Role of quantum coherence in chirped dynamic nuclear polarization.

Dynamic Nuclear Polarization (DNP) is transforming nuclear magnetic resonance and MRI by significantly enhancing sensitivity through the transfer of polarization from electron spins to nuclear spins via microwave irradiation. However, the use of monochromatic continuous-wave irradiation limits the efficiency of DNP for systems with heterogeneous, broad electron paramagnetic resonance lines. Broadband techniques such as chirp irradiation offer a potential solution, particularly for Solid Effect (SE) DNP in such cases.

Microwave-free nuclear spin hyperpolarization through photo-CIDNP in static and rotating solids.

This study advances the theoretical foundation of photo-chemically induced dynamic nuclear polarization (photo-CIDNP)-a powerful mechanism for enhancing nuclear spin sensitivity without microwave irradiation. Using an operator-based effective Hamiltonian approach, we derive precise resonance matching conditions and identify key dipolar scaling factors governing the photo-CIDNP Hamiltonian under both static and magic-angle spinning conditions. Our analytical formulation of coherent evolution of photoexcited singlet state exhibits strong agreement with numerical simulations, reinforcing the validity of our theoretical framework.

Impact of asymmetric stenosis and heart rate on the left coronary artery hemodynamics in elderly patients: a 3D computational study.

The left coronary main (LCM) artery and its branches, particularly the left anterior descending (LAD) artery, are highly prone to atherosclerosis, especially as arterial stiffness increases with age. Irregularities in arterial geometry further contribute to the development of asymmetric plaques, underscoring the importance of three-dimensional (3D) hemodynamic studies, which remain limited in literature. Moreover, no existing research explores how hemodynamic variables change with different heart rates in the presence of asymmetric plaque in LAD, which is essential for assessing the disease severity and progression.

Optimal control-based nuclear spin cross-polarization in the presence of complicating anisotropic interactions.

Cross-polarization is an indispensable part of solid state nuclear magnetic resonance spectroscopy to enhance sensitivity and extract structural information. However, the presence of certain anisotropic interactions, including chemical shift anisotropy and quadrupolar coupling, makes the inter-nuclear spin correlation experiments challenging. This impedes characterization of numerous materials and pharmaceutical compounds containing isotopes, such as F with large chemical shift anisotropy and Li, Na, Al, , with quadrupolar coupling.

Magic-NOVEL: Suppressing electron-electron coupling effects in pulsed DNP.

Pulsed dynamic nuclear polarization (DNP) enhances the nuclear magnetic resonance sensitivity by coherently transferring electron spin polarization to dipolar coupled nuclear spins. Recently, many new pulsed DNP techniques such as NOVEL, TOP, XiX, TPPM, and BEAM have been introduced. Despite significant progress, numerous challenges remain unsolved.

Numerical assessment of using various outlet boundary conditions on the hemodynamics of an idealized left coronary artery model.

Vascular diseases are greatly influenced by the hemodynamic parameters and the accuracy of determining these parameters depends on the use of correct boundary conditions. The present work carries out a two-way fluid-structure interaction (FSI) simulation to investigate the effects of outlet pressure boundary conditions on the hemodynamics through the left coronary artery bifurcation with moderate stenosis (50%) in the left anterior descending (LAD) branch. The Carreau viscosity model is employed to characterise the shear-thinning behaviour of blood.

Tailoring solid-state DNP methods to the study of α-synuclein LLPS.

Dynamic Nuclear Polarization (DNP) is a technique that leverages the quantum sensing capability of electron spins to enhance the sensitivity of nuclear magnetic resonance (NMR) signals, especially for insensitive samples. Glassing agents play a crucial role in the DNP process by facilitating the transfer of polarization from the unpaired electron spins to the nuclear spins along with cryoprotection of biomolecules. DNPjuice comprising of glycerol-d/DO/HO has been extensively used for this purpose over the past two decades.

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 H NMR characteristic of the presence of electron spin clusters.

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 H NMR at 7 T, supported by experimental data and quantum mechanical simulations. A slow-relaxing ( ≈ 1 ms) 4-ESC is found to require at least two electron spin pairs at <8 Å e-e spin distance to yield H ESC-DNP enhancement, while squeezing the rest of the e-e spin distances to <12 Å results in optimal H ESC-DNP enhancements.

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.

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-β-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.

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 () followed by a spin-polarized doublet ground state (), which hold promise as spin qudits and qubits, respectively.

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 (H-C) in a solid state probe operating at cryogenic temperatures.

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-β-phenylallyl radical (BDPA-d ) was synthesized and characterized by time-resolved optical and electron paramagnetic resonance (EPR) spectroscopies. Photoexcitation of tpPDI-BDPA-d results in ultrafast radical-enhanced intersystem crossing to produce a quartet state (Q) followed by formation of a spin-polarized doublet ground state (D ).

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.

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.

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.

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.

H 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.

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.

Crossover from a Solid Effect to Thermal Mixing H 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 C, but not of the abundant H 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 H 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 - couplings and (ii) hyperpolarization, i.

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.

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.

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.