Relaxation Rate Research Articles

In English

The paper considers the problem of choosing the composition, structure, and size of spherical catalyst nanoparticles for carrying out plasmon-induced polymerization reactions. The concept of reducing the activation energy of the reaction in the presence of a catalyst and, accordingly, increasing the rate of a chemical reaction during heating due to the excitation of surface plasmon resonance is presented. Using the Drude model for the dielectric function, relationships were obtained for the frequency dependences of such characteristics as the real and imaginary parts of the polarizability, heating and the rate of chemical reactions when monometallic and bimetallic nanoparticles are used as catalysts, as well as the amplification of fields in their vicinity. The concepts developed in this work take into account the classical size dependence of the effective electron relaxation rate in monometallic and bimetallic nanoparticles under the assumption of diffuse scattering of electrons. Changes in the positions of the maxima of the imaginary part of the polarizability, heating, and reaction rate are analyzed with a change in the radii of monometallic and bimetallic nanoparticles. It is shown that the maxima of the dependences under study correspond to dipole surface plasmon resonances, and their number depends on the particle morphology. Changes in the amplification of electric fields in the vicinity of nanoparticles of different morphology have been studied. It has been found that the enhancement of the fields in all considered cases is maximum on the surface of the nanoparticle and decreases with distance from it. Practical recommendations are formulated regarding the size, composition and structure of nanoparticles for plasmon catalysis, which provide the highest rates of chemical reactions. Thus, all obtained frequency dependences have one maximum for monometallic and two maxima for bimetallic nanoparticles.

Mapping vascular network architecture in primate brain using ferumoxytol-weighted laminar MRI.

Mapping the vascular organization of the brain is of great importance across various domains of basic neuroimaging research, diagnostic radiology, and neurology. However, the intricate task of precisely mapping vasculature across brain regions and cortical layers presents formidable challenges, resulting in a limited understanding of neurometabolic factors influencing the brain's microvasculature. Addressing this gap, our study investigates whole-brain vascular volume using ferumoxytol-weighted laminar-resolution multi-echo gradient-echo imaging in macaque monkeys. We validate the results with published data for vascular densities and compare them with cytoarchitecture, neuron and synaptic densities. The ferumoxytol-induced change in transverse relaxation rate (ΔR2*), an indirect proxy measure of cerebral blood volume (CBV), was mapped onto twelve equivolumetric laminar cortical surfaces. Our findings reveal that CBV varies 3-fold across the brain, with the highest vascular volume observed in the inferior colliculus and lowest in the corpus callosum. In the cerebral cortex, CBV is notably high in early primary sensory areas and low in association areas responsible for higher cognitive functions. Classification of CBV into distinct groups unveils extensive replication of translaminar vascular network motifs, suggesting distinct computational energy supply requirements in areas with varying cytoarchitecture types. Regionally, baseline R2* and CBV exhibit positive correlations with neuron density and negative correlations with receptor densities. Adjusting image resolution based on the critical sampling frequency of penetrating cortical vessels, allows us to delineate approximately 30% of the arterial-venous vessels. Collectively, these results mark significant methodological and conceptual advancements, contributing to the refinement of cerebrovascular MRI. Furthermore, our study establishes a linkage between neurometabolic factors and the vascular network architecture in the primate brain.

Random singlet-like state in the dimer-based triangular antiferromagnet Ba6Y2Rh2Ti2O17−δ

We present the magnetic, thermodynamic, and muon spin relaxation (μSR) results of the dimer-based triangular antiferromagnet Ba6Y2Rh2Ti2O17−δ. The magnetic susceptibility data show the sub-Curie-Weiss behavior χ(T)∝T−αχ below 100 K, suggesting random magnetism. The isothermal magnetization results reveal the presence of weakly interacting structural orphan spins about 6.1% at 2 K, arising from the oxygen deficiency. The comprehensive μSR experiments exhibit the coexisting relaxing and nonrelaxing components along with the thermally activated behavior in the muon spin relaxation rate, reflecting the fluctuating orphan spins in the dimer singlet background. In addition, we observe the scaling behavior of M(H,T) in H/T and Pz(t) in t/HLF with the scaling exponents αχ=αM=0.75 and αμ=0.72, respectively, but not for the magnetic specific heat data. The failure of the scaling relation in Cm(H,T)/T implies low-energy excitations dressed by the conventional orphan spins. Based on these observations, we find that the magnetic ground state resembles random singlets and discuss the possible configurations of the spin dimer unit Rh2O9. Our results shed light on the role of quenched disorder in the dimer-based frustrated magnets. Published by the American Physical Society 2024

Impaired performance of rapid grip in people with Parkinson's disease and motor segmentation

Bradykinesia, or slow movement, is a defining symptom of Parkinson's disease (PD), but the underlying neuromechanical deficits that lead to this slowness remain unclear. People with PD often have impaired rates of motor output accompanied by disruptions in neuromuscular excitation, causing abnormal, segmented, force-time curves. Previous investigations using single-joint models indicate that agonist electromyogram (EMG) silent periods cause motor segmentation. It is unknown whether motor segmentation is evident in more anatomically complex and ecologically important tasks, such as handgrip tasks. Aim 1 was to determine how handgrip rates of force change compare between people with PD and healthy young and older adults. Aim 2 was to determine whether motor segmentation is present in handgrip force and EMG measures in people with PD. Subjects performed rapid isometric handgrip pulses to 20–60% of their maximal voluntary contraction force while EMG was collected from the grip flexors and extensors. Dependent variables included the time to 90% peak force, the peak rate of force development, the duration above 90% of peak force, the number of segments in the force-time curve, the number of EMG bursts, time to relaxation from 90% of peak force, and the peak rate of force relaxation. People with PD had longer durations and lower rates of force change than young and older adults. Six of 22 people with PD had motor segmentation. People with PD had more EMG bursts compared to healthy adults and the number of EMG bursts covaried with the number of segments. Thus, control of rapid movement in Parkinson's disease can be studied using isometric handgrip. People with PD have impaired rate control compared to healthy adults and motor segmentation can be studied in handgrip.

Extended measurements and calculations of CH3C14N-N2 rotational lineshape parameters

Spectroscopic parameters of methyl cyanide are of interest for astrophysical applications because of presence of this molecule in planetary atmospheres, comets, and interstellar medium. For radiative-transfer modeling a key role is played by the pressure-induced linewidths which are strongly influenced by the collision partner and the temperature. To complete the extremely scarce experimental data available, rotational lines of room-temperature CH3C14N in collision with molecular nitrogen have been recorded in a very large (180–1400 GHz) frequency range for J = 9 → 10, 12 → 13, 15 → 16, 21 → 22, 27 → 28, 33 → 34, 42 → 43, 48 → 49, 63 → 64, 69 → 70, 75 → 76 and K = 0–15. The high sensitivity of the frequency-modulated spectrometer has enabled observation of clear deviations of the recorded lineshapes from the usual Voigt profile. Their additional analyses performed with advanced non-Voigt models have demonstrated that the observed lineshapes are mainly governed by the speed dependence of relaxation rates and that the optical diffusion related to velocity changing collisions (Dicke effect) has a nearly negligible role. Compared to infrared-region results available in the literature, our Voigt-profile values lie systematically lower by about 0.5 MHz/Torr, which argues in favor of observable vibrational dependence for the CH3CN-N2 system. Line-broadening parameters have been also evaluated by a semi-empirical method based on the Anderson-Tsao-Curnutte theory. The model parameters determined from fits on some selected experimental values confirm the tendences previously stated for the case of vibrotational transitions and allow better theoretical predictions for extended ranges of rotational quantum numbers. Being temperature-independent, these parameters can be directly used in calculations for other temperatures concerned by radiative transfer models.

Muon spin relaxation and emergence of disorder-induced unconventional dynamic magnetic fluctuations in Dy2Zr2O7

The disordered pyrochlore oxide Dy2Zr2O7 shows the signatures of field-induced spin freezing with remnant zero-point spin-ice entropy at 5 kOe magnetic field. We have performed zero-field and longitudinal field Muon spin relaxation (µSR) studies on Dy2Zr2O7. Our zero field studies reveal the absence of both long-range ordering and spin freezing down to 62 mK. The µSR relaxation rate exhibits a temperature-independent plateau below 4 K, indicating a dynamic ground state of fluctuating spins similar to the well-known spin ice system Dy2Ti2O7. The low-temperature spin fluctuations persist in the longitudinal field of 20 kOe as well and show unusual field dependence of the relaxation rate, which is uncommon for a spin-liquid system. Our results, combined with the previous studies do not show any evidence of spin ice or spin glass ground state, rather point to a disorder-induced dynamic magnetic ground state in the Dy2Zr2O7 material.

Fast Field-Cycling Nuclear Magnetic Resonance Relaxometry of Perfluorosulfonic Acid Ionomers and Their Perfluorosulfonyl Fluoride Precursors Membranes.

The spin-lattice relaxation rates (R1) of fluorine nuclei in perfluorosulfonic acid (PFSA) ionomer membranes and their precursor solid perfluorosulfonyl fluoride (PFSF) were measured by fast field-cycling (FFC) NMR relaxometry. The XRD profiles of PFSA and PFSF are similar and show a characteristic peak, indicating the alignment of main chains. While the SAXS profiles of the PFSA membranes show two peaks, those of the solid PFSF lack the ionomer peak which is characteristic of hydrophilic side chains in the PFSA ionomer membranes. The Larmor frequency dependence of R1 obeys power law and the indices are dependent on the sample and temperature. The indices of the PFSA membranes change from -1/2 to -1 along with the Larmor frequency and temperature dependence decrease, which is consistent with the generalized defect diffusion model. Estimated activation energies are in good agreement with those obtained from dynamical mechanical analysis and dielectric spectroscopy, indicating the segmental motion of the backbones as the common origin of these observations. On the other hand, the index changes to -3/4 in the case of the PFSFs, which has been predicted by the reptation model.

Sustainable multi-functional additives: Zinc soaps from vegetable oil and fatty acids in natural rubber compounds

Zinc soaps derived from various vegetable oils and fatty acids were synthesized, and the product with the highest yield was chosen for compounding with silica-filled natural rubber (NR). Specifically, zinc soaps of coconut oil and palm oil, with yields of 72% and 73%, respectively, were prepared through precipitation and metathesis methods. Additionally, zinc soaps from palm fatty acid distillate (PFAD) and stearic acid, both with a yield of 70%, were synthesized using modified fusion and precipitation methods, respectively. Subsequently, these zinc soaps were incorporated into silica-filled NR compounds and compared with the commercial dispersing aid, Ultra flow 700 s. The results indicated that the zinc soaps played a significant role in plasticizing and lubricating the rubber compounds, as evidenced by reductions in Mooney viscosity, Mooney relaxation rate, and minimum torque (ML). Furthermore, the zinc soaps influenced curing properties by accelerating the cure process, as reflected in decreased cure time (tc90) and increased cure rate and torque difference compared to compounds without processing aid. Moreover, NR compounded with zinc soap exhibited superior mechanical properties, including higher tensile strength, elongation at break, tear strength, and hardness.

Dynamic monitoring soft tissue healing via visualized Gd-crosslinked double network MRI microspheres

By integrating magnetic resonance-visible components with scaffold materials, hydrogel microspheres (HMs) become visible under magnetic resonance imaging(MRI), allowing for non-invasive, continuous, and dynamic monitoring of the distribution, degradation, and relationship of the HMs with local tissues. However, when these visualization components are physically blended into the HMs, it reduces their relaxation rate and specificity under MRI, weakening the efficacy of real-time dynamic monitoring. To achieve MRI-guided in vivo monitoring of HMs with tissue repair functionality, we utilized airflow control and photo-crosslinking methods to prepare alginate-gelatin-based dual-network hydrogel microspheres (G-AlgMA HMs) using gadolinium ions (Gd (III)), a paramagnetic MRI contrast agent, as the crosslinker. When the network of G-AlgMA HMs degrades, the cleavage of covalent bonds causes the release of Gd (III), continuously altering the arrangement and movement characteristics of surrounding water molecules. This change in local transverse and longitudinal relaxation times results in variations in MRI signal values, thus enabling MRI-guided in vivo monitoring of the HMs. Additionally, in vivo data show that the degradation and release of polypeptide (K2 (SL)6 K2 (KK)) from G-AlgMA HMs promote local vascular regeneration and soft tissue repair. Overall, G-AlgMA HMs enable non-invasive, dynamic in vivo monitoring of biomaterial degradation and tissue regeneration through MRI, which is significant for understanding material degradation mechanisms, evaluating biocompatibility, and optimizing material design.

Flux creep and flux pinning behavior in Cu-doped FeSe0.4Te0.6 single crystals

This paper presents the preparation and comparative study of the superconducting properties and magnetic flux dynamics of FeSe and Fe1-xCuxTe0.6Se0.4 (x = 0, 0.005, 0.01, 0.015) single crystals, with the aim of investigating the origin of the second peak in FeTe0.6Se0.4. The Cu element significantly suppresses the superconducting transition temperature (Tc) of Fe1-xCuxTe0.6Se0.4 from 14.5 K at x = 0 to 9.23 K at x = 0.015, which is close to the 9 K of FeSe, while also suppressing the second peak effect. Additionally, the critical current density anisotropy (γ) is reduced. Dynamic relaxation rates (Q) indicate a crossover from rapid single-vortex pinning near the second peak to collective pinning, linking fast and slow magnetic flux relaxation with the second peak effect. By comparing the pinning properties of FeSe and Fe1-xCuxTe0.6Se0.4 (x = 0, 0.005, 0.01, 0.015), it is found that the second peak effect is closely related to the transition from δl - pinning to δTc - pinning in Fe1-xCuxSe0.4Te0.6 (x = 0, 0.005, 0.01, 0.015). While surface pinning centers dominate in FeSe, the pinning in Fe1-xCuxSe0.4Te0.6 (x = 0, 0.005, 0.01, 0.015) originates from the interaction between the core and normal centers. Furthermore, the electronic transport properties of the FeSe and Fe1-xCuxSe0.4Te0.6 (x = 0, 0.005, 0.01, 0.015) series are also studied. Te substitution suppresses the nematic transition in FeSe, while Cu substitution suppresses the superconducting transition in Fe1-xCuxSe0.4Te0.6 (x = 0, 0.005, 0.01, 0.015) and reduces the residual resistivity. Additionally, the upper critical field is reduced from 150 T in FeSe0.4Te0.6 to 41 T in Fe0.085Cu0.015Se0.4Te0.6, but still higher than the 12.5 T observed in FeSe.

Labeling of methyl groups: a streamlined protocol and guidance for the selection of 2H precursors based on molecular weight.

A streamlined one-day protocol is described to produce isotopically methyl-labeled protein with high levels of deuterium for NMR studies. Using this protocol, the D2O and 2H-glucose content of the media and protonation level of ILV labeling precursors (ketobutyrate and ketovalerate) were varied. The relaxation rate of the multiple-quantum (MQ) state that is present during the HMQC-TROSY pulse sequence was measured for different labeling schemes and this rate was used to predict upper limits of molecular weights for various labeling schemes. The use of deuterated solvents (D2O) or deuterated glucose is not required to obtain 1H-13C correlated NMR spectra of a 50kDa homodimeric protein that are suitable for assignment by mutagenesis. High quality spectra of 100-150kDa proteins, suitable for most applications, can be obtained without the use of deuterated glucose. The proton on the β-position of ketovalerate appears to undergo partial exchange with deuterium under the growth conditions used in this study.

The role of atrial pacing site in reducing filling pressures by accelerated pacing in virtual HFpEF patients

Abstract Background Patients with heart failure with preserved ejection fraction (HFpEF) and pacemakers have been shown to benefit from moderately accelerated pacing rates compared to the standard 60bpm. HFpEF patients often present with prolonged P-wave duration (PWD) and atrial fibrillation. Right atrial appendage pacing (RAAP) lengthens PWD, RA septal (RASP) has a neutral effect, while Bachmann’s bundle pacing (BBP) normalizes or shortens PWD compared to sinus rhythm. The mechanical and hemodynamic effects of atrial pacing site selection remain unknown. Aim To investigate the impact of RAAP, RASP and BBP on cardiac mechanics and hemodynamics in an established cohort of virtual HFpEF patients undergoing accelerated pacing. Method HFpEF with prolonged PWD was simulated using the validated CircAdapt computational model of the human cardiovascular system. First, left ventricular (LV) diastolic dysfunction was simulated by decreasing LV myocardial relaxation rate and compliance, such that mean left atrial (LA) pressure (mLAP) was 15mmHg. Second, PWD was prolonged by prescribing a gradual electrical activation delay from RA to LA of 140ms. We then simulated atrial pacing with three different lead positions (Fig.1, left) and gradually increased pacing rate with a constant 120-ms paced atrioventricular (AV) delay. The CircAdapt model computed regional LA strain and mLAP with RAAP, RASP, and BBP. Cardiac output (5L/min) and mean arterial pressure (92mmHg) were kept constant in all simulations. Results Simulated BBP demonstrated the most synchronous LA mechanical activation and function, characterized by uniform segmental LA strain patterns and highest LA reservoir strain (LASR) (Fig.1, middle, with colored arrows highlighting the mechanical dyssynchrony). Hemodynamically (Fig.1, right), BBP acutely decreased mLAP (-1.0mmHg) at the initial heart rate of 60bpm, while RAAP increased it (+0.3mmHg). As pacing rate accelerated, BBP reduces filling pressure (mLAP: -2.8mmHg), more than RASP (-1.8mmHg) or RAAP (-1.2mmHg) at 80bpm. At high pacing rates, RASP and RAAP adversely increase mLAP, due to the prolonged atrial contraction duration and shorter LV filling time. Conclusion Our simulations of different atrial pacing sites in virtual HFpEF patients suggest that BBP yields the most synchronous LA activation pattern and a more substantial reduction in filling pressures with accelerated atrial pacing compared to RASP. Reduction in mLAP with accelerated pacing was attenuated with RAAP. While our study concentrated on a specific paced AV interval, the favorable outcomes observed with BBP could be further improved by including different, rate-adaptive, AV protocols.Fig 1.

Effect of drawing and heat‐setting process on aggregate structure of Poly(ethylene terephthalate) industrial fiber in large‐scale spinning production

AbstractIt is a vital route to develop new fiber products with various physical‐mechanical properties by which their aggregation structure can be changed via controlling the spinning process parameters. In this study, five groups fiber samples had been obtained by changing the spinneret drawing ratio, two stages drawing ratio and two stages heat‐setting rate. The aggregation structure of the poly(ethylene terephthalate) (PET) industrial fibers from different spinning process was analyzed by combination use of thermal analysis, two‐dimensional wide‐angle X‐ray diffraction (WAXD), small‐angle X‐ray scattering (SAXS), and Infrared Spectroscopy (IR) measurements. It was found that, increasing the spinneret drawing ratio and two stages drawing ratio promoted the orientation and crystallinity within a certain range. For the subsequent two stages heat‐setting process, the disorientation of the amorphous chain is simulated by reducing the relaxation rate and heat setting temperature. Finally, a concise three‐dimensional structure model was established to explain the relationship between aggregation structure and property. These results have important reference for the structure and property analysis of polyester industrial fiber.

Comparison of 2D and 3D oxygen-enhanced MRI of the placenta.

Oxygen-Enhanced Magnetic Resonance Imaging (OE-MRI) of the human placenta is potentially a sensitive marker of in vivo oxygenation. This methodological study shows that full coverage of the placenta is possible using 3D mapping of the change in longitudinal relaxation rate (ΔR1), in a group of healthy pregnant subjects breathing elevated levels of oxygen. Twelve pregnant subjects underwent a comparison of 2D and 3D OE-MRI. ΔR1 was mapped for a single 2D slice (ss-2D), a single matched-slice from the 3D volume (ss-3D) and the full 3D volume (vol-3D). The group-average median ΔR1 values for ss-3D (0.023 s-1) and vol-3D (0.022 s-1) do not differ significantly from ss-2D (0.020 s-1), when compared using a two-tailed paired t-test (ss-3D (p = 0.58) and vol-3D (p = 0.70)). However, median baseline T1 (T1b) for ss-2D was higher (1603 ms) than T1b for ss-3D (1540 ms, p = 0.07) and significantly higher than vol-3D (1515 ms, p = 0.02), when compared using a two-tailed paired t-test. In contrast with previous studies, no correlation of median ΔR1 with gestation age at scan for the normal group (N = 10) was observed for ss-2D, likely due to the smaller gestational range. Full volume OE-MRI maps reveal sensitivity to changes in ΔR1, with some participants showing an enhanced gradient in the intermediate space between the fetal and maternal sides of the placenta in the 3D data. This study shows that it is feasible to acquire whole placental volume OE-MRI data in women with healthy pregnancy.

In vivo demonstration of globotriaosylceramide brain accumulation in Fabry Disease using MR Relaxometry.

How to measure brain globotriaosylceramide (Gb3) accumulation in Fabry Disease (FD) patients in-vivo is still an open challenge. The objective of this study is to provide a quantitative, non-invasive demonstration of this phenomenon using quantitative MRI (qMRI). In this retrospective, monocentric cross-sectional study conducted from November 2015 to July 2018, FD patients and healthy controls (HC) underwent an MRI scan with a relaxometry protocol to compute longitudinal relaxation rate (R1) maps to evaluate gray (GM) and white matter (WM) lipid accumulation. In a subgroup of 22 FD patients, clinical (FAbry STabilization indEX -FASTEX- score) and biochemical (residual α-galactosidase activity) variables were correlated with MRI data. Quantitative maps were analyzed at both global ("bulk" analysis) and regional ("voxel-wise" analysis) levels. Data were obtained from 42 FD patients (mean age = 42.4 ± 12.9, M/F = 16/26) and 49 HC (mean age = 42.3 ± 16.3, M/F = 28/21). Compared to HC, FD patients showed a widespread increase in R1 values encompassing both GM (pFWE = 0.02) and WM (pFWE = 0.02) structures. While no correlations were found between increased R1 values and FASTEX score, a significant negative correlation emerged between residual enzymatic activity levels and R1 values in GM (r = -0.57, p = 0.008) and WM (r = -0.49, p = 0.03). We demonstrated the feasibility and clinical relevance of non-invasively assessing cerebral Gb3 accumulation in FD using MRI. R1 mapping might be used as an in-vivo quantitative neuroimaging biomarker in FD patients.

Piperine enhances contractile force in slow- and fast-twitch muscle.

Piperine has been shown to bind to myosin and shift the distribution of conformational states of myosin molecules from the super-relaxed state to the disordered relaxed state. However, little is known about the implications for muscle force production and potential underlying mechanisms. Muscle contractility experiments were performed using isolated muscles and single fibres from rats and mice. The dose-response effect of piperine on muscle force was assessed at several stimulation frequencies. The potentiation of muscle force was also tested in muscles fatigued by eccentric contractions. Potential mechanisms of force potentiation were assessed by measuring Ca2+ levels during stimulation in enzymatically dissociated muscle fibres, while myofibrillar Ca2+ sensitivity was assessed in chemically skinned muscle fibres. Piperine caused a dose-dependent increase in low-frequency force with no effect on high-frequency force in both slow- and fast-twitch muscle, with similar relative increases in twitch force, rate of force development and relaxation rate. The potentiating effect of piperine on low-frequency force was reversible, and piperine partially recovered low-frequency force in fatigued muscle. Piperine had no effect on myoplasmic free [Ca2+] levels in mouse muscle fibres, whereas piperine substantially augmented the force response to submaximal levels of [Ca2+] in rat MyHCII fibres and MyHCI fibres along with a minor increase in maximum Ca2+-activated force. Piperine enhances low-frequency force production in both fast- and slow-twitch muscle. The effects are reversible and can counteract muscle fatigue. The primary underlying mechanism appears to be an increase in Ca2+ sensitivity. KEY POINTS: Piperine is a plant alkaloid derived from black pepper. It is known to bind to skeletal muscle myosin and enhance resting ATP turnover but its effects on contractility are not well known. We showed for the first time a piperine-induced force potentiation that was pronounced during low-frequency electrical stimulation of isolated muscles. The effect of piperine was observed in both slow and fast muscle types, was reversible, and could counteract the force decrements observed after fatiguing muscle contractions. Piperine treatment caused an increase in myofibrillar Ca2+ sensitivity in chemically skinned muscle fibres, while we observed no effect on intracellular Ca2+ concentrations during electrical stimulation in enzymatically dissociated muscle fibres.

Reductive Dynamic and Static Excited State Quenching of a Homoleptic Ruthenium Complex Bearing Aldehyde Groups.

A new homoleptic Ru polypyridyl complex bearing two aldehyde groups on each bipyridine ligand, [Ru(dab)3](PF6)2, where dab is 4,4'-dicarbaldehyde-2,2'-bipyridine, was synthesized, characterized, and utilized for iodide photo-oxidation studies. In acetonitrile (CH3CN) solution, the complex displayed an intense metal-to-ligand charge transfer (MLCT) absorbance maximum at 475 nm (ε = 22,000 M-1 cm-1) and an infrared (IR) band at 1712 cm-1 assigned to the pendent aldehyde groups. Visible light excitation in air-saturated solution resulted in room temperature photoluminescence (PL) with a maximum at 675 nm, a quantum yield, ϕPL = 0.048, and an excited state lifetime, το = 440 ns, from which radiative and nonradiative relaxation rate constants were extracted, kr = 9.1 × 104 s-1 and knr = 1.8 × 106 s-1. Pulsed visible light excitation yielded transient UV-vis and IR absorption spectra consistent with an MLCT excited state; relaxation occurred with the maintenance of two isosbestic points in the visible region, and a lifetime that agreed with that measured by time-resolved PL. Cyclic voltammetry studies in a CH3CN solution with 0.1 M TBAPF6 electrolyte revealed a quasi-reversible oxidation, E°(RuIII/II) = +1.25 V vs. Fc+/0, and three sequential one-electron reductions at -1.10, -1.25, and -1.54 V vs. Fc+/0. An excited state reduction potential of E°(Ru*2+/+) = +0.89 V vs. Fc+/0 was estimated with the Rehm-Weller expression. Titration of tetrabutylammonium iodide, TBAI, into a CD3CN solution of [Ru(dab)3](PF6)2 resulted in significant shifts in the aldehyde H atom and 3,3'-biypridyl resonances that were analyzed with a 1:1 equilibrium model, from which Keq = 460 M-1 was extracted, increasing to 5800 M-1 when the solvent was changed to acetone-d6. Iodide titrations resulted in a significant quenching of the [Ru(dab)3]*2+ lifetime and quantum yield in both CH3CN and acetone solvents. In CH3CN, the quenching was mainly dynamic and well described by the Stern-Volmer model, from which a quenching rate constant, kq, of 4.5 × 1010 M-1 s-1 and an equilibrium constant, Keq, of 8.3 × 103 M-1 were obtained. In acetone, the static quenching pathway by iodide was greatly enhanced, with a Keq of 1.2 × 104 M-1 and a higher kq of 9.2 × 1010 M-1 s-1.

Suppressing effect of shortening vapor cell stem on polarization-induced magnetic gradient relaxation of Xe in NMR co-magnetometers

The Rb polarization-induced magnetic field gradient is one of the crucial sources of Xe spin relaxation in NMR co-magnetometers. The additional volume of the atomic vapor cell stem can enhance the effective magnetic field gradient through the diffusion effect of the optically polarized-Rb atoms, which affects the spin relaxation properties of Xe and degrades the long-term stability of NMR co-magnetometers. Based on the discrete steps random walk diffusion model, the magnetic gradient relaxation properties of Xe diffusing in an asymmetric cell composed of a cubic part and a cylindrical tube (stem) are characterized. Simulation results indicate that a shorter stem can effectively prolong the nuclear spin relaxation time under a constant magnetic field gradient. To verify this conclusion, a cell stem truncating actuator is developed using a high-power CO2 laser to shorten the cell stem, and the magnetic field gradient coil is used to perform the gradient compensation to examine the impact of various stem lengths on the spin relaxation rate. Experiments indicate that under the influence of atomic diffusive motions, shortening the stem length can effectively suppress the polarization-induced magnetic gradient and increase the 129Xe transverse relaxation time from 4.5 s to 21 s. The study posts practical applications for vapor cells with a stem, which is expected to enhance the performance of atomic spin co-magnetometers.

Spin relaxation rate for baryons in a thermal pion gas

We study the relaxation dynamics of the spin polarization of baryons (nucleon and Λ baryon), in a thermal pion gas as a simple model of the hadronic phase of the QCD plasma produced in relativistic heavy-ion collisions. For this purpose, we formulate the quantum kinetic theory for the spin density matrix of baryons in the leading order of the gradient expansion. Considering the baryon-pion elastic scattering processes as the dominant interaction between baryons and thermal pions, we compute the spin relaxation rate of nucleons and Λ baryons in a pion gas up to temperature 200 MeV. In the case of nucleons, we evaluate the spin relaxation rate in the s-channel resonance approximation, based on the known experimental data on Δ resonances. We also estimate the spin relaxation rate for Λ baryons, based on experimental inputs and theoretical models for the low-energy Λπ scattering, including the chiral perturbation theory. Published by the American Physical Society 2024

Development of Ln(III) Derivatives as 19F Parashift Probes.

19F parashift probes with paramagnetically shifted reporter nuclei provide attractive platforms to develop molecular imaging probes. These probes enable ratiometric detection of molecular disease markers using a direct detection technique. Here, we describe a series of trivalent lanthanide (Ln(III)) complexes that are structural analogues of the clinically approved MR contrast agent (CA) ProHance to obtain LnL 19F parashift probes. We evaluated trans-gadolinium paramagnetic lanthanides compared to diamagnetic YL for 19F chemical shift and relaxation rate enhancement. The paramagnetic contribution to chemical shift (δPCS) for paramagnetic LnL exhibited either shifts to lower frequency (δPCS < 0 for TbL, DyL, and HoL) or shifts to higher frequency (δPCS > 0 for ErL, TmL, and YbL) compared to YL 19F spectroscopic signal. Zero-echo time pulse sequences achieved 56-fold sensitivity enhancement for DyL over YL, while developing probe-specific pulse sequences with fast delay times and acquisition times achieved 0.6-fold enhancement in limit of detection for DyL. DyL provides an attractive platform to develop 19F parashift probes for ratiometric detection of enzymatic activity.