Entropy Research Articles

Effect of the Total Saponins of Bupleurum chinense DC. Water Extracts Following Ultrafiltration Pretreatment on Macroporous Resin Adsorption.

Macroporous resin is an efficient separation technology that plays a crucial role in the separation and purification of traditional Chinese medicine (TCM). However, the application of macroporous resins in TCM pharmaceuticals is hindered by serious fouling caused by the complex materials used in TCM. This study examines the impact of ultrafiltration (UF) membrane technology on the macroporous resin adsorption behavior of TCM extracts. In this paper, Bupleurum chinense DC. (B. chinense) water extracts were included as an example to study the effect of UF pretreatment on the macroporous resin adsorption of total saponins. The study results indicated that the adsorption of total saponins constituents from the water extracts of B. chinense on the macroporous resin followed the pseudo-second-order kinetic model and the Langmuir model. The thermodynamic parameters of adsorption, including enthalpy changes and Gibbs free energies, were negative, while entropy changes were positive. These results demonstrated that the total saponin components form a monolayer adsorption layer by spontaneous thermal adsorption on the macroporous resin, and that the adsorption rate is not determined by the rate of intraparticle diffusion. Following treatment with a UF membrane with an average molecular weight cut-off of 50 kDa, the protein, starch, pectin, tannin, and other impurities in the water extracts of B. chinense were reduced, while the total saponin content was retained at 82.32%. The adsorption kinetic model of the saponin constituents on the macroporous resin remained unchanged and was consistent with both the second-order kinetic model and the Langmuir model; the adsorption rate of the second-order kinetic model increased by 1.3 times and in the Langmuir model at 25 °C, the adsorption performance improved by 1.16 times compared to the original extracts. This study revealed that UF technology as a pretreatment method can reduce the fouling of macroporous resin by TCM extracts and improve the adsorption performance of macroporous resin.

Binding of a Drug (Colchicine) to L-Asparaginase Enzyme Using Multispectroscopic, Thermodynamics, and Simulation Studies: Possible Implication in Acute Lymphoblastic Leukemia Treatment.

The research aims to elucidate how drug interactions affect the activity of L-asparaginase (L-ASNase), an essential enzyme in cancer treatment, especially for acute lymphoblastic leukemia (ALL). Understanding these interactions is crucial for optimizing treatment effectiveness and reducing adverse effects. This study explores the intricate molecular interactions and structural dynamics of L-ASNase upon binding with colchicine. Fluorescence quenching experiments were conducted at various temperatures (298, 303, and 310 K), revealing notable interactions between L-ASNase and colchicine. These interactions were characterized by a reduction in fluorescence intensity and a blue shift in emission maxima. Additional analyses, including the determination of Stern-Volmer quenching constants (KSV), bimolecular quenching rate constants (kq), and thermodynamic parameters, indicated a static quenching mechanism with moderate binding affinities (Ka: 1.40-2.71 × 104 M-1) across different temperatures. Thermodynamic study suggested positive enthalpy and entropy changes (ΔH° = -10.26 kcal mol-1; ΔS° = -14.19 cal mol-1 K-1), suggesting a spontaneous reaction with negative ΔG° values (-5.86 to -6.03 kcal mol-1). FRET measurements supported optimal distances (r and Ro) for FRET occurrence, reinforcing the static quenching mechanism. Molecular docking further supported these findings, revealing a 1:1 stoichiometric binding ratio for L-ASNase:colchicine and elucidating specific binding orientations and interactions critical for complex stability. Subsequent molecular dynamics simulations spanning 100 ns underscored the stability of the L-ASNase-colchicine complex, with minimal deviations observed in key structural parameters such as RMSD, RMSF, Rg, and SASA. Additionally, spectroscopic analyses, including circular dichroism (CD), synchronous fluorescence, and 3D fluorescence provided insights into the conformational changes and alterations in the microenvironment of aromatic amino acid residues in L-ASNase upon colchicine binding. Moreover, L-ASNase activity was slightly reduced by 25% in the presence of colchicine. This comprehensive investigation sheds light on the molecular intricacies of the L-ASNase-colchicine complex, advancing our understanding of drug-target interactions and offering potential avenues for therapeutic applications.

Studies of Kinetics and Non-Isothermal Decomposition of Synthesized Novel Organic Terpolymer Resin

Abstract: The terpolymer resin 2,4-DHP-4-PAF-III was prepared by condensation of 2,4-dihydroxypropiophenone, 4- pyridylamine and formaldehyde in the presence of 2M hydrochloric acid as a catalyst in the temperature range 125 ± 2 0C for 5 hrs in 3:1:5 molar ratios of reactants. Elemental analysis, FT-IR, and 1H-NMR spectral studies have been carried out to confirm the structure of the resin. The thermal degradation behavior of terpolymer was studied using thermogravimetric analysis (TGA) in air atmosphere at a heating rate of 10 0C/min. Sharp-Wentworth and Freeman-Carroll methods were used to calculate thermal activation energy (Ea), entropy change (∆S), free energy change (∆F), apparent entropy change (S*), frequency factor (Z) and order of reaction (n). Thermal activation energy (Ea) calculated by Sharp-Wentworth (28.81 KJ/mole) method and Freeman-Carroll (29.47 KJ/mole) method are in good agreement.

On the nonmagnetic atom disorder influence in the magnetic and magnetocaloric properties of the Er2Cu0.92Si2.76 off-stoichiometric single-phase compound

This paper presents and discusses material aspects, as well as the magnetic and magnetocaloric properties of nominal Er2Cu0.92Si2.76 alloy synthesized by arc melting. The stoichiometric alloy, prepared with a precise 2(Er):1(Cu):3(Si) ratio, adopts dual symmetries manifesting AlB2-type hexagonal and ThSi2-type tetragonal structures. It was observed that stoichiometric deviations by reducing both Cu/Si concentrations imply a decrease in the tetragonal phase fraction. An 8 % reduction in Cu and Si contents leads to the formation of an off-stoichiometric single-phase: the Er2Cu0.92Si2.76 phase - the focus of this investigation. Notably, Er2Cu0.92Si2.76 showed a uniform grain microstructure without porous and with a homogeneous elemental composition. On the other hand, a long-range antiferromagnetic ordering around 5.6 K was noticed, with a weak influence of magnetic frustration likely arising from nonmagnetic atomic disorder and vacancy at the Cu/Si site. An external magnetic field (greater than 10 kOe) induces ferromagnetic-like ordering, with a saturation tendency at ≈ 50 kOe, corresponding to half the expected magnetic moment for fully ordered Er3+ ions. Er2Cu0.92Si2.76 exhibits large magnetocaloric properties, with isothermal entropy change and relative cooling power values reaching 14.6 J/kgK and 312 J/kg, respectively, for a magnetic field change of 50 kOe. The absence of magnetic and thermal hysteresis is also an attractive prospect for this material aimed at magnetic refrigeration applications at low temperatures.

Structure, Optical Properties and Magnetocaloric Effects in Gd3Fe5O12 Garnet Synthesized by Solid State Method

In this work, gadolinium iron garnet (Gd3Fe5O12) was synthesized using the solid-state ceramic method. The structural analysis, confirmed through Rietveld refinement, indicated the formation of a single-phase garnet structure. Scanning electron microscopy studies revealed uniform grain size and homogeneity in the sintered material, while UV-vis absorption studies showed a peak at 300 nm, indicating strong ultraviolet interaction and an optical band gap of 3.64 eV, suggesting optoelectronic potential. The fluorescence emission spectrum shows a band at 435 nm, while the excitation spectrum exhibits bands at 275 and 360 nm. The magnetic measurements demonstrated Gd ion ordering at low temperatures, with a compensation temperature around 290 K. Arrott plots confirmed the second-order magnetic phase transition. Importantly, Gd3Fe5O12 exhibited both normal and inverse magnetocaloric effects, with a maximum magnetic entropy change of 1.05 J kg–1 K–1 at 230 K under 9 T magnetic field. These properties indicate Gd3Fe5O12 material as a promising candidate for magnetic refrigeration and optoelectronic applications.

Demonstration of efficient Thomson cooler by electronic phase transition.

In the 1850s, Lord Kelvin predicted the existence of a thermoelectric cooling effect inside a whole material (the Thomson effect) according to thermodynamics1, in addition to the Peltier effect that enables cooling at the junction between dissimilar materials. However, the Thomson effect is usually negligible (ΔT/T < 2%) in conventional thermoelectric materials because the entropy change in charge carriers is fairly small2, leading to the guiding principles for advancing thermoelectric cooling to be based on the framework of the Peltier effect and that the figure of merit ZT should be maximized to optimize performance. Here, we demonstrate a Thomson-effect-enhanced thermoelectric cooler using a large Thomson coefficient (τ) induced by the direct manipulation of charge entropy through an electronic phase transition in YbInCu4. The devices achieve a steady temperature span (ΔT) of >5 K from T = 38 K. Our findings suggest not only another approach to advance thermoelectric coolers in addition to improving ZT but also technologically opens opportunities for solid-state cryogenic cooling applications.

Co‐Pyrolytic Recycling of Bakelite and Polymethyl Methacrylate: Kinetic, Synergistic, and Thermodynamic Analysis

AbstractBakelite, a thermosetting plastic, has limited feasibility for thermal recycling processes such as pyrolysis, unlike thermoplastics, due to its inherent tendency to get charred upon heating and difficulty in being converted into valuable fuel and chemical compounds. In this study, the co‐pyrolysis of bakelite and poly methyl methacrylate is explored to improve the thermal degradation and thus recycling feasibility of bakelite by pyrolysis. The kinetics and thermodynamics of the co‐pyrolysis of blended samples are analyzed using different kinetics models. The thermal degradation experiments of the sample are conducted from ambient to 1000 °C at five various heating rates of 5, 10, 20, 30, and 50 °C/min in an inert N2 gas environment. The results showed that adding poly methyl methacrylate to bakelite changes the pyrolytic degradation temperature and weight loss trend. The kinetic analysis reveals that the thermal degradation at 220–345 °C follows an F2.5 order‐based model with an average activation energy of 181 kJ/mol, while the degradation at 345–475 °C follows an F2 order‐based model with an average activation energy of 318 kJ/mol. The enthalpy changes and free energy change associated with thermal degradation exhibit a positive trend while that of entropy change shows a negative trend. With blending the free energy change and entropy change decreased while enthalpy change increased. During batch pyrolysis at 450 °C, the PMMA‐Bakelite blend generates oil (49.17 %), wax (12.36 %), residue (15.36 %), and gas (23.11 %). According to FTIR and GC‐MS analyses, the pyrolytic oil produced by the co‐pyrolysis of the blended sample at 450 °C comprises 32.23 % saturated hydrocarbons (C9–40), 20.97 % unsaturated hydrocarbons (C6–24), and 46.80 % oxygenated material (C5–19). These findings can assist in the optimization of pyrolysis reactor design for the recycling of thermosetting plastics.

Phase behavior and interaction of strong polyelectrolyte dextran sulfate and whey protein isolation: Effects of pH, protein/polysaccharide ratio, and salt addition

The strong polyelectrolyte dextran sulfate (DS) is an anionic polysaccharide with a high negative charge, characterized by high stability and pH independence. DS and whey protein isolate (WPI) were selected to study the specific effects of highly negatively charged polysaccharides on the phase behavior and interaction of WPI/DS complexes (1 % w/v) under varying external conditions (pH, WPI:DS ratio, and salt addition). The phase diagrams, zeta potential, and laser confocal scanning microscopy measurements indicated that the WPI/DS complexes did not dissociate even at pH 1 due to the pH independence of DS. The exclusion volume effect of DS promoted WPI self-aggregation at high salt concentrations, which inhibited acidification-induced dissociation. Isothermal titration calorimetry indicated that the WPI/DS interaction is a spontaneous exothermic reaction driven by both enthalpy and entropy changes due to electrostatic interactions. This study provides valuable information on the interactions between highly negatively charged polysaccharides and proteins.

Interface-packing analysis of F1-ATPase using integral equation theory and manifold learning

It has been shown that the translational entropy of water plays a key role in biological processes such as protein folding and ligand binding. Under the physiological condition, tightly packed protein conformations like native structures are achieved so that the translational entropy of water is maximized. In this study, we investigate the rotation mechanism of a rotary protein motor, F1-ATPase, by analyzing the packing at the interfaces between the subunits. The packing at the interface between a subunit pair is analyzed using the change in the solvent entropy upon forming subunit pair, ∆S. It is found that as the γ subunit rotates, the ∆S value of a α-β subunit pair decrease because the interface packing becomes loose. However, because the interface packing of another α-β subunit pair becomes tighter upon the rotation, ∆S of this α-β subunit pair increases, leading to a compensation of the decrease in ∆S. Such compensation would be necessary to maximize the solvent entropy of F1-ATPase. In this study, packing at the interfaces between the subunits is also analyzed using a manifold-learning technique, and it is suggested a possibility that a qualitative estimation of the ∆S values of some α-β subunit pairs can be predicted using a manifold-learning technique.

Optimizing Room‐Temperature Thermoelectric and Magnetocaloric Performance via Constructing Multi‐Scale Interfacial Phases in LaFeSi/BiSbTe Thermo‐Electro‐Magnetic Refrigeration Materials

AbstractFabricating a thermo‐electro‐magnetic material that exhibits simultaneously excellent magnetocaloric (MC) and thermoelectric (TE) performance is challenging since the interfacial reaction causes severe deterioration of MC and TE performance. In this work, a construction of multi‐scale interfaces in LaFe10.4Co0.8Si1.8/Bi0.5Sb1.5Te3 (LFS/BST) composites is realized by adopting a low‐temperature high‐pressure sintering strategy. It is revealed in the atomic‐scale that the interfacial reaction between LFS and BST leads to the formation of (Fe,Co)(Sb,Te)2 micro‐grains and LaTe2 nano‐grains, and the latter form low‐mismatch phase boundaries with LFS matrix. Benefiting from the multi‐scale interfacial phases, excellent MC performance of LFS is preserved alongside a minor impact on TE properties, e.g., a peak zT of 1.04 and a small decrease of 3.0% in relative cooling power are achieved in the 2%LFS/BST composite. Compared with other thermo‐electro‐magnetic materials, a good trade‐off between MC and TE performance is realized in LFS/BST composites with simultaneously high MC and TE performance. The 20%LFS/BST composite exhibits a room‐temperature zT of 0.46 with large maximum magnetic entropy change and relative cooling power of 0.81 J kg−1 K−1 and 44.83 J kg−1, respectively. This work provides an effective material design for developing the all‐solid‐state MC/TE hybrid refrigeration technique.

A point of view of the elastocaloric effect associated with 7M and 5M modulated martensite in Ni–Mn–Ga alloys

Solid-state refrigeration has emerged as the most promising alternative to conventional refrigeration technology. However, for this technology to be applicable, the caloric effects produced in the alloys must be highly reversible. In this context, we compare the elastocaloric effect of two Ni–Mn–Ga alloys with different types of modulated martensite. The elastocaloric effect, quantified as the isothermal entropy change (ΔSela), was investigated in Ni50Mn28Ga22 and Ni50Mn30Ga20 alloys with 5M and 7M modulated martensite, respectively. Maximum ΔSela values obtained were 1.91 J kg−1 K−1 during cooling and 1.83 J kg−1 K−1 during heating in martensite 5M and 0.19 J kg−1 K−1 during cooling and 0.26 J kg−1 K−1 during heating in martensite 7M, for a constant applied stress of 10 MPa. However, although the 7M modulated martensite exhibited a lower ΔSela, its reversibility was higher. Therefore, our results could be useful for selecting a good material to be used in solid-state refrigeration.

Magnetocaloric and Magnetostrictive Properties of the Tb(Co,In)&lt;sub&gt;2&lt;/sub&gt; Laves Phases

Multicomponent polycrystalline TbInxCo2–x (with х = 0–0.2) solid solutions are prepared for the first time, and their crystal structure and magnetic, magnetocaloric, and magnetostrictive properties are studied. X-ray diffraction patterns taken at room temperature demonstrate mainly the presence of the cubic C15 Laves phase in all samples. As the indium content increases to x = 0.1, the lattice parameter is found to increase; the further increase in the indium content to х = 0.2 leads to a decrease in the lattice parameter. In this case, the Curie temperature TC monotonically increases to 245 K. The isotheral magnetic entropy change ΔSmag is calculated in accordance with magnetic measurements using the thermodynamic Maxwell’s relation. At a magnetic field change from 0 to 1.8 T, the maximum entropy change monotonically decreases and, for composition with x = 0.2, is 1.8 J/(kg∙К). As the indium content increases to x = 0.05, the volume magnetostriction increases. The further increase in the indium concentration leads to the decrease in the peak values and their shift to high temperatures.

Entropically driven binding of Camptothecin in the minor groove of salmon testes DNA

The present study focuses on binding association of Camptothecin (CMT) towards natural deoxy-ribonucleic acid (salmon testes, ST) under physiological conditions of pH 7.4. Extensive spectroscopic and computational techniques have been employed to elucidate thermodynamics of the said interaction. UV and fluorescence analyses portrays significant intensity changes (hyper-chromic and hypsochromic) in the spectra, which confirms effective CMT binding to ST DNA. The McGhee-von Hipple method and Scatchard plot analyses estimated the binding affinities in 105 M−1 range. Associated thermodynamic data revealed spontaneous and exothermic nature of binding. Temperature-dependent fluorescence showed negative change in enthalpy and positive change in entropy, leading to the formation of a 1:1 adduct. Non-polyelectrolytic forces appeared to be the driving force of the ligand-DNA interaction, according to salt-dependent fluorescence. Dye displacement assay, viscosity study, DNA melting, iodide quenching, urea denaturation assay examined the minor groove nature of CMT. In silico docking study examined precise molecular representations of the minor groove binding mechanism that formed between the complex, and the study's findings were consistent with the experimental results. Simulation studies also validated the experimental analysis and docking data. These findings could expedite the process of creating new and improved CMT molecular derivatives and help in the creation of DNA-targeted medicines, which may be beneficial from a pharmaceutical point of view.

Patterns of interaction between peptides of various structures and pyrimidine nucleic bases in a buffered saline medium according to the analysis of thermodynamic parameters

Complexation of cytosine, uracil and thymine with the dipeptides glycyl-glycine, glycyl-l-phenylalanine, alanyl-l-glutamine and with the tripeptide γ-l-glutamyl-l-cysteinyl-glycine in a buffered saline has been studied using dissolution calorimetry. The values of the reaction constant, the change in Gibbs energy, enthalpy, and entropy have been found (log Kr, ΔrG, ΔrH, TΔrS). By analyzing the obtained data together with previous results for other peptides, it was found that peptides bind to pyrimidine nucleic bases in a solution in several important patterns. No pattern depending on the charge of the peptide is observed in the obtained thermodynamic values, which indicates a minor role of electrostatic interaction in their binding by the nucleic base. The effect of the structure of the peptide and the nucleobase on the thermodynamic parameters of complexation is manifested in the fine balance of the enthalpy and entropy factors of the process. The Gibbs energy of complexation depends on the number of potential H-bonding sites of the peptide, which shows the major contribution of H-bonding between the reagents. The reduction in the favorable entropy factor is responsible for the tendency of negative ΔrG values to decrease with increasing number of sites. It was found that positive values of entropy change during complex formation increase with increasing hydrophobicity index of the peptide, which is interpreted within the framework of the overlapping hydration sphere model. Strengthening the hydrophobic properties of the nucleic base from uracil to thymine due to the additional CH3 group slightly changes the enthalpy and entropy of the process of binding the +AlaGln− zwitterion but significantly affects the thermodynamic parameters of binding the anion of peptide +/−GluCysGly−.

Excellent Magnetocaloric Properties near 285 K of Amorphous Fe88Pr6Ce4B2 Ribbon

A novel amorphous Fe88Pr6Ce4B2 ribbon with better magnetocaloric properties near 285 K is reported in the present work. The Fe88Pr6Ce4B2 ribbon exhibits a typical second-order ferromagnetic–paramagnetic transition near its Curie temperature (Tc, ~284 K), with a maximum magnetic entropy change (−ΔSmpeak) of ~4.15 J/(kg × K) under 5 T and a maximum adiabatic temperature rise (ΔTad) of ~2.57 K under 5 T, both of which are almost the largest amongst the iron-based metallic glasses with Tc = 285 ± 10 K. The high −ΔSmpeak enables several amorphous hybrids with table-like −ΔSm–T curves to be synthesized by appropriately proportioning the Fe88Pr6Ce4B2 ribbon and other amorphous ribbons with different Tc. The larger average −ΔSm and effective refrigeration capacity, as well as the appropriate temperature range, make the two amorphous hybrids potential candidates for use as refrigerants in household magnetic air conditioners.

Magnetic properties and magnetocaloric effect in thiospinel Fe1-xCuxCr2S4 (x = 0.0, 0.5) compounds

In this study, we investigate the magnetic and magnetocaloric properties of Cr-based spinel sulphides Fe1-xCuxCr2S4 (x = 0.0 and x = 0.5). The magnetic transition temperature of FeCr2S4 (176 K) increases to 330 K when 50 % of Fe in FeCr2S4 structure is substituted with Cu. Temperature-dependent Zero-Field-Cooled (ZFC) and Field-Cooled (FC) magnetic moment measurements show a paramagnetic (PM) to ferrimagnetic (FiM) phase transition in our samples. Magnetocaloric properties were investigated through magnetization isotherm measurements. The maximum magnetic entropy change values are −2.78 J/kg. K and −2.11 J/kg. K under 5 T magnetic field, for x = 0 and x = 0.5 in Fe1-xCuxCr2S4, respectively. Analysis of phenomenological universal curves and Arrott plots indicate a second-order magnetic transition for both compounds. Consequently, Fe0.5Cu0.5Cr2S4 emerges as a promising candidate for magnetic refrigeration applications due to its considerable high magnetic entropy change and its proximity to room temperature transition.

Quasi-isothermal magnetocaloric effect in the DyAl2 alloy in magnetic field up to 14 T

Experimental and analytical studies were carried out on the magnetocaloric effect (MCE) in the rare-earth alloy of the Laves phase DyAl2, which has the second-order magnetic phase transition (PT) in the region of cryogenic temperatures. The measurements are carried out using an extraction magnetic calorimeter with a Bitter electromagnet. A polycrystalline DyAl2 sample was synthesized followed by heat treatment. X-ray diffraction and elemental chemical analyzes are provided. The magnetization of the sample was measured in magnetic fields up to 13.5T. Calculations of the entropy changes of the magnetic subsystem ΔSmag are provided. Measurements of the MCEs ΔT − effect in adiabatic and ΔQ − effect in quasi-isothermal conditions were carried out. The MCE investigated by direct method in the temperature range of 15–110 K and magnetic field up to 14 T. It was found that the maximum of the adiabatic MCE in the region of the Curie temperature of the DyAl2 alloy under adiabatic magnetization in a magnetic field of 14T is ΔT = 12.94K. The obtained values are well approximated by the ΔT∼ΔH2/3, The maximum value of the quasi-isothermal MCE is ΔQ = 3.1kJ/kg. The value corresponds to the maximum of the entropy change of the magnetic subsystem ΔSmag = 32.3J/(kg*K). The influence of thermal contact resistance (TCR) on the results of measuring the MCE under quasi-isothermal conditions is assessed.

Magnetic and magnetocaloric dynamics in [formula omitted] double perovskites: Impact of A and B site variations analyzed through Monte Carlo simulation and Ab initio calculations

We investigate the magnetic and magnetocaloric properties of the double perovskites Sr2FeOsO6,Sr2FeCoO6,Dy2FeOsO6 and Dy2FeCoO6 using a combination of Monte Carlo simulations and Density Functional Theory (DFT). The exchange couplings were calculated using DFT. Sr2FeOsO6 exhibits antiferromagnetic ordering with two transitions at 50 and 150 K, driven by strong antiferromagnetic exchange interactions between Fe³⁺ and Os⁵⁺ ions. In contrast, Sr2FeCoO6 shows ferrimagnetic behavior with a single transition around 75 K, attributed to ferromagnetic coupling between Co2⁺ and Fe³⁺ ions. For the rare-earth-containing compounds, Dy2FeOsO6 demonstrates complex magnetic ordering with transitions at approximately 20 K and 140 K, influenced by the strong spin-orbit coupling of Dy³⁺ ions. Similarly, Dy2FeCoO6 exhibits two transitions at around 60 K and 170 K, reflecting a mix of ferromagnetic and antiferromagnetic interactions involving Dy³⁺, Co2⁺, and Fe³⁺ ions. Sr2FeOsO6 shows a peak magnetic entropy change ΔSm of 0.22 J/kg.K under a 5 T field at 50 K, while Sr2FeCoO6 exhibits a broader peak at 75 K with ΔSm of 1.5 J/kg·K. Dy2FeOsO6 presents significant ΔSm peaks at 20 K and 140 K, reaching 1.9 J/kg·K under a 5 T field. Dy2FeCoO6 displays the highest ΔSm of 4.0 J/kg·K at 60 K.

Magnetocaloric effect, magnetotransport and magnetic properties of polycrystalline Pr(0.65-x)GdxSr0.35MnO3 (x ≤ 0.3) compounds

Polycrystalline Pr0.65-xGdxSr0.35MnO3 (x = 0.01, 0.05, 0.1, 0.2, 0.3) manganites were prepared by conventional solid-state method. Structural analysis has revealed a change in structure with x = 0.2, from Rhombohedral (R-3c) to Orthorhombic (Pbnm) symmetry. Small oxygen deficiency was found in the samples. The electrical measurements revealed typical colossal magnetoresistance (CMR) behavior, with single metal–insulator peak at Tp for all investigated samples. The small polaron hopping (SPH) and variable-range hopping (VRH) models were used to describe the electrical conduction above Tp. Magnetic measurements show an increase in magnetization below the Curie temperature, TC. Values of Tc diminish with increasing Gd3+ content. Isothermal measurements around critical points suggest a possible interaction between the 4f-ions and Mn-sublattice The magnetic critical behavior analysis established the tri-critical mean-field model to be the governing model for the series. Large magnetic entropy change ΔSM at near room temperature (278 K) was exhibited by the x = 0.01 sample at 2.2 J/kgK in μ0ΔH = 1 T and 5.36 J/kgK in μ0ΔH = 4 T. The largest |ΔSM| value was shown by the x = 0.1 sample. The values of the relative cooling power (RCP) and the temperature-averaged entropy change (TEC) increased with substitution qualifying these compounds as magnetocaloric materials.

Contrasting behavior of urea in strengthening and weakening confinement effects on polymer collapse.

Biomolecules inhabit a crowded living cell that is packed with high concentrations of cosolutes and macromolecules that result in restricted, confined volumes for biomolecular dynamics. To understand the impact of crowding on the biomolecular structure, the combined effects of the cosolutes (such as urea) and confinement need to be accounted for. This study involves examining these effects on the collapse equilibria of three model 32-mer polymers, which are simplified models of hydrophobic, charge-neutral, and uncharged hydrophilic polymers, using molecular dynamics simulations. The introduction of confinement promotes the collapse of all three polymers. Interestingly, addition of urea weakens the collapse of the confined hydrophobic polymer, leading to non-additive effects, whereas for the hydrophilic polymers, urea enhances the confinement effects by enhancing polymer collapse (or decreasing the polymer unfolding), thereby exhibiting an additive effect. The unfavorable dehydration energy opposes collapse in the confined hydrophobic and charge-neutral polymers under the influence of urea. However, the collapse is driven mainly by the favorable change in polymer-solvent entropy. The confined hydrophilic polymer, which tends to unfold in bulk water, is seen to have reduced unfolding in the presence of urea due to the stabilizing of the collapsed state by urea via cohesive bridging interactions. Therefore, there is a complex balance of competing factors, such as polymer chemistry and polymer-water and polymer-cosolute interactions, beyond volume exclusion effects, which determine the collapse equilibria under confinement. The results have implications to understand the altering of the free energy landscape of proteins in the confined living cell environment.