Search Results (183)

Protein–polyelectrolyte nanostructures assembled via electrostatic interactions offer versatile applications in biomedicine, tissue engineering, and food science. However, several open questions remain regarding their intermolecular interactions and the influence of external conditions—such as temperature and pH—on their assembly, stability, and responsiveness. This study explores the formation and stability of networks between poly(acrylic acid) (PAA) and lysozyme (LYZ) at the nanoscale upon thermal treatment, using a combination of experimental and simulation measures. Experimental techniques of static and dynamic light scattering (SLS and DLS), Fourier transform infrared spectroscopy (FTIR), and circular dichroism (CD) are combined with all-atom molecular dynamics simulations. Model systems consisting of multiple PAA and LYZ molecules explore collective assembly and complexation in aqueous solution. Experimental results indicate that electrostatic complexation occurs between PAA and LYZ at pH values below LYZ’s isoelectric point. This leads to the formation of nanoparticles (NPs) with radii ranging from 100 to 200 nm, most pronounced at a PAA/LYZ mass ratio of 0.1. These complexes disassemble at pH 12, where both LYZ and PAA are negatively charged. However, when complexes are thermally treated (TT), they remain stable, which is consistent with earlier findings. Atomistic simulations demonstrate that thermal treatment induces partially reversible structural changes, revealing key microscopic features involved in the stabilization of the formed network. Although electrostatic interactions dominate under all pH and temperature conditions, thermally induced conformational changes reorganize the binding pattern, resulting in an increased number of contacts between LYZ and PAA upon thermal treatment. The altered hydration associated with conformational rearrangements emerges as a key contributor to the stability of the thermally treated complexes, particularly under conditions of strong electrostatic repulsion at pH 12. Moreover, enhanced polymer chain associations within the network are observed, which play a crucial role in complex stabilization. These insights contribute to the rational design of protein–polyelectrolyte materials, revealing the origins of association under thermally induced structural rearrangements. Full article

This paper investigates the interplay between rubber network damage, carbon black (CB) network damage, heat exchange, and voiding mechanisms in filled Styrene-butadiene rubber (SBR) under cyclic loading. To do so, three carbon black filled SBR composites, SBR5, SBR30 and SBR60 are studied. The study aims to quantify molecular damage and its role in inducing reversible or irreversible heat flow and voiding behavior to inform the design of more resilient rubber composites with improved fatigue life and thermal management capabilities. The study effectively demonstrated how increasing carbon black content, particularly in SBR60, leads to a shift from mostly reversible to irreversible and cumulative damage mechanisms during cyclic loading, as evidenced by thermal, volumetric, and electrical resistivity changes. In particular, we identify a critical mechanical energy of 7 MJ.m⁻³ associated with such transition. These irreversible changes are strongly linked to the damage and re-arrangement of the carbon black filler network, as well as the rubber chains network and the formation/growth of voids, while reversible mechanisms are likely related to rubber chains alignment associated with entropic elasticity. Full article

Cold environments challenge the structural and functional integrity of membrane proteins, requiring specialized adaptations to maintain activity under low thermal energy. Here, we investigate the molecular basis of cold tolerance in the peptide transporter PepT1 from the Antarctic icefish (Chionodraco hamatus, ChPepT1) using molecular dynamics simulations, binding free energy calculations (MM/GBSA), and dynamic network analysis. We compare ChPepT1 to its human ortholog (hPepT1), a non-cold-adapted variant, to reveal key features enabling psychrophilic function. Our simulations show that ChPepT1 displays enhanced global flexibility, particularly in domains adjacent to the substrate-binding site and the C-terminal domain (CTD). While hPepT1 loses substrate binding affinity as temperature increases, ChPepT1 maintains stable peptide interactions across a broad thermal range. This thermodynamic buffering results from temperature-sensitive rearrangement of hydrogen bond networks and more dynamic lipid interactions. Importantly, we identify a temperature-responsive segment (TRS, residues 660–670) within the proximal CTD that undergoes an α-helix to coil transition, modulating long-range coupling with transmembrane helices. Dynamic cross-correlation analyses further suggest that ChPepT1, unlike hPepT1, reorganizes its interdomain communication in response to temperature shifts. Our findings suggest that cold tolerance in ChPepT1 arises from a combination of structural flexibility, resilient substrate binding, and temperature-sensitive interdomain dynamics. These results provide new mechanistic insight into thermal adaptation in membrane transporters and offer a framework for engineering proteins with enhanced functionality in extreme environments. Full article

Background/Objectives: This study investigates the impact of high humidity (25 °C, 75% relative humidity) on gelatin and hydroxypropyl methylcellulose (HPMC) capsules used in dry powder inhalers (DPIs), focusing on moisture dynamics, structural responses, and mechanical performance, with an emphasis on understanding how different capsule types respond to prolonged exposure to humid conditions. Methods: Capsules were exposed to controlled humidity conditions, and moisture uptake was measured via thermal analysis. Visual observations of silica bead color changes were performed to assess moisture absorption, while surface wettability was measured using the sessile drop method. Hardness testing, mechanical deformation, and puncture tests were performed to evaluate structural and mechanical changes. Positron annihilation lifetime spectroscopy (PALS) was used to analyze free volume expansion. Results: HPMC capsules exhibited rapid moisture uptake, attributed to their lower equilibrium moisture content and ability to rearrange dynamically, preventing brittleness. In contrast, gelatin capsules showed slower moisture absorption but reached higher equilibrium levels, resulting in plasticization and softening. Mechanical testing showed that HPMC capsules retained structural integrity with minimal deformation, while gelatin capsules became softer and exhibited reduced puncture resistance. Structural analysis revealed greater free volume expansion in HPMC capsules, consistent with their amorphous nature, compared with gelatin’s semi-crystalline matrix. Conclusions: HPMC capsules demonstrated superior humidity resilience, making them more suitable for protecting moisture-sensitive active pharmaceutical ingredients (APIs) in DPI formulations. These findings underline the importance of appropriate storage conditions, as outlined in the Summary of Product Characteristics, to ensure optimal capsule performance throughout patient use. Full article

This work investigated the structural response and phase transformation dynamics of silica-bearing cherts subjected to high-temperature processing (up to 1400 °C) and prolonged mechanochemical activation. Through a combination of X-ray diffraction (XRD) with Rietveld refinement, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and transmission electron microscopy (HRTEM), we trace the crystallographic pathways of quartz, moganite, tridymite, and cristobalite under controlled thermal and mechanical stress regimes. The experimental results demonstrated that phase behavior is highly dependent on intrinsic properties such as initial phase composition, impurity presence, and crystallinity. Heating at 1400 °C induced irreversible conversion of quartz, moganite, and tridymite into cristobalite. Samples enriched in cristobalite and tridymite exhibited notable increases in crystallinity, whereas quartz-dominant samples showed either stability or a decline in structural order. Rietveld analyses underscored the critical influence of microstrain and crystallite size on thermal resilience and phase persistence. Thermal profiles revealed by DSC and TGA expose overlapping processes including polymorphic transitions, minor phase dehydration, and redox-driven changes, likely associated with trace components. Mechanochemical processing resulted in partial amorphization and the emergence of phases such as opal and feldspar minerals (microcline, albite, anorthite), interpreted as the product of lattice collapse and subsequent reprecipitation. Heat treatment of chert leads to a progressive rearrangement and recrystallization of its silica phases: quartz collapses around 1000 °C before recovering, tridymite emerges as an intermediate phase, and cristobalite shows the greatest crystallite size growth and least deformation at 1400 °C. These phase changes serve as markers of high-temperature exposure, guiding the identification of heat-altered lithic artefacts, reconstructing geological and diagenetic histories, and allowing engineers to adjust the thermal expansion of ceramic materials. Mechanochemical results provide new insights into the physicochemical evolution of metastable silica systems and offer valuable implications for the design and thermal conditioning of silica-based functional materials used in high-temperature ceramics, glasses, and refractory applications. From a geoarchaeological standpoint, the mechanochemically treated material could simulate natural weathering of prehistoric chert tools, providing insights into diagenetic pathways and lithic degradation processes. Full article

1,2,4-Cyclohexatrienes are strained, reactive intermediates often formed by the tetradehydro-Diels–Alder (TDDA) reaction of a conjugated enyne bearing a tethered alkyne as the enynophile. The ene component is commonly the π-bond of an aromatic group. In this focused study, we investigated the reactivity of a symmetrical substrate in which the pair of terminal ene moieties were simple 2-propenyl groups. The intermediate 1,2,4-cyclohexatriene, now bearing a 5-isopropenyl group, underwent competitive aromatization (the most usual outcome of the strain-relieving event of the cyclohexatriene), along with an intramolecular [1,5]-hydrogen atom migration, ultimately producing a non-benzenoid, pyrrole derivative. This represents a previously unknown process for a 1,2,4-cyclohexatriene derivative. Mechanistic aspects of the competitive processes were revealed by experiments performed in the presence of various protic additives (MeOD and BHT). Full article

First demonstrated in 1942, subcritical and zero-power critical assemblies, also known as piles, are a fundamental tool for research and education at universities. Traditionally, their role has been primarily instructional and for measuring the fundamental properties of neutron diffusion and transport. However, these assemblies could hold potential for modern applications and nuclear research. The Purdue University subcritical pile previously lacked a substantial testing volume, limiting its utility to simple neutron activation experiments for the purpose of undergraduate education. Following the design and addition of a mechanical and electrical testbed, this paper aims to provide an overview of the testbed design and characterize the neutron flux of the rearranged Purdue subcritical pile, justifying its use as a modern scientific instrument. The newly installed 1.5 × 10⁵ cubic-centimeter volume testbed enables a systematic investigation of neutron and gamma effects on materials and the generation of a comprehensive data set with the potential for machine learning applications. The neutron flux throughout the pile is measured using gold-197 and indium-115 foil activation alongside cadmium-covered foils for two-group neutron energy classification. The neutron flux measurements are then used to benchmark a detailed geometrically and materialistically accurate Monte Carlo model using OpenMC 0.15.0 and MCNP 6.3. The experimental measurements reveal that the testbed has a neutron environment with a total neutron flux approaching 9.5 × 10³ n/cm² × s and a thermal flux of 6.5 × 10³ n/cm² × s. This work establishes that the modified Purdue subcritical pile can provide fair neutron and gamma fluxes within a large volume to enable the radiation testing of integral electronic components and can be a versatile research instrument with the potential to support material testing and limited isotope activation, while generating valuable training data sets for machine learning algorithms in nuclear applications. Full article

In contrast to traditional hydrogels, which are susceptible to water evaporation and structural degradation, non-hydrogel materials are engineered for superior stability and consistent performance. Here, we report an innovative piezoelectric polyvinyl chloride/multi-walled carbon nanotube polymer gel (PVC/MWCNT polymer gel, PMPG) with exceptional linearity (as low as 1.31%), high sensitivity (50–310.17 mV), rapid response (172–189 ms), and thermal stability. Under strain induction, ordered rearrangement of dipoles in PMPG and the enhancement of MWCNTs generate a potential difference. Increasing MWCNT content enhances output voltage, sensitivity, conductivity, maximum stress, Young’s modulus, and toughness, while reducing nonlinear error. Higher dibutyl adipate (DBA) content increases output voltage and slightly improves sensitivity but decreases mechanical strength. The optimal PMPG (PVC:DBA = 1:5, 1 wt% MWCNTs) exhibited outstanding performance. It exhibits a nonlinear error as low as 1.31%, a conductivity of 25.4 μS/cm, an 80% compressive strain tolerance (273 kPa stress), and dimensional stability for 90 days in air. By integrating PMPG with machine learning algorithms, soft robotic grippers gain advanced contact perception capabilities, enabling applications in medicine, rescue, exploration, and other fields requiring fine manipulation and adaptability. This work highlights PMPG’s potential as a stable, high-performance material for soft robotics and beyond. Full article

The influence of aging and thermal shock processes on polymer coating reinforced with various rubber fillers on an aluminum substrate was investigated. The coatings were made from a polyurethane matrix and two different reinforcement materials: EPDM and SBR rubber waste fillers. The samples were subjected to 100 thermal shock cycles. Each cycle lasted 1 h, comprising 30 min at 100 °C followed by 30 min at 40 °C. The aging tests were conducted in a SUNTEST XLS+ aging chamber from Atlas Material Testing Technology GmbH, in accordance with the applicable ISO 4892-1:2016 standard. Thermal shocks increased the impact resistance of coatings with EPDM and SBR fillers. Neither UV aging nor thermal shocks affected the impact or abrasion resistance of unfilled polyurethane coatings. FTIR analysis revealed that UV exposure significantly accelerates chemical degradation of PUR, though fillers—especially EPDM—enhanced stability by mitigating this effect. Thermal shocks induced surface-level changes, including the formation of oxygenated groups and the rearrangement of hydrogen bonds. Rubber waste fillers influenced surface and thermal properties, with EPDM maintaining better hydrophobicity and oxidation resistance, while SBR-filled coatings demonstrated higher thermal stability but greater flexibility and susceptibility to degradation after aging. Full article

This paper presents novel soluble (co)poly(hydroxyimide)s ((co)PIOH) based on 4,4′-oxydiphthalic anhydride (ODPA), 3,3′-dihydroxybenzidine (HAB), and 3,6-diaminodurene (D) with the 3/1, 1/1, and 1/3 HAB/D ratios. This chemical structure of the compounds provides the possibility of their future modification through the thermal rearrangement (polybenzoxazoles) or functionalization via Mitsunobu reaction (azo side-chain polyimides), i.e., obtaining new materials with interesting properties and therefore with expanded applications. Copolymers were characterized via FTIR, NMR, XRD, and GPC methods to confirm their structure, composition, and molar masses. The effect of copolymer composition on the thermal, mechanical, optical, and permeation properties studied for He, O₂, N₂, and CO₂, as well as hydrophobicity, was investigated. They exhibited a large interval between the glass transition temperature and the decomposition temperature, making them promising for the thermoforming technique. Transmittance above 90% was noted in the visible range for all (co)PIOH films deposited on a glass substrate. Young’s modulus of fabricated membranes was in the range of 2.37 to 3.38 GPa. The highest permeability coefficients were recorded for (co)PIOH with a 1:3 HAB-to D-ratio. Full article

Laser annealing plays a significant role in the fabrication of scaled-down semiconductor devices by activating dopant ions and rearranging silicon atoms in ion-implanted silicon wafers, thereby improving material properties. Precise temperature control is crucial in wafer annealing, particularly for repeated processes where repeatability affects uniformity. In this study, we employ a three-dimensional time-dependent thermal simulation model to numerically analyze the multiple static laser annealing processes based on a CO₂ laser with a center wavelength of 9.3 μm and a pulse repetition rate of 10 kHz. The heat transfer equation is solved using a multiphysics coupling approach to accurately simulate the effects of different numbers of CO₂ laser pulses on wafer temperature rise and repeatability. Additionally, a pyrometer is used to collect and convert the surface temperature of the wafer. Radiation intensity is converted to temperature via Planck’s law for real-time monitoring. Post-processing is performed to fit the measured temperature and the actual temperature into a linear relationship, aiding in obtaining the actual temperature under small beam spots. According to the simulation conditions, a wafer annealing device using a CO₂ laser as the light source was independently built for verification, and a stable and uniform annealing effect was realized. Full article

The eco-friendly flame retardancy of polycarbonate (PC) was achieved by blending with phosphorylated-PC in the range of 1–5% w/w. Dynamic properties were characterized using broadband dielectric relaxation spectroscopy (DRS), while structural and thermal properties were investigated using Fourier transform infrared spectroscopy, wide-angle X-ray diffraction, small-angle X-ray scattering, differential scanning calorimetry, and thermogravimetric analysis. A reduction in the single glass transition temperature with increasing phosphorylated-PC content was observed, indicating that the blends were miscible. No crystalline phases were detected in any of the samples. The thermo-oxidative stability and UL-94 ratings of flame-retardant polycarbonates (FRPCs) improved compared to neat PC, with char residue increasing as the phosphorylated-PC content rose. DRS analysis revealed the formation of a well-defined local (β) relaxation in the FRPC samples, originating from the motion of phosphorylated branches. All samples exhibited the segmental (α) relaxation of PC chains above the glass transition temperature. The size of the cooperatively rearranging domain played a significant role in the dynamic fragility of the rigid FRPCs. Additionally, DRS analysis highlighted the presence of physical crosslinks from nanoclusters of phosphorylated polar groups, approximately 14 nm in size. Full article

Herein, the effectiveness of astaxanthin (AX) as functional feed ingredient was assessed by enhancing its stability and bioavailability using encapsulation methods. Spray-drying and liposome entrapment were applied to a natural AX source from shrimp by-products, along with two commercially synthetic alternatives. Encapsulated AX formulations were evaluated for their physico-chemical properties, thermal stability, and in vitro performance using RTL-W1, a rainbow trout (Oncorhynchus mykiss) liver-derived cell line. Both techniques achieved high encapsulation efficiency (73–89%) and provided remarkable protection to AX during thermal treatments, maintaining its stability at 80 °C for up to 2 h and at 100 °C for 30 min. Nevertheless, neither encapsulation methods significantly mitigated water absorption over time. Additionally, morphological characterization revealed spray-dried microcapsules with typical round, partially collapsed particles with a broad size distribution, while liposomes further stabilized into dry powders by spray-drying showed structural rearrangements and an increase in size upon rehydration, although maintaining a uniform and stable distribution. In vitro testing revealed enhanced RTL-W1 cell viability and reduced reactive oxygen species (ROS) production when encapsulation was employed. Overall, these findings demonstrate the potential of the selected encapsulation techniques to optimize the stability, bioavailability, and functionality of AX, providing valuable insights to improve its utilization as a functional ingredient in fish feed formulations. Full article

Deep temperate lakes are increasingly reported to suffer consequences of climate warming, affecting thermal stratification and plankton seasonality. Long-term studies offer a unique opportunity for detecting changes in the zooplankton taxa composition related to climate change. Sampling zooplankton organisms alongside abiotic variables, such as water column temperature, enables the linking of changes in plankton communities with variations in the stratification regime. This provides evidence of direct and indirect warming effects. Our study in Lake Maggiore investigated variations in the population density and persistence of Diaphanosoma brachyurum, a thermophile species that is a member of the original zooplankton community of the lake, along with the increase in water temperature and the duration of the thermal stratification during the period 2013–2023. Our results highlighted an increase in the abundance and persistence of Diaphanosoma during the study period, along with an increase in the mean water temperature of the layer 0–10 m and of the length of the thermal stratification. Such changes, affecting the population dynamics of predators and competitors and their food sources (i.e., small algae), might lead to a rearrangement of the structure of the pelagic food chain. Full article

Edible insect honeybee brood and natural honey are rich in proteins and saccharides, with inherent bioactive properties such as antioxidant activity. To enhance their antioxidative potential under simple thermal conditions, this research employed spontaneous aging via a moist-dried heating process, primarily driven by the Maillard reaction. Honeybee brood bio-peptides (HBb-BPs), produced through Rhizopus oligosporus fermentation, were mixed with honey in varying ratios of 70:30, 50:50, and 30:70 (%w/w). The mixtures underwent interaction under controlled conditions (60 °C for 20 days at ~75% relative humidity). A comparative analysis was performed on the mixtures before and after the thermal interaction, focusing on chemical characterization and antioxidant activity (ABTS, DPPH, and FRAP assays). Results revealed that the post-process mixtures exhibited significantly enhanced antioxidant activity, with higher honey concentrations correlating to greater antioxidative effects. Furthermore, allulose and mannose were detected after processing, while levels of fructose, glucose, and free amino acids decreased. These changes likely indicate the formation of complex compounds, molecular rearrangements, and the production of phenolic compounds that contributed to the increased antioxidative capacity. This study highlights the pivotal role of the Maillard reaction in augmenting antioxidant activity, elucidates changes in sugar–amino acid interactions, and validates the effectiveness of the moist-dried heating process. These findings provide valuable insights for potential future applications of this simple and scalable method. Full article