Decrease In Relaxation Time Research Articles

The Spin‐Selective Channels in Fully‐Exposed PtFe Clusters Enable Fast Cathodic Kinetics of Li‐O2 Batter y

In Li‐O2 batteries (LOBs), the electron transfer between triplet O2 and singlet Li2O2 possesses a spin‐dependent character but is still neglected, while the spin‐conserved electron transfer without losing phase information should guarantee fast kinetics and reduced energy barriers. Here, we provide a paradigm of spin‐selective catalysis for LOB that the ferromagnetic quantum spin exchange interactions between Pt and Fe atoms in fully‐exposed PtFe clusters filter directional e‐spins for spin‐conserved electron transfer at Fe‐Fe sites. The kinetics of O2/Li2O2 redox reaction is markedly accelerated as predicted by theoretical calculations, showing dramatically decreased relaxation time of the rate determining step for more than one order of magnitude, compared with the Fe clusters without spin‐selective behavior. In consequence, the assembled LOB provides ultrahigh energy conversion efficiency of 89.6% at 100 mA g‐1 under a discharge‐charge overpotential of only 0.32 V. This work provides new insights into the spin‐dependent mechanisms of O2/Li2O2 redox reaction, and the strategy of constructing spin catalysts at atomic level.

The Spin-Selective Channels in Fully-Exposed PtFe Clusters Enable Fast Cathodic Kinetics of Li-O2 Batter y.

In Li-O2 batteries (LOBs), the electron transfer between triplet O2 and singlet Li2O2 possesses a spin-dependent character but is still neglected, while the spin-conserved electron transfer without losing phase information should guarantee fast kinetics and reduced energy barriers. Here, we provide a paradigm of spin-selective catalysis for LOB that the ferromagnetic quantum spin exchange interactions between Pt and Fe atoms in fully-exposed PtFe clusters filter directional e-spins for spin-conserved electron transfer at Fe-Fe sites. The kinetics of O2/Li2O2 redox reaction is markedly accelerated as predicted by theoretical calculations, showing dramatically decreased relaxation time of the rate determining step for more than one order of magnitude, compared with the Fe clusters without spin-selective behavior. In consequence, the assembled LOB provides ultrahigh energy conversion efficiency of 89.6% at 100 mA g-1 under a discharge-charge overpotential of only 0.32 V. This work provides new insights into the spin-dependent mechanisms of O2/Li2O2 redox reaction, and the strategy of constructing spin catalysts at atomic level.

Strain induced crystal lattice softening and improved thermoelectric performance of hydrogenated silicene for energy harvesting applications

In recent years, Silicene has attracted great interest in various fields but does not fit well in the field of thermoelectrics due to the absence of electronic band gap. Nevertheless, hydrogenation of silicene (SiH) delocalize the free electrons and induces gap widening (2.19 eV), but its thermoelectric performance is still limited due to the larger band gap. Thermoelectric performance can be effectively improved using strain engineering, which allows modulation of crystal as well as electronic energy levels of a material. We studied the effect of biaxial tensile strain on structure, stability and thermoelectric properties of SiH monolayer. Taking clue regarding the stability from phonon dispersion, tensile strain upto 14% is incorporated and results are discussed. The distortion of crystal structure with strain manipulates the characteristics of electronic band structure such that there is an indirect to direct band gap transition along with decrease in band gap, effective mass and relaxation time of carriers. As a result, the Seebeck coefficient falls and attains minimum value at 14% strain while electrical conductivity and electronic thermal conductivity shows increasing trend and maximize at 14% strain. Another crucial consequence of strain is that tensile strain led to a considerable decrease in lattice thermal conductivity. At a strain of 14%, the lattice thermal conductivity at 700 K (0.28) decreased by approximately 43% compared to its unstrained counterpart (0.49 K), which is highly beneficial for achieving high ZT. To assess the efficiency of thermoelectric conversion, the ZT is computed, revealing an increase from 1.66 in the unstrained state to 2.83 at a strain of 14% and a temperature of 700 K. The calculations unveil a nearly twofold increase in ZT with the implementation of strain engineering, underscoring its effectiveness in augmenting the efficiency of thermoelectric devices.

Interactions Between Cationic Micellar Solution and Aromatic Hydrotropes with Subtle Structural Variations.

Wormlike micelles (WLMs) with tunable viscoelastic characteristics have emerged as indispensable smart materials with a wide range of applications, which have garnered intense interest over the past few decades. However, quantitatively predicting the effect of various hydrotropes on the rheological behaviors of WLMs remains a challenge. In this article, micelles were formed in a mixture of 3-hexadecyloxy-2-hydroxypropyltrimethylammonium bromide (R16HTAB) and aromatic hydrotropes (e.g., sodium benzoate, sodium cinnamate and their derivatives, respectively) in an aqueous solution. The phase behavior, viscoelasticity and thickening mechanism were systematically studied by macroscopic observation, rheological measurements, electrostatic potential analysis and cryogenic transmission electron microscopy (Cryo-TEM). Rheological measurements were used to probe the remarkable viscoelastic properties of micelles stemming from their lengthening and entanglement under the interaction between R16HTAB and hydrotropes with structural variations. For an equimolar system of R16HTAB and cosolute (40 mM), the relaxation time decreases in the following order: SpMB > SoHB > S4MS > SmMB > S5MS > SB > SmHB > SoMB > SpHB. These results allow us to predict the possible rules for the self-assembly of R16HTAB and aromatic hydrotropes, which is conductive to directionally designing and synthesizing smart wormlike micelles.

Spectral induced polarization of corrosion of sulfur modified Iron in sediments

Spectral induced polarization (SIP) responses are not well understood within the context of remediation applications at contaminated sites. Systematic SIP studies are needed to gain further insights into the complex electrical response of dynamic, biogeochemical states to enable the use of SIP for subsurface site characterization and remediation monitoring. Although SIP measurements on zero valent iron have been previously published, the SIP response for sulfur modified iron (SMI), a similar potential subsurface reductive amendment, has not yet been reported. Hence, the purpose of this laboratory-scale study was to evaluate SIP for nonintrusive monitoring of SMI under relevant subsurface conditions. SMI was separately mixed with silica sand or sediments from the Hanford Site (Washington, USA) and then packed into columns for geochemical and SIP analysis for up to 77 days under fully saturated conditions. SMI exhibited distinguishable phase peaks between 0.1 and 1.0 Hz, which changed in magnitude based on content and were detected as low as 0.3 wt%. In the initial days, the complex conductivity, phase maxima, and chargeability increased while the peak locations shifted to higher frequency (decreasing relaxation times), suggesting an initial increase in polarization and concurrent decrease in the length scales (potentially due to changes in particle size and mineralogy). Then, after 77 days, the phase maxima and chargeability decreased with a concurrent increase in relaxation times, suggesting that over longer periods, less polarizable phases are forming and particle size or connectivity of polarizable phases is increasing. These results demonstrated a unique SIP response to SMI transformations that might be applied to monitoring of SMI emplaced as a subsurface barrier or injected in the field.

Physicochemical and Morphological Changes in Long-Grain Brown Rice Milling: A Study Using Image Visualization Technologies

This study evaluated the changes in physicochemical properties and appearance quality of long-grain rice during the grinding process using image technologies and aimed to provide reference for future research. The brown rice milling process was divided into three stages, and flatbed scanning, scanning electron microscopy (SEM), X-ray micro-computed tomography (micro-CT), low-field nuclear magic resonance (LF-NMR), and headspace–gas chromatography–ion mobility spectrometry (HS–GC–IMS) were employed to examine the physicochemical and volatile properties of the samples. Results revealed a continuous increase in the degree of milling, with a broken rice rate and a whiteness value increasing by 50.84% and 21.13%, respectively, compared with those during the initial stage; dietary fiber and vitamin B1 contents were reduced by 54.41% and 66.67%, respectively. The image results visualized showed that the cortex of brown rice was gradually peeled off with the increase in milling degree; the cortical thickness was gradually reduced, the endosperm was gradually exposed, and the surface was smoother and shinier. T2 populations exhibited a shift toward longer relaxation times, followed by a decrease in relaxation time during the milling process. Additionally, 31 target compounds impacting rice flavor, mainly ketones, alcohols, and esters, were identified, and the concentration of volatile substances in the B region decreased with the reduction in the bran layer; the concentration of volatile substances in the C region provided rice flavor, which increased with the milling process. This study showed changes in the physicochemical properties and appearance quality of long-grain brown rice during milling. Furthermore, the use of various image processing techniques offers significant insights for optimizing processing parameters and enhancing overall quality and taste.

Sodium-Poor, Hydroxyl-Rich, Defective Na2Ti3O7 Prepared by γ-Irradiation and Its Enhanced Proton Conductivity.

The use of γ-irradiation to tailor the physicochemical properties of materials is not widely applied to layered alkali metal oxides. Herein, we show that γ-irradiation (up to 400 kGy) of Na2Ti3O7 leads to a sodium-poor, hydroxyl-rich analogue where the layered structure, plate-like morphology, and textural properties are preserved. The deintercalation of sodium ions modifies the Ti-O bond lengths and expands the unit cell; the latter is supported by density functional theory (DFT) calculations. 23Na solid-state NMR suggests the transport of the symmetric, 7-fold Na2 sites to an intermediate environment, which is closer to the asymmetric, 9-fold Na1 sites. An 8 wt % mass loss (1.4 mol water/mol titanate) is observed, indicating an increased concentration of protons/hydroxyls. These hydroxyl groups (i.e., lattice protons) possess higher thermal stability than solely surface-adsorbed ones in the nonirradiated sample. At 200-400 kGy, the proton conduction (50 °C and ∼70% RH) of ∼10-6 S·cm-1 is 1 order of magnitude larger than that in the nonirradiated sample; the relaxation time decreases from 30 to 2-6 μs with γ-irradiation. The γ-dose dependence of dielectric loss is also present and analyzed using the Jonscher universal power law, indicating the low-frequency dispersion behavior characteristics of high charge densities.

Feed Forward Modeling: an efficient approach for mathematical modeling of the force frequency relationship in the rabbit isolated ventricular myocyte

Background and Objective. This study addresses the Force-Frequency relationship, a fundamental characteristic of cardiac muscle influenced by β 1-adrenergic stimulation. This relationship reveals that heart rate (HR) changes at the sinoatrial node lead to alterations in ventricular cell contractility, increasing the force and decreasing relaxation time for higher beat rates. Traditional models lacking this relationship offer an incomplete physiological depiction, impacting the interpretation of in silico experiment results. To improve this, we propose a new mathematical model for ventricular myocytes, named ‘Feed Forward Modeling’ (FFM). Methods. FFM adjusts model parameters like channel conductance and Ca2+ pump affinity according to stimulation frequency, in contrast to fixed parameter values. An empirical sigmoid curve guided the adaptation of each parameter, integrated into a rabbit ventricular cell electromechanical model. Model validation was achieved by comparing simulated data with experimental current–voltage (I-V) curves for L-type Calcium and slow Potassium currents. Results. FFM-enhanced simulations align more closely with physiological behaviors, accurately reflecting inotropic and lusitropic responses. For instance, action potential duration at 90% repolarization (APD90) decreased from 206 ms at 1 Hz to 173 ms at 4 Hz using FFM, contrary to the conventional model, where APD90 increased, limiting high-frequency heartbeats. Peak force also showed an increase with FFM, from 8.5 mN mm−2 at 1 Hz to 11.9 mN mm−2 at 4 Hz, while it barely changed without FFM. Relaxation time at 50% of maximum force (t50) similarly improved, dropping from 114 ms at 1 Hz to 75.9 ms at 4 Hz with FFM, a change not observed without the model. Conclusion. The FFM approach offers computational efficiency, bypassing the need to model all beta-adrenergic pathways, thus facilitating large-scale simulations. The study recommends that frequency change experiments include fractional dosing of isoproterenol to better replicate heart conditions in vivo.

Free radical mechanisms of ammonium sulfate as intensively used industrial materials on suppressing organic pollutants

Organic free radicals are critical intermediates for the generation and inhibition of organic pollutants during industrial processes. Clarifying the free radical mechanism of pollutant inhibition is significant for their efficient control. Ammonium sulfate is intensively used in industrial materials to suppress organic pollutants. In this study, organic free radical intermediate species in metal-catalyzed reactions inhibited by ammonium sulfate were identified using continuous-wave electron paramagnetic resonance (EPR) spectroscopy, providing direct evidence for the free radical mechanisms of organic pollutants inhibition. The transverse (T2) and longitudinal (T1) relaxation time variations catalyzed by different metal catalysts in the presence of ammonium sulfate were compared using pulsed-wave EPR. Consequently, after the addition of ammonium sulfate, the observed increase in T2 suggests that ammonium sulfate leads to radical concentration reduction. A decrease in the T1 relaxation time suggests the enhanced interaction between organic radicals and metals, which is an obstacle to subsequent radical reactions. Therefore, ammonium sulfate dominantly changed the free radical intermediates species, concentrations, and their reactivity, and then inhibited the organic pollutants formations. The inhibition mechanisms of ammonium sulfate on metal-catalyzed pollutants were then proposed combining EPR analysis, X-ray characterization, and high-resolution mass spectrometry screening. As a result, (1) occupying the active sites of metal catalysis and (2) inhibiting free radical intermediates are the two main intrinsic inhibition mechanisms of ammonium sulfate. The findings provide new perspectives on the efficient inhibition of organic pollutants in industrial processes involving various metal catalysts.

Boltzmann's H-function for molecules with orientational degrees of freedom: Emergence of unique features.

Boltzmann's H-function H(t), often regarded as an analog of time-dependent entropy, holds a venerable place in the history of science. However, accurate numerical evaluation of H(t) for particles other than atoms is rare. To remove this lacuna, we generalize Boltzmann's H-function to a gas of molecules with orientational degrees of freedom and evaluate H(t) from the time-dependent joint probability distribution function f(p, L, t) for linear (p) and angular (L) momenta, evolving from an initial nonequilibrium state, by molecular dynamics simulations. We consider both prolate- and oblate-shaped particles, interacting via the well-known Gay-Berne potential and obtain the relaxation of the generalized molecular H(t) from initial (t = 0) nonequilibrium states. In the long-time limit, the H function saturates to its exact equilibrium value, which is the sum of translational and rotational contributions to the respective entropies. Both the translational and rotational components of H(t) decay nearly exponentially with time; the rotational component is more sensitive to the molecular shape that enters through the aspect ratio. A remarkable rapid decrease in the rotational relaxation time is observed as the spherical limit is approached, in a way tantalizingly reminiscent of Hu-Zwanzig hydrodynamic prediction with the slip boundary condition. In addition, we obtain H(t) analytically by solving the appropriate translational and rotational Fokker-Planck equation and obtain a modest agreement with simulations. We observe a remarkable signature of translation-rotation coupling as a function of molecular shape, captured through a physically meaningful differential term that quantifies the magnitude of translation-rotation coupling.

Photodynamic Therapy of Atherosclerotic Plaque Monitored by T1 and T2 Relaxation Times of Magnetic Resonance Imaging

Atherosclerosis, marked by plaque accumulation within arteries, results from lipid dysregulation, inflammation, and vascular remodeling. Plaque composition, including lipid-rich cores and fibrous caps, determines stability and vulnerability. Photodynamic therapy (PDT) has emerged as a promising treatment, leveraging photosensitizers to induce localized cytotoxicity upon light activation. PDT targets plaque components selectively, reducing burden and inflammation. Challenges remain in optimizing PDT parameters and translating preclinical success to clinical efficacy. Nonetheless, PDT offers a minimally invasive strategy for atherosclerosis management, promising personalized interventions for cardiovascular health. The objective of the current study was to present the findings from quantitative non-contrast MRI of atherosclerosis post-PDT by assessing relaxation times. The study aimed to utilize and optimize a 1.5T MRI system. Clinical scanners were used for MRI examinations. The research involved analyzing T1 and T2 relaxation times. Following treatment of the samples with Rose Bengal and exposure to pure oxygen, PDT irradiation was administered. The results indicated that the therapy impacted the crus, evidenced by a significant decrease in relaxation times in the MRI data.

Extracorporeal shockwave therapy for degenerative meniscal tears results in a decreased T2 relaxation time and pain relief: An exploratory randomized clinical trial.

The optimal management of degenerative meniscal tears remains controversial. Extracorporeal shockwave therapy (ESWT) has been shown to promote tissue repair in both preclinical and clinical studies; however, its effect on degenerative meniscal tears remains unknown. This study aimed to examine whether ESWT improves meniscal degeneration. This randomized trial was conducted between 2020 and 2022 and involved patients with degenerative medial meniscal tears. Patients were allocated to receive either focused ESWT (0.25 mJ/mm2, 2000 impulses, 3 sessions with a 1-week interval) or sham treatment. Patients were evaluated using magnetic resonance imaging (MRI) before treatment and at 12 months after treatment. The primary endpoint was improvement in meniscal degeneration, as assessed by the change in T2 relaxation time from baseline on MRI T2 mapping. Knee pain and clinical outcomes were also examined at the same time. Of 29 randomized patients, 27 patients (mean age 63.9 ± 8.7 years; females 37%; ESWT group 14 patients; control group 13 patients) were included in the final analysis. At 12 months postintervention, patients in the ESWT group showed a greater decrease in the T2 relaxation time (ESWT group -2.9 ± 1.7 ms vs. control group 1.0 ± 1.9 ms; p < 0.001) and had less knee pain (p = 0.04). The clinical outcomes at 12 months post-treatment were not statistically significant. No adverse events were reported. ESWT decreased the T2 relaxation time in the meniscus at 12 months post-treatment. ESWT also provided pain relief, but no differences were observed in clinical outcomes. Level II.

Modulating electrical response and impedance in Co–Cr substituted M-phase barium hexaferrites: Examining microstructure, grain boundaries, charge transport, and computational modeling

This study explores the influence of Co2+ and Cr3+ doping on the microstructure and electrical properties of Ba-hexagonal ferrite synthesized using the sol-gel method. X-ray diffraction (XRD) confirmed the formation of the anticipated hexagonal M-type crystal structure. Field emission scanning electron microscopy (FESEM) revealed the evolution of grain morphology with increasing doping levels, showcasing the formation of needle-like grains. Electrical characterization using an impedance analyzer investigated dielectric, impedance, electric modulus, and conductivity properties at room temperature. The analysis of the dielectric spectra indicated a decrease in dielectric constant and an increase in loss tangent with increasing dopant concentration. The electric modulus spectra provided evidence for non-Debye relaxation behavior, further supported by observations of relaxation processes at varying frequencies in the conductivity spectra. Additionally, an increase in doping led to a decrease in both relaxation time and AC conductivity. Electrochemical impedance spectroscopy (EIS) measurements yielded complex impedance curves. These curves exhibited good agreement with the values obtained through software-based simulations of grain and grain boundary characteristics. Furthermore, the distribution of grains and grain boundaries observed in FESEM micrographs aligned with the patterns predicted by the EIS software.

Effect of temperature on the drag reduction characteristics of xanthan gum in the liquid ring vacuum pump

Xanthan gum (XG) solution has been proven to be an effective working fluid in the liquid ring vacuum (LRV) pump to achieve significant energy savings. As an important influencing factor of the LRV pump performance, the effect of temperature on the drag reduction performance, rheological properties, and microstructure of XG solution in the LRV pump were experimentally investigated in this paper. The results indicate that with the increase of temperature, the drag reduction rate of the XG solution in the LRV pump initially rise and subsequently decline, and XG solutions with different concentrations show different optimal drag reduction temperatures. The microscopic parallel double-chain structure of XG has the same change pattern as the drag reduction performance, while the steady-state and dynamic shear characteristics of the XG solution manifest a downtrend. For instance, as the temperature of 4000 ppm XG solution increases from 10 °C to 60 °C, the drag reduction rate decreases by 20 %; the parallel double-chain structure decreases from 91.3 % to 89.9 %; the yield stress and relaxation time decrease from 4.63993 Pa to 4477.56 s to 3.37808 Pa and 143.27 s, respectively; the drag reduction rate reaches the maximum value when the temperature is 40 °C.

Impact of temperature on ophthalmic viscosurgical devices and clinical implications: a pilot study.

To evaluate how temperature affects the rheology of common ophthalmic viscosurgical devices (OVDs) and clinical implications. Tennent Institute of Ophthalmology, Glasgow, with Department of Mechanical and Aerospace Engineering, and Advanced Materials Research Laboratory, University of Strathclyde, Glasgow, United Kingdom. Laboratory pilot study. The viscous and elastic responses of 3 OVDs (Eyefill-SC/Eyefill-C/Eyefill-HD) were measured using rotational and extensional rheometers at clinically relevant temperatures (5°C, 25°C, 37°C). Thermal properties were evaluated using differential scanning calorimetry and laser-flash analysis. The OVDs tested exhibited viscoelastic properties and shear-thinning behavior. Apparent viscosities and relaxation time were higher at lower temperatures. The Eyefill-C and Eyefill-SC exhibited predominantly viscous character at low frequencies with a transition to predominantly elastic behavior at high frequencies. An increase in temperature led to a decrease in relaxation time under shear and extension. At low frequencies, Eyefill-C and Eyefill-SC moduli increase with decreasing temperatures. Eyefill-HD at 25°C and 37°C displays 2 crossover points, with the storage modulus dominating at low and high frequencies indicating a predominantly elastic behavior. Thermal property analysis revealed Eyefill-C had the lowest thermal conductivity. This pilot study confirms our clinical experience that OVD properties are affected by low temperatures, with increased viscosities at low shear rates and higher relaxation times. Cold OVD can cause greater resistance to initiation of intraocular lens (IOL) injection system forces (compared with warmer OVD). Excessively forced injection using cold OVD could contribute to inadvertent cannula detachment if incorrectly assembled, or uncontrolled IOL release leading to avoidable injury.

Effects of a medium cut-off dialyzer on inflammation and cardiac and vascular function in hemodialysis patients with heart failure.

Expanded hemodialysis (HDx) could provide clearance of larger middle-molecule uremic toxins. We compared the effect of hemodialysis with medium cut-off membranes and high-flux (HFHD) membranes regarding changes in inflammation and vascular and left ventricular function. This was a single-center, prospective, parallel-group comparative study. Patients were divided into two groups (HDx: 25 patients and HFHD: 26 patients). All measurements were performed at baseline and 12 weeks. Serum c-reactive protein, interkelukin-18, pentraxin-3, β-2 microglobulin, and brain natriuretic peptide were measured. We used pulse wave velocity and augmentation index to assess arterial stiffness and echocardiography to evaluate left and right ventricular function. We enrolled 51 patients. Although serum c-reactive protein, interkelukin-18, pentraxin 3, and β-2 microglobulin were significantly decreased in the HDx group (p = 0.02, p < 0.001, p = 0.002, and p = 0.02, respectively), there was no significant change in HFHD group at 12th week. Serum c-reactive protein and interkelukin-18were significantly lower in the HDx group compared to the HFHD group in the 12th week (p = 0.007 and p = 0.03, respectively). We observed a significant decrease in pulse wave velocity in the HDx group at the end of the study (p = 0.03). Although there was no significant change in pulse wave velocity in the HFHD group, pulse wave velocity was similar between the HDx and HFHD groups in the 12th week. We detected a significant decrease in the mean isovolumetric relaxation time in the HDx group (p = 0.006). However, there was no significant difference in isovolumetric relaxation time between the HDx and HFHD groups in the 12th week. HDx provides better clearance of middle molecular uremic toxins and inflammatory biomarkers, and it may be associated with better central hemodynamic parameters and diastolic functions.

In Situ Study on the Structural Evolution of Flexible Ionic Gel Sensors

With the development of society, the demand for smart coatings is increasing. The development of flexible strain sensors using block copolymer self-assembled ionic gel materials provides a promising method for promoting the development of smart coatings. The ionic liquid in the ionic part of the material is crucial for the performance of the sensor. In this study, the structural changes within FDA/dEAN (self-assembly of acrylated Pluronic F127 (F127-DA) in partially deuterated ethylammonium nitrate (dEAN)) triblock copolymer ionic gel during uniaxial tensile flow were characterized using an in situ SAXS technique. The results revealed that the characteristics of the responses of the ionic gel to strain resistance were intricately linked to the evolution of its microstructure during the tensile process. At low levels of strain, the face-centered cubic lattice arrangement of the micelles tended to remain unchanged. However, when subjected to higher strains, the molecular chains aligned along the stretching direction, resulting in a more ordered structure with reduced entropy. This alignment led to significant disruption in bridging structures within the material. Furthermore, this research explored the impact of the stretching rate on the relaxation process. It was observed that higher stretching rates led to decreases in the average relaxation time, indicating rate dependence in the microstructure’s behavior. These findings provide valuable insights into the behavior and performance of flexible strain sensors based on ionic gel materials in smart coatings.

Shear relaxation behavior for degraded polypropylene melt in torque rheometer

AbstractShear relaxation behavior for polymer melt exists in different processing techniques and influences the dimensional accuracy and production efficiency of polymer products. A micro physical and mathematical model based on microstructure of polymer chains and processing parameters was established and verified by experimental results obtained from a torque rheometer. The shear relaxation time of polypropylene degraded by di‐tert‐butyl peroxide was characterized with torque rheometer. The effects of microstructure and processing parameters on the shear relaxation time was investigated. The results showed that a wider molecular weight distribution could result in a decrease in shear relaxation time and polypropylene chains with higher molecular weight were more sensitive to molecular weight distribution. The shear relaxation time declined exponentially with shear rate and increased with internal pressure. The temperature could enhance the movement of polymer chains and reduce the shear relaxation time linearly, but polypropylene with lower molecular weight was less sensitive to temperature. The insight obtained from the mathematical and experimental results can be profoundly applied in practical process control to manufacture product with better dimensional stability and production efficiency for viscoelastic polymer.Highlights A physical and mathematical model based on microstructure and processing parameters of molecular chains was established to explore the shear relaxation mechanism. Shear relaxation time of polypropylene degraded by di‐tert‐butyl peroxide was characterized with the help of torque rheometer. The effects of microstructure and processing parameters on shear relaxation time was investigated to optimize the manufacturing of polypropylene products.

Longitudinal analysis of T2 relaxation time variations following radiotherapy for prostate cancer

Aim of this paper is to evaluate short and long-term changes in T2 relaxation times after radiotherapy in patients with low and intermediate risk localized prostate cancer. A total of 24 patients were selected for this retrospective study. Each participant underwent 1.5T magnetic resonance imaging on seven separate occasions: initially after the implantation of gold fiducials, the required step for Cyberknife therapy guidance, followed by MRI scans two weeks post-therapy and monthly thereafter. As part of each MRI scan, the prostate region was manually delineated, and the T2 relaxation times were calculated for quantitative analysis. The T2 relaxation times between individual follow-ups were analyzed using Repeated Measures Analysis of Variance that revealed a significant difference across all measurements (F (6, 120) = 0.611, p << 0.001). A Bonferroni post hoc test revealed significant differences in median T2 values between the baseline and subsequent measurements, particularly between pre-therapy (M0) and two weeks post-therapy (M1), as well as during the monthly interval checks (M2 - M6). Some cases showed a delayed decrease in relaxation times, indicating the prolonged effects of therapy. The changes in T2 values during the course of radiotherapy can help in monitoring radiotherapy response in unconfirmed patients, quantifying the scarring process, and recognizing the therapy failure.

Analyzing atomic scale structural details and nuclear spin dynamics of four macrolide antibiotics: erythromycin, clarithromycin, azithromycin, and roxithromycin.

The current investigation centers on elucidating the intricate molecular architecture and dynamic behavior of four macrolide antibiotics, specifically erythromycin, clarithromycin, azithromycin, and roxithromycin, through the application of sophisticated solid-state nuclear magnetic resonance (SSNMR) methodologies. We have measured the principal components of chemical shift anisotropy (CSA) parameters, and the site-specific spin-lattice relaxation time at carbon nuclei sites. To extract the principal components of CSA parameters, we have employed 13C 2DPASS CP-MAS SSNMR experiments at two different values of magic angle spinning (MAS) frequencies, namely 2 kHz and 600 Hz. Additionally, the spatial correlation between 13C and 1H nuclei has been investigated using 1H-13C frequency switched Lee-Goldburg heteronuclear correlation (FSLGHETCOR) experiment at a MAS frequency of 24 kHz. Our findings demonstrate that the incorporation of diverse functional groups, such as the ketone group and oxime group with the lactone ring, exerts notable influences on the structure and dynamics of the macrolide antibiotic. In particular, we have observed a significant decrease in the spin-lattice relaxation time of carbon nuclei residing on the lactone ring, desosamine, and cladinose in roxithromycin, compared to erythromycin. Overall, our findings provide detailed insight into the relationship between the structure and dynamics of macrolide antibiotics, which is eventually correlated with their biological activity. This knowledge can be utilized to develop new and more effective drugs by providing a rational basis for drug discovery and design.