins using microwave pulses. Here, we explore the use of shaped pulses for controlled narrowband selective and broadband non-selective excitation of spin-correlated radical pairs in two model donor-bridge-acceptor triads, characterised by different spectral widths, at X- and Q-band frequencies. We demonstrate selective excitation with close to rectangular excitation profiles using BURP (band-selective, uniform response, pure-phase) pulses and complete non-selective excitation of both spins of the radical pair using frequency-swept chirp pulses. The use of frequency-swept pulses in out-of-phase ESEEM experiments enables increased modulation depths and, combined with echo transient detection and Fourier transformation, correlation of the dipolar frequencies with the EPR spectrum and therefore the potential to extract additional information on the donor-acceptor pair geometry.

Enhancing Coherence Times of Chromophore-Radical Molecular Qubits and Qudits by Rational Design.

An important criterion for quantum operations is long qubit coherence times. To elucidate the influence of molecular structure on the coherence times of molecular spin qubits and qudits, a series of molecules featuring perylenediimide (PDI) chromophores covalently linked to stable nitroxide radicals were synthesized and investigated by pulse electron paramagnetic resonance spectroscopy. Photoexcitation of PDI in these systems creates an excited quartet state (Q) followed by a spin-polarized doublet ground state (D0), which hold promise as spin qudits and qubits, respectively. By tailoring the molecular structure of these spin qudit/qubit candidates by selective deuteration and eliminating intramolecular motion, coherence times of Tm = 9.1 ± 0.3 and 4.2 ± 0.3 μs at 85 K for D0 and Q, respectively, are achieved. These coherence times represent a nearly 3-fold enhancement compared to those of the initial molecular design. This approach offers a rational structural design protocol for effectively extending coherence times in molecular spin qudits/qubits.

Pulse and CW EPR Oximetry Using Oxychip in Gemcitabine-Treated Murine Pancreatic Tumors

PurposeThe goal of this work was to compare pO2 measured using both continuous wave (CW) and pulse electron paramagnetic resonance (EPR) spectroscopy. The Oxychip particle spin probe enabled longitudinal monitoring of pO2 in murine pancreatic tumor treated with gemcitabine during the course of therapy.ProceduresPancreatic PanO2 tumors were growing in the syngeneic mice, in the leg. Five doses of saline in control animals or gemcitabine were administered every 3 days, and pO2 was measured after each dose at several time points. Oxygen partial pressure was determined from the linewidth of the CW EPR signal (Bruker E540L) or from the T2 measured using the electron spin echo sequence (Jiva-25™).ResultsThe oxygen sensitivity was determined from a calibration curve as 6.1 mG/mm Hg in CW EPR and 68.5 ms−1/mm Hg in pulse EPR. A slight increase in pO2 of up to 20 mm Hg was observed after the third dose of gemcitabine compared to the control. The maximum delta pO2 during the therapy correlated with better survival.ConclusionsBoth techniques offer fast and reliable oximetry in vivo, allowing to follow the effects of pharmaceutic intervention.

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.

Pulse EPR spectroscopy and molecular modeling reveal the origins of the local heterogeneity of dietary fibers

Optimizing human diet by including dietary fibers would be more efficient when the fibers' chain interactions with other molecules are understood in depth. Thereby, it is important to develop methods for characterizing the fiber chain to be able to monitor its structural alterations upon intermolecular interactions. Here, we demonstrate the utility of the electron paramagnetic resonance (EPR) spectroscopy, complemented by simulations in probing the atomistic details of the chain conformations for spin-labeled fibers. Barley β-glucan, a native polysaccharide with linear chain, was utilized as a test fiber system to demonstrate the technique's capabilities. Pulse dipolar EPR data show good agreement with results of the fiber chain modeling, revealing sinuous chain conformations and providing polymer shape descriptors: the gyration tensor, spin-spin distance distribution function, and information about proton density near the spin probe. Results from EPR measurements point to the fiber aggregation in aqueous solution, which agrees with the results of the dynamic light scattering. We propose that the combination of pulse EPR measurements with modeling can be a perfect experimental tool for in-depth structural investigation of dietary fibers and their interaction under such conditions, and that the presented methodology can be extended to other weakly ordered or disordered macromolecules.

Inorganic Chemistry in Dalian University of Technology: Fundamental Science and Solution for Renewable Energy, Environment, Health, and Materials

Inorganic Chemistry in Dalian University of Technology: Fundamental Science and Solution for Renewable Energy, Environment, Health, and Materials

High-resolution spectroscopy of a single nitrogen-vacancy defect at zero magnetic field

We report a study of high-resolution microwave spectroscopy of nitrogen-vacancy (NV) centers in diamond crystals at and around zero magnetic field. We observe characteristic splitting and transition imbalance of the hyperfine transitions, which originate from level anti-crossings (LACs) in the presence of a transverse effective field. We use pulsed electron spin resonance spectroscopy to measure the zero-field spectral features of single NV centers for clearly resolving such LACs. To quantitatively analyze the magnetic resonance behavior of the hyperfine spin transitions in the presence of the effective field, we present a theoretical model, which describes the transition strengths under the action of an arbitrarily polarized microwave magnetic field. Our results are of importance for the optimization of the experimental conditions for the polarization-selective microwave excitation of spin-1 systems in zero or weak magnetic fields.

Recent Developments on Understanding Charge Transfer in Molecular Electron Donor-Acceptor Systems.

Charge transfer (CT) in molecular electron donor-acceptor systems is pivotal for artificial photosynthesis, photocatalysis, photovoltaics and fundamental photochemistry. We summarized the recent development in study of CT and discussed its application in thermally activated delayed fluorescence (TADF) emitters. The direct experimental proof of the spin multiplicity of the charge separated (CS) state with pulsed laser excited time-resolved electron paramagnetic resonance (TREPR) spectroscopy was discussed. Experimental determination of the electron exchange energy (J) of the CS state, with magnetic field effect on its yield or lifetime was introduced. The electron spin transfer accompanying the CT, studied with pulsed EPR spectra was briefly discussed. Tuning of the CT yield and kinetics with selective vibration excitation of the linker (the bridge) with IR pulse was presented. Above all, these studies show that there are more fun than simply monitoring the formation of the cations and anions and the kinetics or CS yields in this area.