Spin Pairs Research Articles

Enhanced TROSY Effect in [2-19 F, 2-13 C] Adenosine and ATP Analogs Facilitates NMR Spectroscopy of Very Large Biological RNAs in Solution.

Large RNAs are central to cellular functions, but characterizing such RNAs remains challenging by solution NMR. We present two labeling technologies based on [2-19 F, 2-13 C]-adenosine, which allow the incorporation of aromatic 19 F-13 C spin pairs. The labels when coupled with the transverse relaxation optimized spectroscopy (TROSY) enable us to probe RNAs comprising up to 124 nucleotides. With our new [2-19 F, 2-13 C]-adenosine-phosphoramidite, all resonances of the human hepatitis B virus epsilon RNA could be readily assigned. With [2-19 F, 2-13 C]-adenosine triphosphate, the 124 nt pre-miR-17-NPSL1-RNA was produced via in vitro transcription and the TROSY spectrum of this 40 kDa [2-19 F, 2-13 C]-A-labeled RNA featured sharper resonances than the [2-1 H, 2-13 C]-A sample. The mutual cancelation of the chemical-shift-anisotropy and the dipole-dipole-components of TROSY-resonances leads to narrow linewidths over a wide range of molecular weights. With the synthesis of a non-hydrolysable [2-19 F, 2-13 C]-adenosine-triphosphate, we facilitate the probing of co-factor binding in kinase complexes and NMR-based inhibitor binding studies in such systems. Our labels allow a straightforward assignment for larger RNAs via a divide-and-conquer/mutational approach. The new [2-19 F, 2-13 C]-adenosine precursors are a valuable addition to the RNA NMR toolbox and will allow the study of large RNAs/RNA protein complexes in vitro and in cells.

Ground-state phase diagram and universality of sequential topological valence-bond-solid quantum transitions in a mixed tetramer chain

The ground-state ordering of a quantum mixed-spin Heisenberg tetramer chain composed of an alternate sequence of s = 1 and S=3/2 dimers is studied in detail as a function of two considered exchange interactions ascribed to similar and dissimilar spin pairs. At zero magnetic field, the ferrimagnetic mixed spin-(1, 1, 3/2, 3/2) Heisenberg tetramer chain displays, depending on a mutual interplay between two considered exchange interactions, three distinct gapped valence-bond-solid phases separated by gap-closing quantum critical points. Using density-matrix renormalization group calculations we construct the full ground-state phase diagram as a function of the interaction ratio and magnetic field, which exhibits besides three gapped valence-bond-solid phases special Kosterlitz–Thouless and topological quantum critical points. A tangential finite-size scaling analysis is employed to obtain precise estimates of the zero-field valence-bond-solid transitions and unveil their common logarithmic correction to a power-law scaling of the correlation length.

Theoretical examination of nuclear spin diffusion in light-induced spin coherences in photosystem I

Microsecond coherence times are predicted in spin dynamics calculations of a donor–acceptor electron spin pair P+A1A− created upon light excitation of photosystem I (PSI). The effects of nuclear spin diffusion (NSD) due to the anisotropic protein environment on the predicted coherence times TM are studied. Closely positioned pairs and triples of protons located 5–8 Å from the electron spin are shown to largely control TM. Knowledge of the crystal structure of PSI allows for spin dynamics calculations where specific cofactors and amino acid residues are removed or replaced and the identification of anisotropic environmental features controlling electronic decoherence. Finally, we show that NSD alone cannot explain the >3× shorter experimentally observed coherence times and suggest that methyl groups at key protein sites may explain this discrepancy.

A possible coexistence of spontaneous magnetic order and thermal entanglement in a spin-1/2 Ising–Heisenberg diamond-decorated square lattice

The spin-1/2 Ising–Heisenberg model on a diamond-decorated square lattice is exactly solved by the decoration-iteration transformation, which establishes an exact mapping correspondence with the spin-1/2 Ising model on a square lattice with an effective temperature-dependent interaction between the nearest-neighbor spins. Exact results for the pair correlation function and spontaneous magnetization of the Heisenberg spins gained from the exact mapping equivalence allow a straightforward implementation of the concurrence, which may serve as a measure of the bipartite entanglement within decorating Heisenberg spin pairs. It is evidenced that the concurrence gradually diminishes upon increase of temperature above a disordered monomer-dimer ground state until it completely vanishes at a threshold temperature, while the concurrence is either always zero above a spontaneously ordered ferrimagnetic ground state or it shows a peculiar thermally assisted reentrance accompanied with a mutual coexistence of the spontaneous ferrimagnetic long-range order and the thermal entanglement.

Pauli blockade catalogue and three- and four-particle Kondo effect in bilayer graphene quantum dots

Pauli blockade is a fundamental quantum phenomenon that also serves as a powerful tool for qubit manipulation and readout. While most systems exhibit a simple even-odd pattern of double-dot Pauli spin blockade due to the preferred singlet pairing of spins, the additional valley degree of freedom offered by bilayer graphene greatly alters this pattern. Inspecting bias-triangle measurements at double-dot charge degeneracies with up to four electrons in each dot reveals a much richer double-dot Pauli blockade catalog with both spin and/or valley blockade. In addition, we use single-dot Kondo effect measurements to substantiate our understanding of the three- and four-particle state spectra by analyzing their magnetic field dependence. With high controllability and reported long valley- and spin-relaxation times, bilayer graphene is a rising platform for hosting semiconductor quantum dot qubits. A thorough understanding of state spectra is crucial for qubit design and manipulation, and the rich Pauli blockade catalog provides an abundance of qubit operational possibilities and opportunities to explore intriguing spin and valley physics. Published by the American Physical Society 2024

NMR spectroscopy of a 18O-labeled rhodium paddlewheel complex: Isotope shifts, 103Rh-103Rh spin-spin coupling, and 103Rh singlet NMR.

Despite the importance of rhodium complexes in catalysis, and the favorable 100% natural abundance of the spin-1/2 103Rh nucleus, there are few reports of 103Rh nuclear magnetic resonance (NMR) parameters in the literature. In part, this is the consequence of the very low gyromagnetic ratio of 103Rh and its dismal NMR sensitivity. In a previous paper [Harbor-Collins et al., J. Chem. Phys. 159, 104 307 (2023)], we demonstrated an NMR methodology for 1H-enhanced 103Rh NMR and demonstrated an application to the 103Rh NMR of the dirhodium formate paddlewheel complex. In this paper, we employ selective 18O labeling to break the magnetic equivalence of the 103Rh spin pair of dirhodium formate. This allows the estimation of the 103Rh-103Rh spin-spin coupling and provides access to the 103Rh singlet state. We present the first measurement of a 18O-induced 103Rh secondary isotope shift as well as the first instance of singlet order generated in a 103Rh spin pair. The field-dependence of 103Rh singlet relaxation is measured by field-cycling NMR experiments.

The synthesis of specifically isotope labelled fluorotryptophan and its use in mammalian cell-based protein expression for 19F-NMR applications.

19F nuclei serve as versatile sensors for detecting protein interactions and dynamics in biomolecular NMR spectroscopy. Although various methods have been developed to incorporate fluorine-containing aromatic residues into proteins using E. coli or cell-free expression techniques, similar approaches for protein production in mammalian cell lines remain limited. Here, we present a cost-effective synthetic route to obtain selectively deuterated, carbon-13 labeled fluorotryptophan and demonstrate its use in introducing 19F-13C spin pairs into carbonic anhydrase 2 and superoxide dismutase, following an expression protocol utilizing HEK cells.

Perovskite-based two-dimensional ferromagnet Sr<sub>2</sub>RuO<sub>4</sub> monolayer

At present, the research on two-dimensional (2D) ferromagnets is mainly concentrated in the field of van der Waals materials, while the successful preparation of strain-free freestanding 2D perovskite films provides a great opportunity for the design of 2D ferromagnets beyond van der Waals materials. Perovskite oxide SrRuO<sub>3</sub>, as a typical perovskite itinerant ferromagnet, has broad application prospects in many fields. In this paper, the lattice dynamics, ground-state structure, electronic and magnetic properties of its perovskite monolayer with formula Sr<sub>2</sub>RuO<sub>4</sub>, as well as the effect of external electric field, are studied by combining first-principles calculation, symmetry analysis and Monte Carlo simulation. The influence of the Hubbard parameter <i>U</i> is also revealed. The results indicate that the ground-state structure under all <i>U</i> values is the structural phase (space group <inline-formula><tex-math id="M2">\begin{document}$P4/mbm$\end{document}</tex-math></inline-formula>) generated by octahedral rotation distortion. Similar to the SrRuO<sub>3</sub> bulk, the ground-state phase of the Sr<sub>2</sub>RuO<sub>4</sub> monolayer exhibits ferromagnetism, which is independent of the <i>U</i> value and thus robust. Density functional theory calculation with Hubbard parameter <i>U</i> predicts the ground-state phase of the monolayer to be a ferromagnetic half metal with out-of-plane easy-magnetization axis, while excluding the <i>U</i> parameter predicts the ground-state phase to be a ferromagnetic metallic state. The ferromagnetism mainly originates from the strong ferromagnetic exchange interaction between the nearest neighbor spin pairs. The simulated Curie temperature of the Sr<sub>2</sub>RuO<sub>4</sub> monolayer is 177 K, which is close to the value (150 K) of its bulk phase. The out-of-plane electric field does not change the ground-state structure and ferromagnetism of the Sr<sub>2</sub>RuO<sub>4</sub> monolayer, but can significantly modulate its electronic and magnetic properties. When an external electric field exceeding 0.3 V/Å is applied, the system undergoes a transition from a ferromagnetic half-metal state to a ferromagnetic metallic state. This work indicates the potential application of Sr<sub>2</sub>RuO<sub>4</sub> monolayer in low-dimensional spintrnic devices, and provides a reference for the development of perovskite-based 2D ferromagnets and the realization of controlling 2D magnetism by electric field.

Distinguishing Different Hydrogen-Bonded Helices in Proteins by Efficient 1H-Detected Three-Dimensional Solid-State NMR.

Helical structures in proteins include not only α-helices but also 310 and π helices. These secondary structures differ in the registry of the C═O···H-N hydrogen bonds, which are i to i + 4 for α-helices, i to i + 3 for 310 helices, and i to i + 5 for π-helices. The standard NMR observable of protein secondary structures are chemical shifts, which are, however, insensitive to the precise type of helices. Here, we introduce a three-dimensional (3D) 1H-detected experiment that measures and assigns CO-HN cross-peaks to distinguish the different types of hydrogen-bonded helices. This hCOhNH experiment combines efficient cross-polarization from CO to HN with 13C, 15N, and 1H chemical shift correlation to detect the relative proximities of the COi-Hi+jN spin pairs. We demonstrate this experiment on the membrane-bound transmembrane domain of the SARS-CoV-2 envelope (E) protein (ETM). We show that the C-terminal five residues of ETM form a 310-helix, whereas the rest of the transmembrane domain have COi-Hi+4N hydrogen bonds that are characteristic of α-helices. This result confirms the recent high-resolution solid-state NMR structure of the open state of ETM, which was solved in the absence of explicit hydrogen-bonding restraints. This C-terminal 310 helix may facilitate proton and calcium conduction across the hydrophobic gate of the channel. This hCOhNH experiment is generally applicable and can be used to distinguish not only different types of helices but also different types of β-strands and other hydrogen-bonded conformations in proteins.

Spin-polarized pairing induced by the magnetic field in the Bernal bilayer graphene

Recent experimental findings have demonstrated the occurrence of superconductivity in Bernal bilayer graphene when induced by a magnetic field. In this study, we conduct a theoretical investigation of the potential pairing symmetry within this superconducting system. By developing a theoretical model, we primarily calculate the free energy of the system with p + ip-wave parallel spin pairing, p + ip-wave anti-parallel spin pairing and d + id-wave pairing symmetry. Our results confirm that the magnetic field is indeed essential for generating the superconductivity. We discover that the p + ip-wave parallel spin pairing leads to a lower free energy for the system. The numerical calculations of the energy band structure, zero-energy spectral function and density of states for each of the three pairing symmetries under consideration show a strong consistency with the free energy results.

Relaxation dynamics of an unlike spin pair system

Relaxation dynamics of an unlike spin pair system

Coherences of Photoinduced Electron Spin Qubit Pair States in Photosystem I.

This publication presents the first comprehensive experimental study of electron spin coherences in photosynthetic reaction center proteins, specifically focusing on photosystem I (PSI). The ultrafast electron transfer in PSI generates spin-correlated radical pairs (SCRPs), which are entangled spin pairs formed in well-defined spin states (Bell states). Since their discovery in our group in the 1980s, SCRPs have been extensively used to enhance our understanding of structure-function relationships in photosynthetic proteins. More recently, SCRPs have been utilized as tools for quantum sensing. Electron spin decoherence poses a significant challenge in realizing practical applications of electron spin qubits, particularly the creation of quantum entanglement between multiple electron spins. This work is focused on the systematic characterization of decoherence in SCRPs of PSI. These decoherence times were measured as electron spin echo decay times, termed phase memory times (TM), at various temperatures. Decoherence was recorded on both transient SCRP states P700+A1- and thermalized states. Our study reveals that TM exhibits minimal dependence on the biological species, biochemical treatment, and paramagnetic species. The analysis indicates that nuclear spin diffusion and instantaneous diffusion mechanisms alone cannot explain the observed decoherence. As a plausible explanation we discuss the assumption that the low-temperature dynamics of methyl groups in the protein surrounding the unpaired electron spin centers is the main factor governing the loss of the spin coherence in PSI.

Quantum Phase Transition in Magnetic Nanographenes on a Lead Superconductor.

Quantum spins, also known as spin operators that preserve SU(2) symmetry, lack a specific orientation in space and are hypothesized to display unique interactions with superconductivity. However, spin-orbit coupling and crystal field typically cause a significant magnetic anisotropy in d/f shell spins on surfaces. Here, we fabricate atomically precise S = 1/2 magnetic nanographenes on Pb(111) through engineering sublattice imbalance in the graphene honeycomb lattice. Through tuning the magnetic exchange strength between the unpaired spin and Cooper pairs, a quantum phase transition from the singlet to the doublet state has been observed, consistent with the quantum spin models. From our calculations, the particle-hole asymmetry is induced by the Coulomb scattering potential and gives a transition point about kBTk ≈ 1.6Δ. Our work demonstrates that delocalized π electron magnetism hosts highly tunable magnetic bound states, which can be further developed to study the Majorana bound states and other rich quantum phases of low-dimensional quantum spins on superconductors.

Systematic determination of coupling constants in spin clusters from broken-symmetry mean-field solutions.

Quantum-chemical calculations aimed at deriving magnetic coupling constants in exchange-coupled spin clusters commonly utilize a broken-symmetry (BS) approach. This involves calculating several distinct collinear spin configurations, predominantly by density-functional theory. The energies of these configurations are interpreted in terms of the Heisenberg model, H̃=∑i<jJijs̃i⋅s̃j, to determine coupling constants Jij for spin pairs. However, this energy-based procedure has inherent limitations, primarily in its inability to provide information on isotropic spin interactions beyond those included in the Heisenberg model. Biquadratic exchange or multi-center terms, for example, are usually inaccessible and hence assumed to be negligible. The present work introduces a novel approach employing BS mean-field solutions, specifically Hartree-Fock wave functions, for the construction of effective spin Hamiltonians. This expanded method facilitates the extraction of a broader range of coupling parameters by considering not only the energies, but also Hamiltonian and overlap elements between different BS states. We demonstrate how comprehensive s=12 Hamiltonians, including multi-center terms, can be straightforwardly constructed from a complete set of BS solutions. The approach is exemplified for small clusters within the context of the half-filled single-band Hubbard model. This allows to contrast the current strategy against exact results, thereby offering an enriched understanding of the spin-Hamiltonian construction from BS solutions.

Tetrafluorenofulvalene as a sterically frustrated open-shell alkene

Electronic and steric effects are known to greatly influence the structure, characteristics and reactivity of organic compounds. A typical π bond is weakened by oxidation (corresponding to the removal of electrons from bonding orbitals), by reduction (through addition of electrons to antibonding orbitals) and by unpairing of the bonding electrons, such as in the triplet state. Here we describe tetrafluorenofulvalene (TFF), a twisted, open-shell alkene for which these general rules do not hold. Through the synthesis, experimental characterization and computational analysis of its charged species spanning seven redox states, the central alkene bond in TFF is shown to become substantially stronger in the tri- and tetraanion, generated by chemical reduction. Furthermore, although its triplet state contains a weaker alkene bond than the singlet, in the quintet state its bond order increases substantially, yielding a flatter structure. This behaviour originates from the doubly bifurcated topology of the underlying spin system and can be rationalized by the balancing effects of benzenoid aromaticity and spin pairing.

Controlling Intramolecular Singlet Fission Dynamics via Torsional Modulation of Through-Bond versus Through-Space Couplings.

Covalent dimers, particularly pentacenes, are the dominant platform for developing a mechanistic understanding of intramolecular singlet fission (iSF). Numerous studies have demonstrated that a photoexcited singlet state in these structures can rapidly and efficiently undergo exciton multiplication to form a correlated pair of triplets within a single molecule, with potential applications from photovoltaics to quantum information science. One of the most significant barriers limiting such dimers is the fast recombination of the triplet pair, which prevents spatial separation and the formation of long-lived triplet states. There is an ever-growing need to develop general synthetic strategies to control the evolution of triplets following iSF and enhance their lifetime. Here, we rationally tune the dihedral angle and interchromophore separation between pairs of pentacenes in a systematic series of bridging units to facilitate triplet separation. Through a combination of transient optical and spin-resonance techniques, we demonstrate that torsion within the linker provides a simple synthetic handle to tune the fine balance between through-bond and through-space interchromophore couplings that steer iSF. We show that the full iSF pathway from femtosecond to microsecond timescales is tuned through the static coupling set by molecular design and structural fluctuations that can be biased through steric control. Our approach highlights a straightforward design principle to generate paramagnetic spin pair states with higher yields.

Zero- to low-field relaxometry of chemical and biological fluids

Nuclear magnetic resonance (NMR) relaxometry is an analytical method that provides information about molecular environments, even for NMR “silent” molecules (spin-0), by analyzing the properties of NMR signals versus the magnitude of the longitudinal field. Conventionally, this technique is performed at fields much higher than Earth’s magnetic field, but our work focuses on NMR relaxometry at zero and ultra-low magnetic fields (ZULFs). Operating under such conditions allows us to investigate slow (bio)chemical processes occurring on a timescale from milliseconds to seconds, which coincide with spin evolution. ZULFs also minimize T2 line broadening in heterogeneous samples resulting from magnetic susceptibility. Here, we use ZULF NMR relaxometry to analyze (bio)chemical compounds containing 1H-13C, 1H-15N, and 1H-31P spin pairs. We also detected high-quality ULF NMR spectra of human whole-blood at 0.8 μT, despite a shortening of spin relaxation by blood proteomes (e.g., hemoglobin). Information on proton relaxation times of blood, a potential early biomarker of inflammation, can be acquired in under a minute using inexpensive, portable/small-size NMR spectrometers based on atomic magnetometers.

Resonant Mixing Dynamic Nuclear Polarization.

We propose a mechanism for dynamic nuclear polarization that is different from the well-known Overhauser effect, solid effect, cross effect, and thermal mixing processes. We term it Resonant Mixing (RM), and we show that it arises from the evolution of the density matrix for a simple electron-nucleus coupled spin pair subject to weak microwave irradiation, the same interactions as the solid effect. However, the SE is optimal when the microwave field is off-resonance, whereas RM is optimal when the microwave field is on-resonance and involves the mixing of states by the microwave field together with the electron-nuclear coupling. Finally, we argue that this mechanism is responsible for the observed dispersive-shaped DNP field profile for trityl samples near the electron paramagnetic resonance center.

Primary amines as ligands and linkers in complexes of tripyrrindione radicals

Biopyrrin pigments, which result from the degradation of heme in biological settings, feature three or two pyrrole rings and characteristic pyrrolin-2-one termini. These scaffolds serve as redox-active ligands and electron reservoirs in coordination compounds. Tripyrrin-1,14-dione coordinates divalent transition metals as a dianionic ligand hosting a delocalized radical. Herein, we report the synthesis and characterization of palladium(II) and platinum(II) tripyrrindione complexes featuring a primary amine (i.e., aniline, tert-butylamine, 1,2-ethylenediamine) at the fourth coordination site within square planar geometries. Interligand hydrogen-bonding interactions are observed between the coordinated amine and the carbonyl groups on the tripyrrindione scaffold. Notably, 1,2-ethylenediamine is employed to link two Pt(II) tripyrrindione complexes. As revealed by optical absorption and electron paramagnetic resonance (EPR) spectroscopy, all resulting complexes present ligand-based radicals that are stable at room temperature and when exposed to air. Spin pairing through multicenter interactions leads to [Formula: see text]-dimerization of the tripyrrindione radicals and a decrease in the EPR signal at low temperatures. Electrochemical measurements indicate that the ligand system undergoes quasi-reversible one-electron oxidation and reduction, thus confirming the ability of tripyrrindione to form square planar complexes in three different redox states.

High-fidelity direct contrast synthesis from magnetic resonance fingerprinting.

This work was aimed at proposing a supervised learning-based method that directly synthesizes contrast-weighted images from the Magnetic Resonance Fingerprinting (MRF) data without performing quantitative mapping and spin-dynamics simulations. To implement our direct contrast synthesis (DCS) method, we deploy a conditional generative adversarial network (GAN) framework with a multi-branch U-Net as the generator and a multilayer CNN (PatchGAN) as the discriminator. We refer to our proposed approach as N-DCSNet. The input MRF data are used to directly synthesize T1-weighted, T2-weighted, and fluid-attenuated inversion recovery (FLAIR) images through supervised training on paired MRF and target spin echo-based contrast-weighted scans. The performance of our proposed method is demonstrated on in vivo MRF scans from healthy volunteers. Quantitative metrics, including normalized root mean square error (nRMSE), peak signal-to-noise ratio (PSNR), structural similarity (SSIM), learned perceptual image patch similarity (LPIPS), and Fréchet inception distance (FID), were used to evaluate the performance of the proposed method and compare it with others. In-vivo experiments demonstrated excellent image quality with respect to that of simulation-based contrast synthesis and previous DCS methods, both visually and according to quantitative metrics. We also demonstrate cases in which our trained model is able to mitigate the in-flow and spiral off-resonance artifacts typically seen in MRF reconstructions, and thus more faithfully represent conventional spin echo-based contrast-weighted images. We present N-DCSNet to directly synthesize high-fidelity multicontrast MR images from a single MRF acquisition. This method can significantly decrease examination time. By directly training a network to generate contrast-weighted images, our method does not require any model-based simulation and therefore can avoid reconstruction errors due to dictionary matching and contrast simulation (code available at:https://github.com/mikgroup/DCSNet).