Contribution To Relaxation Research Articles

Magnetic response and hardness enhancement by spontaneous directional coarsening of Fe2AlB2 in quasicrystal-rich matrix

This study investigates the Al55Cu20Fe15B10 alloy system to understand the characteristics of the Fe2AlB2 (Cmmm) phase and its interactions with a quasicrystal-rich matrix. The alloy’s composition was chosen for its boron content, which promotes the formation of well-defined Fe2AlB2 crystals. We examined how different heat treatments affect the alloy’s microstructure, magnetic properties and hardness. Microstructural and Electron Backscatter Diffraction analyses revealed the stable icosahedral Al59Cu27Fe12B2 quasicrystalline phase and a metastable Al70Fe20Cu10 approximant that is isostructural with C2/m Fe4Al13. Additionally, the alloy contained Al-Cu phases known from meteorites, such as AlCu stolperite and Al2Cu khatyrkite. Heat treatments at 706∘C and 828∘C yielded favorable microstructure for ballistic armor, characterized by Fe2AlB2 lamellae embedded within the quasicrystalline matrix, reinforced by AlB2 precipitation on the grain boundaries. Vickers hardness improvements were attributed to Hall-Petch strengthening and grain orientation effects. Notably, annealing at 943∘C nearly tripled the magnetic entropy change. Quantum Diamond Microscopy confirmed that Fe2AlB2 significantly contributed to magnetization. The improvement of magnetic properties was found to be due to preferential orientation of Fe2AlB2 grains along the [010] zone axis, as a consequence of directional coarsening induced by annealing. The enhanced magnetocaloric properties observed at 943∘C are primarily due to intrinsic changes in the Fe2AlB2 phase rather than strain relaxation or phase contributions from the quasicrystalline matrix.

Time-Dependent Relationship Between Endothelial Dysfunction and High Blood Pressure in Fructose Drinking Rats.

This study aims to investigate the duration required for endothelium dysfunction to develop in the fructose drinking-induced hypertension and examine the relative contributions of endothelium-dependent relaxing factors to changes in mesenteric arterial reactivity in male Wistar Albino rats. Metabolic parameters (water intake and food consumption) and hemodynamic parameters systolic blood pressure (SBP) and diastolic blood pressure (DBP)-were monitored in vivo. Vascular reactivity was examined in the isolated organ bath. Endothelium-dependent relaxation (EDR) to acetylcholine was observed in the absence and presence of pharmacological inhibitors of endothelial nitric oxide (NO) synthase, cyclooxygenase, and KCa2.3 channels. Contractile responses to phenylephrine and relaxation of sodium nitroprusside (SNP) were also determined. A significant increase in daily water intake and decrease in food consumption were typically observed in rats treated with 10% fructose for 4 weeks (p < 0.05). SBP and DBP increased significantly as early as 2 weeks of induction and continued to rise gradually throughout the induction period (p < 0.05). Fructose consumption significantly impaired EDR at week 3 and worsened at week 4 (p < 0.05). Impairment of the KCa3.1 channel-mediated component of endothelium-dependent hyperpolarisation (EDH)-type relaxation contributed to worsening EDR, whereas the contribution of NO-mediated relaxation was not apparent compared with the controls. The reduction in EDH-type relaxation in fructose-fed rats appears to be partially compensated by increased NO sensitivity in the smooth muscle region, as fructose induction increased SNP relaxation compared with the control. These data provide evidence of early endothelial dysfunction developing concurrently with increased blood pressure in 10% fructose-fed rats. Decreased KCa3.1-mediated part of EDH-type relaxation appears to contribute to the impairment of endothelium-dependent vasorelaxation over time in this model.

Modified Debye-Hückel-Onsager theory for electrical conductivity in aqueous electrolyte solutions: Account of ionic charge nonlocality.

This paper presents a mean field theory of electrolyte solutions, extending the classical Debye-Hückel-Onsager theory to provide a detailed description of the electrical conductivity in strong electrolyte solutions. The theory systematically incorporates the effects of ion specificity, such as steric interactions, hydration of ions, and their spatial charge distributions, into the mean-field framework. This allows for the calculation of ion mobility and electrical conductivity, while accounting for relaxation and hydrodynamic phenomena. At low concentrations, the model reproduces the well-known Kohlrausch's limiting law. Using the exponential (Slater-type) charge distribution function for solvated ions, we demonstrate that experimental data on the electrical conductivity of aqueous 1:1, 2:1, and 3:1 electrolyte solutions can be approximated over a broad concentration range by adjusting a single free parameter representing the spatial scale of the nonlocal ion charge distribution. Using the fitted value of this parameter at 298.15K, we obtain good agreement with the available experimental data when calculating electrical conductivity across different temperatures. We also analyze the effects of temperature and electrolyte concentration on the relaxation and electrophoretic contributions to total electrical conductivity, explaining the underlying physical mechanisms responsible for the observed behavior.

Dynamics of ionic liquid-polymer gel membranes-Insight from NMR relaxometry for [BMIM][BF4]-PVDF-HFP systems.

1H spin-lattice relaxation experiments have been performed for ionic liquid-polymer gel membranes, including 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]) and poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) with different proportions. The experiments have been performed in a broad range of resonance frequencies (from about 5Hz to 40MHz) vs temperature and complemented with analogous studies for [BMIM][BF4] in bulk as a reference. A model of the relaxation processes in the membranes has been proposed. The model includes two relaxation contributions. One of them corresponds to the concept of restricted, two-dimensional translation diffusion with a residence lifetime, while the second one has the form characteristic of polymers (mathematically similar to the limiting behavior of two-dimensional translation diffusion with a very long residence lifetime). The extensive dataset has been consistently interpreted in terms of the model, revealing two dynamical processes on the time scales of 10-7s (for the second relaxation contribution) and 10-9s (for the first one). The relationship of these relaxation contributions to the motion of the polymer or ionic liquid-polymer complexes and to the translation diffusion of BMIM cations in the matrix has been discussed.

Postseismic deformation due to the 2021 MW 7.4 Maduo (China) earthquake and implications for regional rheology and seismic hazards around the Bayan Har block

GPS and InSAR observations of the first ∼1.5 years of postseismic deformation caused by the 2021 MW 7.4 Maduo earthquake provide a valuable opportunity to investigate fault interactions and regional rheological structure, as well as the future seismic potential around the Bayan Har block, northeastern Tibetan Plateau. We develop an integrated model to simulate the afterslip and viscoelastic relaxation contributions to the observed postseismic displacements, and found that afterslip driven by the coseismic stress is concentrated downdip of rupture, and dominates the postseismic deformation in the early stage (∼0.4 year after the event). Because afterslip decays quickly over time, viscoelastic relaxation should become the main postseismic mechanism as time goes on. The two mechanisms produce similar displacements during 0.4–1.5 years after the earthquake, but at 1.5 years after the earthquake the velocity caused by viscoelastic relaxation is larger than that caused by afterslip. Viscoelastic models assuming either a Burgers body or power-law rheology produce very similar predictions, with the Burgers body model having a slightly lower overall misfit. The rheological structure constrained by the postseismic observations supports the 35-km thick elastic upper crust overlying a Burgers body viscoelastic lower curst with a Maxwell viscosity of 3 × 1019 Pa s (5 - 50 × 1018 Pa s at 95% confidence), assuming the Kelvin viscosity is equal to 10% of that value. This is different from the regional rheology inferred by the postseismic investigations on the 2001 MW 7.8 Kokoxili and the 2008 MW 7.8 Wenchuan events, and the preferred thickness of the elastic crust is also different from that inferred from magnetotelluric profiles deployed in previous studies. We thus infer that the rheological structure within the Bayan Har block is possibly heterogeneous from west to east. Finally, the normal stress changes triggered by the coseismic rupture and postseismic process are estimated to be negative, but the shear stress changes to be positive on the western Kunlun fault, the eastern Dari fault and Bayan-Har Mountain fault. However, the current observations and studies are quite insufficient on those fault segments, therefore, we need to focus on their faulting behavior and seismic risk in the future.

Water Dynamics in Fish Collagen Gels-Insight from NMR Relaxometry.

1H spin-lattice relaxation experiments have been performed for gels based on fish collagen in order to analyze water dynamics. The covered frequency range ranges from 10 kHz to 10 MHz; in some cases, the temperature has varied as well. The relaxation data have been reproduced in terms of two models of water motion-a model including two relaxation contributions associated with the diffusion of water molecules on the macromolecular surfaces and a second model being just a phenomenological power law. The concept of surface diffusion has led to a very good agreement with the experimental data and a consistent set of parameters, with the diffusion coefficients being about five orders of magnitude slower compared to bulk water for one of the pools and considerably faster for the second one (smaller by factors between 2 and 20 compared to bulk water). In some cases, the attempt to reproduce the data in terms of a power law has led to a good agreement with the experimental data (the power law factor varying between 0.41 and 0.57); however, in other cases, the discrepancies are significant. This outcome favors the concept of surface diffusion.

Intermediate scattering function for polymer molecules: An approach based on relaxation mode analysis.

The theory of polymer dynamics describes the intermediate scattering function for a polymer molecule in terms of relaxation modes defined by normal coordinates for the corresponding coarse-grained model. However, due to the difficulty of defining the normal coordinates for arbitrary polymer molecules, it is generally challenging to express the intermediate scattering function for a polymer molecule in terms of relaxation modes. To overcome this challenge, we propose a general method to calculate the intermediate scattering function for a polymer molecule on the basis of a relaxation mode analysis approach [Takano and Miyashita, J. Phys. Soc. Jpn. 64, 3688 (1995)]. In the proposed method, relaxation modes defined by eigenfunctions in a Markov process are evaluated on the basis of the simulation results for a polymer molecule and used to calculate the intermediate scattering function for that molecule. To demonstrate the effectiveness of the present method, we simulate the dynamics of a linear polymer molecule in a dilute solution and apply it to the calculation of the intermediate scattering function for the polymer molecule. The evaluation results regarding the relaxation modes reasonably describe the intermediate scattering function on the length scale of the radius of gyration of the polymer molecule. Accordingly, we examine the contributions of the pure relaxation and oscillatory relaxation processes to the entire intermediate scattering function.

Kinetic study of in vitro release of curcumin from chitosan biopolymer and the evaluation of biological efficacy

Sustained release of curcumin from the polymeric carrier system chitosan, a natural biopolymer material derived from chitin originated from natural shrimp shell waste, was studied. Six kinetic models, zero order, first order, Korsmeyer–Peppas (KP), Peppas – Sahlin (PS), Higuchi, and Hixson–Crowell, were applied to study the drug release kinetics. The release mechanism of the drug from the curcumin-chitosan composite was evaluated by changing the pH, ionic strength of the release media, and drug concentration. KP and PS models were selected among the studied models to investigate the drug release mechanism from the chitosan biopolymer based on the R2 values (R2 > 0.99). The model constants m in the PS model and n in the KP model stand for the case II relaxation and Fickian diffusion contribution, respectively. The n being < 0.43 in the KP model suggests that the Fickian diffusion governs the drug release. Furthermore, there is a noticeable difference between the values obtained for model parameters m and n in the PS and KP models, indicating that Case II relaxation and Fickian diffusion play crucial roles in the curcumin release mechanism from chitosan. Polymer relaxation has been proven to play a predominant role in releasing curcumin from the composite at lower ionic strengths and higher pH values. Anti-inflammatory activity was tested using the egg-albumin denaturation assay, and the diphenyl-2-picrylhydrazyl assay was carried out to determine the antioxidant activity of the composite. The composite material showed IC50 values of 0.29 mg/ mL and 1.08 mg/ mL for anti-inflammatory and anti-oxidant activities, respectively. The drug composite has shown antibacterial activity against Pseudomonas aeruginosa, Klebsiella pneumoniae, and Staphylococcus aureus, which are highly effective against S.aureus. The resulting inhibition zones for S.aureus were 13.34 ± 0.34 mm, 16.34 ± 0.60 mm, and 13.34 ± 0.73 mm for 5, 10, and 20 mg/ml concentrations, respectively. The drug composite’s minimum inhibitory concentration/ minimum bactericidal concentration ratio for S.aureus, K. pneumoniae, and P.aeruginosa was greater than 4, suggesting that they cause bacteriostatic effects.

Universal 1H Spin-Lattice NMR Relaxation Features of Sugar-A Step towards Quality Markers.

1H fast field-cycling and time-domain nuclear magnetic resonance relaxometry studies have been performed for 15 samples of sugar of different kinds and origins (brown, white, cane, beet sugar). The extensive data set, including results for crystal sugar and sugar/water mixtures, has been thoroughly analyzed, with a focus on identifying relaxation contributions associated with the solid and liquid fractions of the systems and non-exponentiality of the relaxation processes. It has been observed that 1H spin-lattice relaxation rates for crystal sugar (solid) vary between 0.45 s-1 and 0.59 s-1, and the relaxation process shows only small deviations from exponentiality (a quantitative measure of the exponentiality has been provided). The 1H spin-lattice relaxation process for sugar/water mixtures has turned out to be bi-exponential, with the relaxation rates varying between about 13 s-1-17 s-1 (for the faster component) and about 2.1 s-1-3.5 s-1 (for the slower component), with the ratio between the amplitudes of the relaxation contributions ranging between 2.8 and 4.2. The narrow ranges in which the parameters vary make them a promising marker of the quality and authenticity of sugar.

Ultrasonic monitoring of enzymatic hydrolysis of proteins. 2. relaxation effects

The paper investigates the occurrence of relaxation processes in enzymatic hydrolysis of whey proteins in phosphate buffer using high-resolution ultrasonic spectroscopy. The hydrolysis produces a frequency-dependent evolution of ultrasonic velocity and attenuation originated by the proton transfer between the phosphate ions and the terminal −NH2 group of protein hydrolysates. Such frequency dependence is absent in other systems, e.g., Tris buffer. Real-time profiles of ultrasonic velocity and attenuation measured during the hydrolysis of β–lactoglobulin, α–lactalbumin and bovine serum albumin by α–chymotrypsin were employed in quantitative analysis of the relaxation mechanisms, relaxation times, determination of the proton transfer rate constants and the reaction volume. The proton transfer is characterised by the rate constant 9.4 × 107 L mol−1 s−1 and the adiabatic reaction volume 24 × 10−6 m3 mol−1. The obtained reaction volume agrees well with thermodynamic data for ionisation volumes and enthalpies of the terminal amino group and phosphate. The described methodology for estimating the relaxation contribution to ultrasonic characteristics allows for precision real-time ultrasonic measurements of the concentration of peptide bonds cleaved during protein hydrolysis in a broad range of environmental conditions.

Mobility of sodium ions in agarose gels probed through combined single- and triple-quantum NMR

Metal ions, including biologically prevalent sodium ions, can modulate electrostatic interactions frequently involved in the stability of condensed compartments in cells. Quantitative characterization of heterogeneous ion dynamics inside biomolecular condensates demands new experimental approaches. Here we develop a 23Na NMR relaxation-based integrative approach to probe dynamics of sodium ions inside agarose gels as a model system. We exploit the electric quadrupole moment of spin-3/2 23Na nuclei and, through combination of single-quantum and triple-quantum-filtered 23Na NMR relaxation methods, disentangle the relaxation contribution of different populations of sodium ions inside gels. Three populations of sodium ions are identified: a population with bi-exponential relaxation representing ions within the slow motion regime and two populations with mono-exponential relaxation but at different rates. Our study demonstrates the dynamical heterogeneity of sodium ions inside agarose gels and presents a new experimental approach for monitoring dynamics of sodium and other spin-3/2 ions (e.g. chloride) in condensed environments.

Dynamical properties of solid and hydrated collagen: Insight from nuclear magnetic resonance relaxometry.

1H spin-lattice Nuclear Magnetic Resonance relaxometry experiments have been performed for collagen and collagen-based artificial tissues in the frequency range of 10 kHz-20MHz. The studies were performed for non-hydrated and hydrated materials. The relaxation data have been interpreted as including relaxation contributions originating from 1H-1H and 1H-14N dipole-dipole interactions, the latter leading to Quadrupole Relaxation Enhancement effects. The 1H-1H relaxation contributions have been decomposed into terms associated with dynamical processes on different time scales. A comparison of the parameters for the non-hydrated and hydrated systems has shown that hydration leads to a decrease in the dipolar relaxation constants without significantly affecting the dynamical processes. In the next step, the relaxation data for the hydrated systems were interpreted in terms of a model assuming two-dimensional translational diffusion of water molecules in the vicinity of the macromolecular surfaces and a sub-diffusive motion leading to a power law of the frequency dependencies of the relaxation rates. It was found that the water diffusion process is slowed down by at least two orders of magnitude compared to bulk water diffusion. The frequency dependencies of the relaxation rates in hydrated tissues and hydrated collagen are characterized by different power laws (ωH-β, where ωH denotes the 1H resonance frequency): the first of about 0.4 and the second close to unity.

Dynamic of binary molecular systems-Advantages and limitations of NMR relaxometry.

1H spin-lattice relaxation studies have been performed for binary systems, including glycerol as the first component and alanine, glycine, and aspartic acid (with different levels of deuteration) as the second one. The relaxation studies have been performed in the frequency range from 10kHz to 10MHz vs temperature. A theoretical framework, including all relevant 1H-1H and 1H-2H relaxation pathways, has been formulated. The theory has been exploited for a thorough interpretation of a large set of the experimental data. The importance of the 1H-2H relaxation contributions has been discussed, and the possibility of revealing dynamical properties of individual liquid components in binary liquids has been carefully investigated. As far as the dynamical properties of the specific binary liquids, chosen as an example, are considered, it has been shown that in the presence of the second component (alanine, glycine, and aspartic acid), both molecular fractions undergo dynamics similar to that of glycerol in bulk.

Electronic Structures of Radical-Pair-Forming Cofactors in a Heliobacterial Reaction Center.

Photosynthetic reaction centers (RCs) are membrane proteins converting photonic excitations into electric gradients. The heliobacterial RCs (HbRCs) are assumed to be the precursors of all known RCs, making them a compelling subject for investigating structural and functional relationships. A comprehensive picture of the electronic structure of the HbRCs is still missing. In this work, the combination of selective isotope labelling of 13C and 15N nuclei and the utilization of photo-CIDNP MAS NMR (photochemically induced dynamic nuclear polarization magic-angle spinning nuclear magnetic resonance) allows for highly enhanced signals from the radical-pair-forming cofactors. The remarkable magnetic-field dependence of the solid-state photo-CIDNP effect allows for observation of positive signals of the electron donor cofactor at 4.7 T, which is interpreted in terms of a dominant contribution of the differential relaxation (DR) mechanism. Conversely, at 9.4 T, the emissive signals mainly originate from the electron acceptor, due to the strong activation of the three-spin mixing (TSM) mechanism. Consequently, we have utilized two-dimensional homonuclear photo-CIDNP MAS NMR at both 4.7 T and 9.4 T. These findings from experimental investigations are corroborated by calculations based on density functional theory (DFT). This allows us to present a comprehensive investigation of the electronic structure of the cofactors involved in electron transfer (ET).

Highlighting the interdependence between volumetric contribution of fragility and cooperativity for polymeric segmental relaxation.

The blurring around the link between the isobaric fragility and the characteristic size of cooperative rearranging region for glass-forming liquids has been cleared up by considering volumetric and thermal contributions of the structural relaxation. The measurement of these contributions is carried out for three amorphous thermoplastic polymers using broadband dielectric spectroscopy under pressure, providing an understanding of the link between isobaric fragilities, glass transition temperatures, and microstructures. The cooperative rearranging region (CRR) volume is calculated as a function of pressure using the extended Donth's approach, and the values are compared with the activation volume at the glass transition under different isobaric conditions. By combining these different results, a link between the chemical structure and the influence of pressure/temperature on the molecular mobility can be established. Furthermore, this study shows also a strong correlation between the activation volume, leading to the volumetric contribution of the isobaric fragility, and the CRR volume. Finally, this work highlights the influence of inter- and intra-molecular interactions on thermal and volumetric contributions of the isobaric fragility as a function of pressure.

The cardiomyocyte origins of diastolic dysfunction: cellular components of myocardial "stiffness".

The impaired ability of the heart to relax and stretch to accommodate venous return is generally understood to represent a state of "diastolic dysfunction" and often described using the all-purpose noun "stiffness." Despite the now common qualitative usage of this term in fields of cardiac patho/physiology, the specific quantitative concept of stiffness as a molecular and biophysical entity with real practical interpretation in healthy and diseased hearts is sometimes obscure. The focus of this review is to characterize the concept of cardiomyocyte stiffness and to develop interpretation of "stiffness" attributes at the cellular and molecular levels. Here, we consider "stiffness"-related terminology interpretation and make links between cardiomyocyte stiffness and aspects of functional and structural cardiac performance. We discuss cross bridge-derived stiffness sources, considering the contributions of diastolic myofilament activation and impaired relaxation. This includes commentary relating to the role of cardiomyocyte Ca2+ flux and Ca2+ levels in diastole, the troponin-tropomyosin complex role as a Ca2+ effector in diastole, the myosin ADP dissociation rate as a modulator of cross bridge attachment and regulation of cross-bridge attachment by myosin binding protein C. We also discuss non-cross bridge-derived stiffness sources, including the titin sarcomeric spring protein, microtubule and intermediate filaments, and cytoskeletal extracellular matrix interactions. As the prevalence of conditions involving diastolic heart failure has escalated, a more sophisticated understanding of the molecular, cellular, and tissue determinants of cardiomyocyte stiffness offers potential to develop imaging and molecular intervention tools.

Novel core-shell microcapsules incorporating macro/micronutrients in PVA/starch matrix

Enhanced efficiency fertilizers (EEFs) have been widely used due to their ability to meet crop nutritional needs and reduce the main problem of leaching. In this work, we compared the effects of spray-dryer microspheres and microcapsules on nutrient encapsulation and identified the spheres and core-shell structures by fluorescence microscopy using Rhodamine B (RB) as the fluorescent material. The microsphere matrix was based on starch, and the microcapsules consisted of starch as the core and poly (vinyl alcohol) as the shell. The fluorescent images confirmed that the RB was incorporated into the starch, as the overlap of fluorescence and brightfield images covered the entire area for microspheres and only the core for microcapsules. Microspheres exhibited an irregular and non-spherical morphology, whereas microcapsules presented a spherical shape with a smooth and homogeneous surface featuring small aggregated particles. The microparticle structures remained unchanged even after incorporating KNO3, Fe, Cu, and Mn. Thermal analysis indicated lower initial mass loss temperatures for the microcapsules, suggesting polymer interactions during drying and formation. FTIR further supported this, which revealed structural changes and partial oxidation during drying, contributing to reduced thermodegradation. Notably, micronutrient-based microcapsules demonstrated a significantly lower burst release than macro/micronutrient-based microcapsules and micronutrient-based microspheres. Fe and Cu were released most rapidly from microspheres in the first hour, reaching 84.2% and 79.4%, respectively. In contrast, macro/micronutrient-based microcapsules released 66.1% and 67.7%, while micronutrient-based microcapsules released 53.1% and 61.5%. As for Mn, macro/micronutrient-based microcapsules exhibited the highest initial release at 72.4%, followed by micronutrient-based microcapsules at 62.2%, with microspheres releasing at 55.8%. Additionally, the Peppas-Sahlin model provided the best fit, indicating diffusional and polymer relaxation contributions. The morphology, release, and kinetics behaviors confirmed that the core-shell prolonged the nutrient release by reducing the initial burst release, thanks to the diffusion barrier provided by the PVA layer.

Remote imprinting of moiré lattices.

Two-dimensional moiré materials are formed by overlaying two layered crystals with small differences in orientation or/and lattice constant, where their direct coupling generates moiré potentials. Moiré materials have emerged as a platform for the discovery of new physics and device concepts, but while moiré materials are highly tunable, once formed, moiré lattices cannot be easily altered. Here we demonstrate the electrostatic imprinting of moiré lattices onto a target monolayer semiconductor. The moiré potential-created by a lattice of electrons that is supported by a Mott insulator state in a remote MoSe2/WS2 moiré bilayer-imprints a moiré potential that generates flat bands and correlated insulating states in the target monolayer and can be turned on/off by gate tuning the doping density of the moiré bilayer. Additionally, we studied the interplay between the electrostatic and structural relaxation contributions to moiré imprinting. Our results demonstrate a pathway towards gate control of moiré lattices.

In situ hydrolysis of a carbophosphazene ligand leads to one-dimensional lanthanide coordination polymers. Synthesis, structure and dynamic magnetic studies.

An in situ hydrolysis of the P-Cl bonds of the carbophosphazene [{NC(NMe2)}2{NPCl2}] (LPCl2) in the presence of hydrated lanthanide(III) nitrates in a dichloromethane and methanol (2 : 1) solvent mixture afforded a series of novel 1D coordination polymers: [{Ln(LHPO2)3(NO3)2(CH3OH)(H2O)} (Cl)]n {where Ln(III) = Gd (1), Tb (2), Dy (3), or Er (4) and LHPO2 is the hydrolyzed carbophosphazene (LPCl2) ligand}. X-ray crystallographic analysis revealed that complexes 1-4 are isostructural and crystallized in the monoclinic crystal system having P21/c space group. The coordination polymers are formed because of the involvement of the geminal P(O)(OH) moieties of the carbophosphazene ligand. Each lanthanide(III) ion is 9-coordinate (9O) in a distorted muffin geometry. Magnetic measurements revealed that both DyIII and ErIII analogues exhibit field-induced single-molecule magnet (SMM) behavior at 0.8 kOe and 2.2 k Oe, respectively. At such dc fields, the dynamic magnetic susceptibility displays complex behavior with a triple magnetic relaxation contribution for 3, while two contributions were identified for 4. The observed static and dynamic magnetic behavior for complexes 1-4 were further rationalized with the aid of BS-DFT and CASSCF/SO-RASSI/SINGLE_ANISO calculations.

Water Dynamics in Dextran-Based Hydrogel Micro/Nanoparticles Studied by NMR Diffusometry and Relaxometry.

Water dynamics in mesoporous dextran hydrogel micro/nanoparticles was investigated by means of nuclear magnetic resonance (NMR) techniques. High-resolution 1H NMR spectra and pulsed field gradient (PFG) NMR diffusometry measurements obtained on swollen state dextran micro/nanogel revealed the existence of different fractions of water molecules based on their interaction with the gel matrix. In addition to the translational diffusion of bulk water, two more diffusion processes characterized with self-diffusion coefficients 1 and 2 orders of magnitude smaller than that of bulk water were identified. 1H spin-lattice relaxation dispersion profiles obtained for a broad range of Larmor frequencies using fast field cycling (FFC) and conventional NMR relaxometry techniques allowed us to further clarify the mechanisms of molecular motion. According to the water proton pool fractions and associated self-diffusion coefficients, it is shown that the relaxation contribution associated with reorientation-mediated translational motions (RMTDs) dominates the relaxation dispersion observed at intermediate frequencies. At very low frequencies, the spin-lattice relaxation rate is dominated by the slow solid-gel dynamics probed by the water molecules interacting with the pores' surface hydroxyl groups due to the rapid chemical exchange between surface hydroxyl groups and free water. The correlation time for the thumbling-like motion of the dextran gel was found to be in the submillisecond range. The values of the self-diffusion and coherence lengths associated with motion of water molecules interacting with the solid-gel particles are consistent with the particle size and pore size distributions obtained for the studied dextran gels.