Dipolar Order Induced Electron Spin Hyperpolarization.

The structure of coupled electron spin systems is of fundamental interest to many applications, including dynamic nuclear polarization (DNP), enhanced nuclear magnetic resonance (NMR), the generation of electron spin qubits for quantum information science (QIS), and quantitative studies of paramagnetic systems by electron paramagnetic resonance (EPR). However, the characterization of electron spin coupling networks is nontrivial, especially at high magnetic fields. This study focuses on a system containing high concentrations of trityl radicals that give rise to a DNP enhancement profile of 1H NMR characteristic of the presence of electron spin clusters. When this system is subject to selective microwave saturation through pump-probe ELectron DOuble Resonance (ELDOR) experiments, electron spin hyperpolarization is observed. We show that the generation of an out-of-equilibrium longitudinal dipolar order is responsible for the transient hyperpolarization of electron spins. Notably, the coupled electron spin system needs to form an AX-like system (where the difference in the Zeeman interactions of two spins is larger than their coupling interaction) such that selective microwave irradiation can generate signatures of electron spin hyperpolarization. We show that the extent of dipolar order, as manifested in the extent of electron spin hyperpolarization generated, can be altered by tuning the pump or probe pulse length, or the interpulse delay in ELDOR experiments that change the efficiency to generate or readout longitudinal dipolar order. Pump-probe ELDOR with selective saturation is an effective means for characterizing coupled electron spins forming AX-type spin systems that are foundational for DNP and quantum sensing.

Dynamic Nuclear Polarization Using Electron Spin Cluster.

Dynamic nuclear polarization (DNP) utilizing narrow-line electron spin clusters (ESCs) to achieve nuclear spin resonance matching (ESC-DNP) by microwave irradiation is a promising way to achieve NMR signal enhancements with a wide design scope requiring low microwave power at high magnetic field. Here we present the design for a trityl-based tetra-radical (TetraTrityl) to achieve DNP for 1H NMR at 7 T, supported by experimental data and quantum mechanical simulations. A slow-relaxing (T1e ≈ 1 ms) 4-ESC is found to require at least two electron spin pairs at <8 Å e-e spin distance to yield 1H ESC-DNP enhancement, while squeezing the rest of the e-e spin distances to <12 Å results in optimal 1H ESC-DNP enhancements. Fast-relaxing ESCs (T1e ≈ 10 µs) are found to require a weakly coupled narrow-line radical (sensitizer) to extract polarization from the ESC. These results provide design principles for achieving a power-efficient DNP at high field via ESC-DNP.

P1 Center Electron Spin Clusters Are Prevalent in Type Ib Diamonds.

Understanding the spatial distribution of the P1 centers is crucial for diamond-based sensors and quantum devices. P1 centers serve as polarization sources for dynamic nuclear polarization (DNP) quantum sensing and play a significant role in the relaxation of nitrogen vacancy (NV) centers. Additionally, the distribution of NV centers correlates with the distribution of P1 centers, as NV centers are formed through the conversion of P1 centers. We utilized DNP and pulsed electron paramagnetic resonance (EPR) techniques that revealed strong clustering of a significant population of P1 centers that exhibit exchange coupling and produce asymmetric line shapes. The 13C DNP frequency profile at a high magnetic field revealed a pattern that requires an asymmetric EPR line shape of the P1 clusters with electron-electron (e-e) coupling strengths exceeding the 13C nuclear Larmor frequency. EPR and DNP characterization at high magnetic fields was necessary to resolve energy contributions from different e-e couplings. We employed a two-frequency pump-probe pulsed electron double resonance technique to show cross-talk between the isolated and clustered P1 centers. This finding implies that the clustered P1 centers affect all of the P1 populations. Direct observation of clustered P1 centers and their asymmetric line shape offers a novel and crucial insight into understanding magnetic noise sources for quantum information applications of diamonds and for designing diamond-based polarizing agents with optimized DNP efficiency for 13C and other nuclear spins of analytes. We propose that room temperature 13C DNP at a high field, achievable through straightforward modifications to existing solution-state NMR systems, is a potent tool for evaluating and controlling diamond defects.

Multi Electron Spin Cluster Enabled Dynamic Nuclear Polarization with Sulfonated BDPA.

Dynamic nuclear polarization (DNP) can amplify the solid-state nuclear magnetic resonance (NMR) signal by several orders of magnitude. The mechanism of DNP utilizing α,γ-bisdiphenylene-ß-phenylallyl (BDPA) variants as Polarizing Agents (PA) has been the subject of lively discussions on account of their remarkable DNP efficiency with low demand for microwave power. We propose that electron spin clustering of sulfonated BDPA is responsible for its DNP performance, as revealed by the temperature-dependent shape of the central DNP profile and strong electron-electron (e-e) crosstalk seen by Electron Double Resonance. We demonstrate that a multielectron spin cluster can be modeled with three coupled spins, where electron J (exchange) coupling between one of the e-e pairs matching the NMR Larmor frequency induces the experimentally observed absorptive central DNP profile, and the electron T1e modulated by temperature and magic-angle spinning alters the shape between an absorptive and dispersive feature. Understanding the microscopic origin is key to designing new PAs to harness the microwave-power-efficient DNP effect observed with BDPA variants.

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.

Design of a cryogen-free high field dual EPR and DNP probe.

We present the design and construction of a cryogen free, dual electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) probe for novel dynamic nuclear polarization (DNP) experiments and concurrent "in situ" analysis of DNP mechanisms. We focus on the probe design that meets the balance between EPR, NMR, and low temperature performance, while maintaining a high degree of versatility: allowing multi-nuclear NMR detection as well as broadband DNP/EPR excitation/detection. To accomplish high NMR/EPR performance, we implement a novel inductively coupled double resonance NMR circuit (1H-13C) in a solid state probe operating at cryogenic temperatures. The components of the circuit were custom built to provide maximum NMR performance, and the physical layout of this circuit was numerically optimized via magnetic field simulations to allow maximum microwave transmission to the sample for optimal EPR performance. Furthermore this probe is based around a cryogen free gas exchange cryostat and has been designed to allow unlimited experiment times down to 8.5 Kelvin with minimal cost. The affordability of EPR/DNP experiment is an extremely important aspect for broader impact with magnetic resonance measurements. The purpose of this article is to provide as complete information as we have available for others with interest in building a dual DNP/EPR instrument based around a cryogen-free cryostat.

Optical Spin Polarization of a Narrow-Linewidth Electron-Spin Qubit in a Chromophore/Stable-Radical System.

Photoexcited organic chromophores appended to stable radicals can serve as qubit and/or qudit candidates for quantum information applications. 1,6,7,12-Tetra-(4-tert-butylphenoxy)-perylene-3,4 : 9,10-bis(dicarboximide) (tpPDI) linked to a partially deuterated α,γ-bisdiphenylene-ß-phenylallyl radical (BDPA-d16 ) was synthesized and characterized by time-resolved optical and electron paramagnetic resonance (EPR) spectroscopies. Photoexcitation of tpPDI-BDPA-d16 results in ultrafast radical-enhanced intersystem crossing to produce a quartet state (Q) followed by formation of a spin-polarized doublet ground state (D0 ). Pulse-EPR experiments confirmed the spin multiplicity of Q and yielded coherence times of Tm =2.1±0.1 µs and 2.8±0.2 µs for Q and D0 , respectively. BDPA-d16 eliminates the dominant 1 H hyperfine couplings, resulting in a single narrow line for both the Q and D0 states, which enhances the spectral resolution needed for good qubit addressability.

Unique thiol metabolism in trypanosomatids: Redox homeostasis and drug resistance.

Trypanosomatids are mainly responsible for heterogeneous parasitic diseases: Leishmaniasis, Sleeping sickness, and Chagas disease and control of these diseases implicates serious challenges due to the emergence of drug resistance. Redox-active biomolecules are the endogenous substances in organisms, which play important role in the regulation of redox homeostasis. The redox-active substances like glutathione, trypanothione, cysteine, cysteine persulfides, etc., and other inorganic intermediates (hydrogen peroxide, nitric oxide) are very useful as defence mechanism. In the present review, the suitability of trypanothione and other essential thiol molecules of trypanosomatids as drug targets are described in Leishmania and Trypanosoma. We have explored the role of tryparedoxin, tryparedoxin peroxidase, ascorbate peroxidase, superoxide dismutase, and glutaredoxins in the anti-oxidant mechanism and drug resistance. Up-regulation of some proteins in trypanothione metabolism helps the parasites in survival against drug pressure (sodium stibogluconate, Amphotericin B, etc.) and oxidative stress. These molecules accept electrons from the reduced trypanothione and donate their electrons to other proteins, and these proteins reduce toxic molecules, neutralize reactive oxygen, or nitrogen species; and help parasites to cope with oxidative stress. Thus, a better understanding of the role of these molecules in drug resistance and redox homeostasis will help to target metabolic pathway proteins to combat Leishmaniasis and trypanosomiases.

Investigating the Dimensional Accuracy of the Cavity Produced by ABS P400 Polymer-Based Novel EDM Electrode.

In the present study, cylindrical ABS P400 polymer parts (diameter 6.5 mm) to be used as die-sinking EDM (electric discharge machining) novel electrodes were fabricated using a fused deposition modeling (FDM) process. To meet the conductivity requirement in EDM, ABS parts were metallized using an innovative method that comprised putting aluminum-charcoal (Al-C) on them followed by their copper electroplating. Real-time EDM of the mild steel workpiece was performed using novel electrodes, and machining performance of the electrodes, measured in terms of dimensional accuracy, i.e., change in diameter (ΔD) and change in depth (ΔH) of the cavity, under varying levels of three EDM factors, i.e., current (I), pulse on time (Ton), and pulse off time (Toff), was investigated. Machining results were analyzed using analysis of variance (ANOVA), perturbation graphs, and 3D surface plots. The optimal setting of the EDM parameters for minimizing ΔD and ΔH was determined using the desirability function approach. The suitability of the novel electrodes for EDM was ascertained by comparing their machining results with those of solid copper (SC) electrodes and electrodes fabricated by FDM and metallized using the electro-deposition method (FDM-EM), already reported in the literature, under similar machining conditions. From the results, it was found that ΔD and ΔH were less when EDM was performed using novel electrodes.

Role of electron spin dynamics and coupling network in designing dynamic nuclear polarization.

Dynamic nuclear polarization (DNP) has emerged as a powerful sensitivity booster of nuclear magnetic resonance (NMR) spectroscopy for the characterization of biological solids, catalysts and other functional materials, but is yet to reach its full potential. DNP transfers the high polarization of electron spins to nuclear spins using microwave irradiation as a perturbation. A major focus in DNP research is to improve its efficiency at conditions germane to solid-state NMR, at high magnetic fields and fast magic-angle spinning. In this review, we highlight three key strategies towards designing DNP experiments: time-domain "smart" microwave manipulation to optimize and/or modulate electron spin polarization, EPR detection under operational DNP conditions to decipher the underlying electron spin dynamics, and quantum mechanical simulations of coupled electron spins to gain microscopic insights into the DNP mechanism. These strategies are aimed at understanding and modeling the properties of the electron spin dynamics and coupling network. The outcome of these strategies is expected to be key to developing next-generation polarizing agents and DNP methods.

Floquet theory in magnetic resonance: Formalism and applications.

Floquet theory is an elegant mathematical formalism originally developed to solve time-dependent differential equations. Besides other fields, it has found applications in optical spectroscopy and nuclear magnetic resonance (NMR). This review attempts to give a perspective of the Floquet formalism as applied in NMR and shows how it allows one to solve various problems with a focus on solid-state NMR. We include both matrix- and operator-based approaches. We discuss different problems where the Hamiltonian changes with time in a periodic way. Such situations occur, for example, in solid-state NMR experiments where the time dependence of the Hamiltonian originates either from magic-angle spinning or from the application of amplitude- or phase-modulated radiofrequency fields, or from both. Specific cases include multiple-quantum and multiple-frequency excitation schemes. In all these cases, Floquet analysis allows one to define an effective Hamiltonian and, moreover, to treat cases that cannot be described by the more popularly used and simpler-looking average Hamiltonian theory based on the Magnus expansion. An important example is given by spin dynamics originating from multiple-quantum phenomena (level crossings). We show that the Floquet formalism is a very general approach for solving diverse problems in spectroscopy.

1H Thermal Mixing Dynamic Nuclear Polarization with BDPA as Polarizing Agents.

Dynamic Nuclear Polarization (DNP) is a sensitivity enhancing technique for Nuclear Magnetic Resonance. A recent discovery of Overhauser Effect (OE) DNP in insulating systems under cryogenic conditions using 1,3-bisdiphenylene-2-phenylallyl (BDPA) as the polarizing agent (PA) has caught attention due to its promising DNP performance at a high magnetic field and under fast magic angle spinning conditions. However, the mechanism of OE in insulating-solids/BDPA is unclear. We present an alternative explanation that the dominant underlying DNP mechanism of BDPA is Thermal Mixing (TM). This is ascertained with the discovery that TM effect is enhanced by multi-electron spin coupling, which is corroborated by an asymmetric electron paramagnetic resonance line shape signifying the coexistence of clustered and isolated BDPA species, and by hyperpolarized electron spin populations giving rise to an electron spin polarization gradient which are characteristic signatures of TM DNP. Finally, quantum mechanical simulations using spatially asymmetrically coupled three electron spins and a nuclear spin demonstrate that triple-flip DNP, with hyperfine fluctuations turned off, can yield the 1H DNP profile as observed with BDPA. Clarifying the DNP mechanism is critical to develop design principles for optimizing the PA for achieving optimal DNP efficiency.

Balancing dipolar and exchange coupling in biradicals to maximize cross effect dynamic nuclear polarization.

Dynamic nuclear polarization (DNP) by the cross effect (CE) has become a game changer for solid-state nuclear magnetic resonance (NMR) spectroscopy. The efficiency of CE-DNP depends on the strength of the electron-electron coupling in biradical polarizing agents. Hence, the focus lately has been on designing biradicals with a large net exchange (J) and dipolar (D) coupling. In this study, we reveal that the crucial factor for CE-DNP is not the large sum, J + D, but rather the relative magnitude of J and D, expressed as the J/D ratio. We show that the mechanistic basis of this interference lies in the isotropic vs. the anisotropic nature of the J and D couplings, respectively. This interference can lead to a small (effective) electron-electron coupling for many orientations even when J + D is large, resulting in non-adiabatic rotor-events. We find that when 0 < |J/D| < 1 the CE-DNP efficiency is attenuated for the majority of orientations, with greater attenuation observed at higher magnetic fields and faster magic-angle spinning (MAS) frequency. The interference effect of J and D coupling introduced in this study can explain why many biradicals with high or comparable J + D still show significantly divergent DNP performances. We debut J/D as a consequential criteria for designing efficient biradicals to robustly perform across a large range of B0 fields and MAS frequencies.

Crossover from a Solid Effect to Thermal Mixing 1H Dynamic Nuclear Polarization with Trityl-OX063.

Trityl-OX063 is a narrow-line, water-soluble, and biocompatible polarizing agent, widely used for dynamic nuclear polarization (DNP) amplified NMR of 13C, but not of the abundant 1H nuclear spin, for which the ineffective solid effect (SE) is expected to be operational. Surprisingly, we observed a crossover from SE to thermal mixing (TM) DNP of 1H with increasing Trityl-OX063 concentration at 7 T. We experimentally ascertained diagnostic signatures of TM-DNP that have only been theoretically predicted: (i) an electron paramagnetic resonance (EPR) spectrum that maintains an asymmetrically broadened EPR line from strong e-e couplings and (ii) hyperpolarization, i.e., cooling of select electron-spin populations, manifested in a characteristic pump-probe electron double-resonance spectrum under DNP conditions. Low microwave power requirements, high polarization transfer rates, and efficient DNP at high magnetic fields are the key benefits of TM-DNP.

Pulse-Shaped Dynamic Nuclear Polarization under Magic-Angle Spinning.

Dynamic nuclear polarization (DNP) under magic-angle spinning (MAS) is transforming the scope of solid-state NMR by enormous signal amplification through transfer of polarization from electron spins to nuclear spins. Contemporary MAS-DNP exclusively relies on monochromatic continuous-wave (CW) irradiation of the electron spin resonance. This limits control on electron spin dynamics, which renders the DNP process inefficient, especially at higher magnetic fields and non cryogenic temperatures. Pulse-shaped microwave irradiation of the electron spins is predicted to overcome these challenges but hitherto has never been implemented under MAS. Here, we debut pulse-shaped microwave irradiation using arbitrary-waveform generation (AWG) which allows controlled recruitment of a greater number of electron spins per unit time, favorable for MAS-DNP. Experiments and quantum mechanical simulations demonstrate that pulse-shaped DNP is superior to CW-DNP for mixed radical system, especially when the electron spin resonance is heterogeneously broadened and/or when its spin-lattice relaxation is fast compared to the MAS rotor period, opening new prospects for MAS-DNP.

Electron spin density matching for cross-effect dynamic nuclear polarization.

A new design principle for a mixed broad (TEMPO) and narrow (Trityl) line radical to boost the dynamic nuclear polarization efficiency is electron spin density matching, suggesting a polarizing agent of one Trityl tethered to at least two TEMPO moieties.

Biradical rotamer states tune electron J coupling and MAS dynamic nuclear polarization enhancement.

Cross Effect (CE) Dynamic Nuclear Polarization (DNP) relies on the dipolar (D) and exchange (J) coupling interaction between two electron spins. Until recently only the electron spin D coupling was explicitly included in quantifying the DNP mechanism. Recent literature discusses the potential role of J coupling in DNP, but does not provide an account of the distribution and source of electron spin J coupling of commonly used biradicals in DNP. In this study, we quantified the distribution of electron spin J coupling in AMUPol and TOTAPol biradicals using a combination of continuous wave (CW) X-band electron paramagnetic resonance (EPR) lineshape analysis in a series of solvents and at variable temperatures in solution - a state to be vitrified for DNP. We found that both radicals show a temperature dependent distribution of J couplings, and the source of this distribution to be conformational dynamics. To qualify this conformational dependence of J coupling in both molecules we carry out Broken Symmetry DFT calculations which show that the biradical rotamer distribution can account for a large distribution of J couplings, with the magnitude of J coupling directly depending on the relative orientation of the electron spin pair. We demonstrate that the electron spin J couplings in both AMUPol and TOTAPol span a much wider distribution than suggested in the literature. We affirm the importance of electron spin J coupling for DNP with density matrix simulations of DNP in Liouville space and under magic angle spinning, showcasing that a rotamer with high J coupling and optimum relative g-tensor orientation can significantly boost the DNP performance compared to random orientations of the electron spin pair. We conclude that moderate electron spin J coupling above a threshold value can facilitate DNP enhancements.

A unified heteronuclear decoupling picture in solid-state NMR under low radio-frequency amplitude and fast magic-angle-spinning frequency regime.

Heteronuclear spin decoupling is a highly important component of solid-state NMR experiments to remove undesired coupling interactions between unlike spins for spectral resolution. Recently, experiments using a unification strategy of standard decoupling schemes were presented for high radio-frequency (RF) amplitudes and slow-intermediate magic-angle-spinning (MAS) frequencies, in the pursuit of deeper understanding of spin decoupling under phase-modulated RF irradiation [A. Equbal et al., J. Chem. Phys. 142, 184201 (2015)]. The approach, unified two-pulse heteronuclear decoupling (UTPD), incorporates the simultaneous time- and phase-modulation strategies, commonly used in solid-state NMR. Here, the UTPD based decoupling scheme is extended to the experimentally increasingly important regime of low RF amplitudes and fast MAS frequencies. The unified decoupling approach becomes increasingly effective in identifying the deleterious dipole-dipole and, in particular, J recoupling conditions which become critical for the low-amplitude RF regime. This is because J coupling is isotropic and therefore not averaged out by sample spinning unlike the anisotropic dipole-dipole coupling. Numerical simulations and analytic theory are used to understand the effects of various nuclear spin interactions on the decoupling performance of UTPD, in particular, the crucial difference between the low-phase and high-phase UTPD conditions with respect to J coupling. In the UTPD scheme, when the cycle-frequency of the pulse-sequence is comparable to the RF nutation frequency, the existence of a non-zero effective rotation in the basic two-pulse scheme becomes an essential feature for the efficient and robust averaging out of the scalar J coupling. This broad viewpoint is expected to bring different optimum low-power decoupling pulse schemes under a common footing.

Cross-Effect Dynamic Nuclear Polarization Explained: Polarization, Depolarization, and Oversaturation.

The scope of this Perspective is to analytically describe NMR hyperpolarization by the three-spin cross effect (CE) dynamic nuclear polarization (DNP) using an effective Hamiltonian concept. We apply, for the first time, the bimodal operator-based Floquet theory in the Zeeman-interaction frame for two and three coupled spins to derive the known interaction Hamiltonian for CE-DNP. With a unified understanding of CE-DNP, and supported by empirical observation of the state of electron spin polarization under the given experimental conditions, we explain diverse manifestations of CE from oversaturation, enhanced hyperpolarization by broad-band saturation, to nuclear spin depolarization under magic-angle spinning.

Tuning nuclear depolarization under MAS by electron T1e.

The Cross-Effect (CE) Dynamic Nuclear Polarization (DNP) mechanism under Magic Angle Spinning (MAS) induces depletion or "depolarization" of the NMR signal, in the absence of microwave irradiation. In this study, the role of T1e on nuclear depolarization under MAS was tested experimentally by systematically varying the local and global electron spin concentration using mono-, bi- and tri-radicals. These spin systems show different depolarization effects that systematically tracked with their different T1e rates, consistent with theoretical predictions. In order to test whether the effect of T1e is directly or indirectly convoluted with other spin parameters, the tri-radical system was doped with different concentrations of GdCl3, only tuning the T1e rates, while keeping other parameters unchanged. Gratifyingly, the changes in the depolarization factor tracked the changes in the T1e rates. The experimental results are corroborated by quantum mechanics based numerical simulations which recapitulated the critical role of T1e. Simulations showed that the relative orientation of the two g-tensors and e-e dipolar interaction tensors of the CE fulfilling spin pair also plays a major role in determining the extent of depolarization, besides the enhancement. This is expected as orientations influence the efficiency of the various level anti-crossings or the "rotor events" under MAS. However, experimental evaluation of the empirical spectral diffusion parameter at static condition showed that the local vs. global e-e dipolar interaction network is not a significant variable in the commonly used nitroxide radical system studied here, leaving T1e rates as the major modulator of depolarization.