Phase Memory Time Research Articles

Protein-Protein Interaction and Conformational Change in the Alpha-Helical Membrane Transporter BtuCD-F in the Native Cellular Envelope.

Alpha-helical membrane proteins perform numerous critical functions essential for the survival of living organisms. Traditionally, these proteins are extracted from membranes using detergent solubilization and reconstitution into liposomes or nanodiscs. However, these processes often obscure the effects of nanoconfinement and the native environment on the structure and conformational heterogeneity of the target protein. We demonstrate that pulsed dipolar electron spin resonance spectroscopy, combined with the Gd3+-nitroxide spin pair, enables the selective observation of the vitamin B12 importer BtuCD-F in its native cellular envelope. Despite the high levels of non-specific labeling in the envelope, this orthogonal approach combined with the long phase-memory time for the Gd3+ spin enables the observation of the target protein complex at a few micromolar concentrations with high resolution. In the native envelope, vitamin B12 induces a distinct conformational shift at the BtuCD-BtuF interface, which is not observed in the micelles. This approach offers a general strategy for investigating protein-protein and protein-ligand/drug interactions and conformational changes of the alpha-helical membrane proteins in their native envelope context.

Unlocking the potential of photoexcited molecular electron spins for room temperature quantum information processing

Abstract Future information processing technologies like quantum memory devices have the potential to store and transfer quantum states to enable quantum computing and networking. A central consideration in practical applications for such devices is the nature of the light-matter interface which determines the storage state density and efficiency. Here, we employ an organic radical, α,γ-bisdiphenylene-β-phenylallyl doped into an o-terphenyl host to explore the potential for using tuneable and high-performance molecular media in microwave-based quantum applications. We demonstrate that this radical system exhibits millisecond-long spin-lattice relaxation and microsecond-long phase memory times at room temperature, while also having the capability to generate an oscillating spin-polarized state using a co-dissolved photo-activated tetraphenylporphyrin moiety, all enabled by using a viscous liquid host. This latest system builds upon collective wisdom from previous molecules-for-quantum literature by combining careful host matrix selection, with dynamical decoupling, and photoexcited triplet-radical spin polarisation to realise a versatile and robust quantum spin medium.

Investigation of slow magnetic relaxation in a series of 1D polymeric cyclobutane-1,1-dicarboxylates based on LnIIIVIV2 units (LnIII = Tb, Dy, Ho, Er, Tm, Yb): rare examples of VIV-4f single-molecule magnets.

The reactions of VOSO4·3H2O with Na2(cbdc) (cbdc2- - dianion of cyclobutane-1,1-dicarboxylic acid) and lanthanide(III) nitrates taken in a molar ratio of 1 : 2 : 1 were found to yield a series of isostructural heterometallic compounds [NaLn(VO)2(cbdc)4(H2O)10]n (1Ln, Ln = Tb, Dy, Ho, Er, Tm, Yb). These compounds are constructed from trinuclear anionic units [Ln(VO)2(cbdc)4(H2O)8]- ({LnV2}-) linked by Na+ ions into 1D polymeric chains. The crystal structures of 1Dy and 1Er were determined by single-crystal X-ray diffraction (XRD), and their isostructurality with 1Tb, 1Ho, 1Tm, and 1Yb was proved by powder X-ray diffraction (PXRD). According to alternating current (ac) magnetic susceptibility measurements, 1Dy, 1Er, and 1Yb exhibited field-induced slow relaxation of magnetization. Compound 1Er is the first representative of ErIII-VIV single-molecule magnets. Measuring the temperature dependences of the phase memory time (Tm) for 1Dy and 1Yb using pulsed EPR spectroscopy allowed us to observe the phenomenon of phase relaxation enhancement (PRE) at temperatures below 30 K. In future, this phenomenon may contribute to the evaluation of relaxation times of the lanthanide ions.

Room-Temperature Quantum Coherence of Reversible Photo-Generated Radical and its Film.

Electron spin qubits are becoming an important research direction in the field of quantum computing and information storage. However, the quantum decoherence has seriously hindered the development of this field. So far, few qubits exhibit long phase memory time (Tm), and even fewer qubits that can reach room temperature. Some reports show that the coherence times of radicals are generally long, so radicals may be the preferred spin carriers for qubits. Here, we demonstrate the qubit properties of a photogenerated radical (1 a) based on 2,4,6-Tri(4-pyridyl)-1,3,5-triazine (tpt, 1). More importantly, the photogenerated radical is a spin self-diluting complex, which the dilution is generally used in the investigation of qubits to reduce the interference of environment on qubits in order to overcome the decoherence of qubits. It is surprised that radical tpt has a stable Tm=1.1 μs above 20 K, even keep it to room temperature. In addition, the tpt-film prepared by the vacuum evaporation is significantly increase the T1 and Tm at low temperature.

Luminescent Organic Triplet Diradicals as Optically Addressable Molecular Qubits.

Optical-spin interfaces that enable the photoinitialization, coherent microwave manipulation, and optical read-out of ground state spins have been studied extensively in solid-state defects such as diamond nitrogen vacancy (NV) centers and are promising for quantum information science applications. Molecular quantum bits (qubits) offer many advantages over solid-state spin centers through synthetic control of their optical and spin properties and their scalability into well-defined multiqubit arrays. In this work, we report an optical-spin interface in an organic molecular qubit consisting of two luminescent tris(2,4,6-trichlorophenyl)methyl (TTM) radicals connected via the meta-positions of a phenyl linker. The triplet ground state of this system can be photoinitialized in its |T0⟩ state by shelving triplet populations as singlets through spin-selective excited-state intersystem crossing with 80% selectivity from |T+⟩ and |T-⟩. The fluorescence intensity in the triplet manifold is determined by the ground-state polarization, and we show successful optical read-out of the ground-state spin following microwave manipulations by fluorescence-detected magnetic resonance spectroscopy. At 85 K, the lifetime of the polarized ground state is 45 ± 3 μs, and the ground state phase memory time is Tm = 5.9 ± 0.1 μs, which increases to 26.8 ± 1.6 μs at 5 K. These results show that luminescent diradicals with triplet ground states can serve as optically addressable molecular qubits with long spin coherence times, which marks an important step toward the rational design of spin-optical interfaces in organic materials.

Encapsulated Atomic Hydrogen in Octamethyl-POSS Cages: A Pulsed EPR Study.

Encapsulated atomic hydrogen in polyhedral oligomeric silsesquioxane (POSS) cages is a promising candidate for spin-based quantum technologies. Key parameters such as spin relaxation times and magnetic interactions with surrounding electron and nuclear spins can be typically probed with advanced electron paramagnetic resonance (EPR) methods. Here we present a detailed pulsed EPR study of the species H@Si8O12R8 with R=CH3, namely encapsulated atomic hydrogen in the octamethyl POSS derivative. The temperature dependence of the spin-lattice relaxation rate 1/ is analyzed in terms of a Raman process with a Debye temperature of K and a thermally activated process with (552 cm-1), whereas, the phase memory time shows the typical shortening behaviour at K observed for all methyl-containing derivatives. The hyperfine coupling of the cage Si nuclei is measured by hyperfine sublevel correlation (HYSCORE) spectroscopy and is found to fulfil the so-called "matching condition" at the low-field EPR transition. The potential of this paramagnetic molecule to perform one-qubit quantum operations is probed by room-temperature Rabi oscillations.

Ligand Effects on the Spin Relaxation Dynamics and Coherent Manipulation of Organometallic La(II) Potential Qudits.

We present pulsed electron paramagnetic resonance (EPR) studies on three La(II) complexes, [K(2.2.2-cryptand)][La(Cp')3] (1), [K(2.2.2-cryptand)][La(Cp″)3] (2), and [K(2.2.2-cryptand)][La(Cptt)3] (3), which feature cyclopentadienyl derivatives as ligands [Cp' = C5H4SiMe3; Cp″ = C5H3(SiMe3)2; Cptt = C5H3(CMe3)2] and display a C3 symmetry. Long spin-lattice relaxation (T1) and phase memory (Tm) times are observed for all three compounds, but with significant variation in T1 among 1-3, with 3 being the slowest relaxing due to higher s-character of the SOMO. The dephasing times can be extended by more than an order of magnitude via dynamical decoupling experiments using a Carr-Purcell-Meiboom-Gill (CPMG) sequence, reaching 161 μs (5 K) for 3. Coherent spin manipulation is performed by the observation of Rabi quantum oscillations up to 80 K in this nuclear spin-rich environment (1H, 13C, and 29Si). The high nuclear spin of 139La (I = 7/2), and the ability to coherently manipulate all eight hyperfine transitions, makes these molecules promising candidates for application as qudits (multilevel quantum systems featuring d quantum states; d >2) for performing quantum operations within a single molecule. Application of HYSCORE techniques allows us to quantify the electron spin density at ligand nuclei and interrogate the role of functional groups to the electron spin relaxation properties.

Spin qubits of Cu(II) doped in Zn(II) metal-organic frameworks above microsecond phase memory time.

With the aim of creating Cu(II) spin qubits in a rigid metal-organic framework (MOF), this work demonstrates a doping of 5 %, 2 %, 1 %, and 0.1 % mol of Cu(II) ions into a perovskite-type MOF [CH6 N3 ][ZnII (HCOO)3 ]. The presence of dopant Cu(II) sites are confirmed with anisotropic g-factors (gx =2.07, gy =2.12, and gz =2.44) in the S=1/2 system by experimentally and theoretically. Magnetic dynamics indicate the occurrence of a slow magnetic relaxation via the direct and Raman processes under an applied field, with a relaxation time (τ) of 3.5 ms (5 % Cu), 9.2 ms (2 % Cu), and 15 ms (1 % Cu) at 1.8 K. Furthermore, pulse-ESR spectroscopy reveals spin qubit properties with a spin-spin relaxation (phase memory) time (T2 ) of 0.21 μs (2 %Cu), 0.39 μs (1 %Cu), and 3.0 μs (0.1 %Cu) at 10 K as well as Rabi oscillation between MS =±1/2 spin sublevels. T2 above microsecond is achieved for the first time in the Cu(II)-doped MOFs. It can be observed at submicrosecond around 50 K. These spin relaxations are very sensitive to the magnetic dipole interactions relating with cross-relaxation between the Cu(II) sites and can be tuned by adjusting the dopant concentration.

Probing decoherence in molecular 4f qubits.

We probe herein the fundamental factors that induce decoherence in ensembles of molecular magnetic materials. This is done by pulse Electron Paramagnetic Resonance measurements at X-band (∼9.6 GHz) on single crystals of Gd@Y(trensal) at 0.5, 10-1, 10-2 and 10-3% doping levels, using Hahn echo, partial refocusing and CPMG sequences. The phase memory time, T m, obtained by the Hahn echo sequence at X-band is compared to the one previously determined at higher frequency/magnetic field (∼240 GHz). The combined information from these experiments allows to gain insight into the contributions to decoherence originating from various relaxation mechanisms such as spin-lattice relaxation, electron and nuclear spin diffusion and instantaneous diffusion. We show that while at high magnetic fields T m is limited by spin-lattice relaxation seemingly attributed to a direct process, at lower fields the limiting factor is spectral diffusion. At X-band, for Gd@Y(trensal) we determine a T m in the range 1-12 μs, at 5 K, depending on the magnetic field and concentration of Gd(trensal) in the isostructural diamagnetic host Y(trensal). Importantly, Gd@Y(trensal) displays measurable coherence at temperatures above liquid nitrogen ones, with 125 K being the upper limit. At the lowest dilution level of 10-3% and under dynamic decoupling conditions, the ratio of T m versus the time it takes to implement a quantum gate, T G, reaches the order of 104, in the example of a single qubit π-rotation, which corresponds to an upper limit of gate fidelity of the order of 99.99%, reaching thus the lower limit of qubit figure of merit required for implementations in quantum information technologies.

Spin labels for 19F ENDOR distance determination: resolution, sensitivity and distance predictability.

19F electron-nuclear double resonance (ENDOR) has emerged as an attractive method for determining distance distributions in biomolecules in the range of 0.7-2 nm, which is not easily accessible by pulsed electron dipolar spectroscopy. The 19F ENDOR approach relies on spin labeling, and in this work, we compare various labels' performance. Four protein variants of GB1 and ubiquitin bearing fluorinated residues were labeled at the same site with nitroxide and trityl radicals and a Gd(III) chelate. Additionally, a double-histidine variant of GB1 was labeled with a Cu(II) nitrilotriacetic acid chelate. ENDOR measurements were carried out at W-band (95 GHz) where 19F signals are well separated from 1H signals. Differences in sensitivity were observed, with Gd(III) chelates providing the highest signal-to-noise ratio. The new trityl label, OXMA, devoid of methyl groups, exhibited a sufficiently long phase memory time to provide an acceptable sensitivity. However, the longer tether of this label effectively reduces the maximum accessible distance between the 19F and the Cα of the spin-labeling site. The nitroxide and Cu(II) labels provide valuable additional geometric insights via orientation selection. Prediction of electron-nuclear distances based on the known structures of the proteins were the closest to the experimental values for Gd(III) labels, and distances obtained for Cu(II) labeled GB1 are in good agreement with previously published NMR results. Overall, our results offer valuable guidance for selecting optimal spin labels for 19F ENDOR distance measurement in proteins.

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.

A nitroxide-containing cathode material for organic radical batteries studied with pulsed EPR spectroscopy

An electron spin echo in a nitroxide-containing polymer cathode film for organic radical batteries is observed for various states of charge at cryogenic temperatures. The EPR-detected state of charge (ESOC), as inferred from the number of paramagnetic centers in the film, is compared to the results of Coulomb counting based on galvanostatic charging. Spin concentration, longitudinal relaxation times T1 and phase memory times Tm strongly correlate with the ESOC. In the discharged film, the spin concentration reaches 5±3×1020 cm−3, causing a phase memory time Tm≪ 100 ns (shorter than the resonator ring-down time) that hinders the detection of the spin echo. In the charged film, the decreased spin concentration results in a longer Tm between 100 ns and 300 ns that enables spin-echo detection, yet limits the length of the microwave pulse sequence. The short, broad-band pulses cause instantaneous diffusion in the unoxidized domains across the oxidized film, affecting the relative peak intensities in the pulsed EPR spectrum. By simulating the spectral distortion caused by instantaneous diffusion, we obtain information on the local spin concentration, which complements the information on the ‘bulk’ spin concentration determined by electrochemistry and continuous-wave EPR spectroscopy.

Electron paramagnetic resonance spectroscopic characterization of the human KCNE3 protein in lipodisq nanoparticles for structural dynamics of membrane proteins

One of the major challenges in solubilization of membrane proteins is to find the optimal physiological environment for their biophysical studies. EPR spectroscopy is a powerful biophysical technique for studying the structural and dynamic properties of macromolecules. However, the challenges in the membrane protein sample preparation and flexible motion of the spin label limit the utilization of EPR spectroscopy to a majority of membrane protein systems in a physiological membrane-bound state. Recently, lipodisq nanoparticles or styrene-maleic acid copolymer-lipid nanoparticles (SMALPs) have emerged as a membrane mimetic system for investigating the structural studies of membrane proteins. However, its detail characterization for membrane protein studies is still poorly understood. Recently, we characterized the potassium channel membrane protein KCNQ1 voltage sensing domain (KCNQ1-VSD) and KCNE1 reconstituted into lipodisq nanoparticles using EPR spectroscopy. In this study, the potassium channel accessory protein KCNE3 containing flexible N- and C-termini was encapsulated into proteoliposomes and lipodisq nanoparticles and characterized for studying its structural and dynamic properties using nitroxide based site-directed spin labeling EPR spectroscopy. CW-EPR lineshape analysis data indicated an increase in spectral line broadenings with the addition of the styrene-maleic acid (SMA) polymer which approaches close to the rigid limit providing a homogeneous stabilization of the protein-lipid complex. Similarly, EPR DEER measurements indicated an enhanced quality of distance measurements with an increase in the phase memory time (Tm) values upon incorporation of the sample into lipodisq nanoparticles, when compared to proteoliposomes. These results agree with the solution NMR structural structure of the KCNE3 and EPR studies of other membrane proteins in lipodisq nanoparticles. This study along with our earlier studies will provide the reference characterization data that will provide benefit to the membrane protein researchers for studying structural dynamics of challenging membrane proteins.

Dipolar-Coupled Entangled Molecular 4f Qubits.

We demonstrate by use of continuous wave- and pulse-electron paramagnetic resonance spectroscopy on oriented single crystals of magnetically dilute YbIII ions in Yb0.01Lu0.99(trensal) that molecular entangled two-qubit systems can be constructed by exploiting dipolar interactions between neighboring YbIII centers. Furthermore, we show that the phase memory time and Rabi frequencies of these dipolar-interaction-coupled entangled two-qubit systems are comparable to the ones of the corresponding single qubits.

A ring of rotaxanes: studies of a large paramagnetic assembly in solution.

Here we report the synthesis and structural characterization of four [7]rotaxanes formed by coordinating hybrid inorganic-organic [2]rotaxanes to a central {Ni12} core. X-ray single crystal diffraction demonstrate that [7]rotaxanes are formed, with a range of conformations in the crystal. Small angle X-ray scattering supported by molecular dynamic simulations demonstrates that the large molecules are stable in solution and also show that the conformers present in solution are not those found in the crystal. Pulsed EPR spectroscopy show that phase memory times for the {Cr7Ni} rings, which have been proposed as qubits, are reduced but not dramatically by the presence of the {Ni12} cage.

Towards Luminescent Vanadium(II) Complexes with Slow Magnetic Relaxation and Quantum Coherence.

Molecular entities with doublet or triplet ground states find increasing interest as potential molecular quantum bits (qubits). Complexes with higher multiplicity might even function as qudits and serve to encode further quantum bits. Vanadium(II) ions in octahedral ligand fields with quartet ground states and small zero-field splittings qualify as qubits with optical read out thanks to potentially luminescent spin-flip states. We identified two V2+ complexes [V(ddpd)2 ]2+ with the strong field ligand N,N'-dimethyl-N,N'-dipyridine-2-yl-pyridine-2,6-diamine (ddpd) in two isomeric forms (cis-fac and mer) as suitable candidates. The energy gaps between the two lowest Kramers doublets amount to 0.2 and 0.5 cm-1 allowing pulsed EPR experiments at conventional Q-band frequencies (35 GHz). Both isomers possess spin-lattice relaxation times T1 of around 300 μs and a phase memory time TM of around 1 μs at 5 K. Furthermore, the mer isomer displays slow magnetic relaxation in an applied field of 400 mT. While the vanadium(III) complexes [V(ddpd)2 ]3+ are emissive in the near-IR-II region, the [V(ddpd)2 ]2+ complexes are non-luminescent due to metal-to-ligand charge transfer admixture to the spin-flip states.

Spin-Lattice Relaxation Decoherence Suppression in Vanishing Orbital Angular Momentum Qubits.

Multifrequency electron paramagnetic resonance spectroscopy on oriented single crystals of magnetically dilute Gd(III) ions in Gd0.004Y0.996(trensal) is used to determine the Hamiltonian parameters of the ground 8S7/2 term and its phase memory time, Tm, characterizing its coherent spin dynamics. The vanishing orbital angular momentum of the 8S7/2 term makes it relatively insensitive to spin-lattice relaxation mediated by magnetoelastic coupling and leads to a Tm of 12 μs at 3 K, which is not limited by spin-lattice relaxation.

Mechanism of Electron Spin Decoherence in a Partially Deuterated Glassy Matrix.

Long electron spin coherence lifetimes are essential for applications in quantum information science and electron paramagnetic resonance, for instance, for nanoscale distance measurements in biomolecular systems using double electron-electron resonance. We experimentally investigate the decoherence dynamics under the Hahn echo sequence of the organic radical d18-TEMPO in a variably deuterated frozen water:glycerol matrix. The coherence time (phase memory time) TM scales with proton concentration as [1H]-0.65. For selectively deuterated matrices, decoherence is accelerated in the presence of proton clustering, that is, substantial short-range density in the proton-proton radial distribution functions (<3 Å). Simulations using molecular dynamics and many-body spin quantum dynamics show excellent agreement with experiment and show that geminal proton pairs such as CH2 and OH2 groups are major decoherence drivers. This provides a predictive tool for designing molecular systems with long electron spin coherence times.

A New Nitronyl‐Nitroxide Ligand for Designing Binuclear LnIII Complexes: Syntheses, Crystal Structures, Magnetic and EPR Studies

AbstractA new nitronyl‐nitroxide ligand (H2L) featuring alcoholic and phenolic groups has been synthesised starting from 2‐hydroxy‐3‐(hydroxymethyl)‐5‐methylbenzaldehyde (A). Using this ligand, three 2p–4 f binuclear complexes have been obtained and crystallographically characterized: [Ln2(HL)2(hfac)4], (Ln=Gd 1, Tb 2, Dy 3). Apart from the desired compounds, two by‐products have been isolated as a molecular alloy containing an intermediate bearing hydroxylamino and N‐oxide groups, i. e. (1‐hydroxy‐2‐(2‐hydroxy‐3‐(hydroxymethyl)‐5‐methylphenyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazole 3‐oxide, B, and the imino‐nitroxide derivative, C. This system was characterized by single crystal X‐ray diffraction, UV‐VIS and EPR spectroscopy. During the synthesis of compounds 1–3, two other complexes have been obtained and characterized: [Ln(C)(hfac)3] (4, Ln=Tb) and [Ln2(A−H)2(hfac)4] (5, Ln=Tb), where (A−H) results from the deprotonation of the phenolic group in A. The synthetic procedure was optimized in order to obtain pure 1–3 complexes. The cryomagnetic properties of compounds 1–3 have been investigated. Continuous‐wave (CW) electron paramagnetic resonance (EPR) measurements were carried out at X‐ and Q‐band for compound 1. Time‐dependent experiments were performed at three magnetic fields. Phase memory times, Tm, were found to be about 1000 ns at 6 K.

Singly and Triply Linked Magnetic Porphyrin Lanthanide Arrays.

The introduction of paramagnetic metal centers into a conjugated π-system is a promising approach toward engineering spintronic materials. Here, we report an investigation of two types of spin-bearing dysprosium(III) and gadolinium(III) porphyrin dimers: singly meso–meso-linked dimers with twisted conformations and planar edge-fused β,meso,β-linked tapes. The rare-earth spin centers sit out of the plane of the porphyrin, so that the singly linked dimers are chiral, and their enantiomers can be resolved, whereas the edge-fused tape complexes can be separated into syn and anti stereoisomers. We compare the crystal structures, UV–vis–NIR absorption spectra, electrochemistry, EPR spectroscopy, and magnetic behavior of these complexes. Low-temperature SQUID magnetometry measurements reveal intramolecular antiferromagnetic exchange coupling between the GdIII centers in the edge-fused dimers (syn isomer: J = −51 ± 2 MHz; anti isomer: J = −19 ± 3 MHz), whereas no exchange coupling is detected in the singly linked twisted complex. The phase-memory times, Tm, are in the range of 8–10 μs at 3 K, which is long enough to test quantum computational schemes using microwave pulses. Both the syn and anti Dy2 edge-fused tapes exhibit single-molecule magnetic hysteresis cycles at temperatures below 0.5 K with slow magnetization dynamics.