Search Results (2,543)

Crystalline defects such as oxygen vacancies have been studied little by electron paramagnetic resonance (EPR) spectroscopy for silicate-based luminescent materials. In this study, lutetium oxyorthosilicate powders were prepared by the sol–gel method, using TEOS (silicon source) and rare earth salts as precursors. The cross-linking agent, Glymo, contributed silicon atoms to the precursor solution in all systems. The addition of Glymo to Lu₂SiO₅, Lu₂SiO₅:Eu and Lu₂SiO₅:Eu/Yb influenced the morphology and chemical structure of the powders, leading to Lu₂Si₂O₇ formation. The crystalline defects in the lutetium silicate systems were investigated by EPR spectroscopy, and several defects related to oxygen were identified, as well as impurities from the precursors. Photoluminescence emission spectra revealed Eu³⁺ transitions between ⁵D₀ → ⁷F₀, ⁵D₀ → ⁷F₁ and ⁵D₀ → ⁷F₂ under 258 nm excitation, in addition to oxygen vacancy emissions between 500 and 550 nm. Oxygen vacancies were identified and confirmed by correlating EPR and photoluminescence studies. Full article

Background/Objectives: Glioblastoma (GBM) is a fatal tumor in the central nervous system (CNS) with a poor prognosis. Preventing tumors from post-surgical recurrence is a significant clinical challenge, since current methods deliver chemotherapeutic agents in a rapid manner and are not effective against the residual tumor cells. To address these limitations, we develop a blue light-crosslinking hydrogel which can be rapidly gelled in situ and tightly adhere on the tissues for controlled chemotherapy, radiotherapy, and enhanced laser interstitial thermal therapy (LITT) to inhibit residual tumor cells from post-surgical recurrence. Methods: We utilize gelatin-MA based hydrogel with crosslinker VA-086 as hydrogel scaffold to encapsulate small-molecule drugs (Epirubicin and Cisplatin) and LITT agent polypyrrole-coated graphine oxide (PPy@GO). The mixture can form into hydrogel in situ by blue light irradiation and performed chemo-LITT and radio therapy simultaneously. Then we determine the prevailing factors that affect efficient encapsulation of therapeutic agents within hydrogels, efficiency of gelation, LITT enhancement, and drug release. Then evaluate efficiency in human cancer cells and an in vivo tumor model. Results: Our results demonstrate that 18 wt% Gelatin MA formulation achieved >95% gelation within 2 min, with drug-loaded gels forming within 5 min. The gelation can perform both in vitro and in vivo without affect the drug efficiency. This multi-treatment system can effectively prevent tumor recurrence and significantly prolong the medium survival of glioma-bearing (MBR-614 or U87-MGFL) mice to above 65 days compared with the control group (36 days). Conclusions: The results demonstrated promising effect of this system as a multi-therapeutic platform which combined chemo-LITT and RT. This synergistic strategy presents a new approach to the development of a local drug delivery system for the prevention of brain tumor recurrence. Full article

The replacement of polyvinylidene fluoride (PVDF) with environmentally friendly binders offers potential advantages in the development of aqueous lithium-ion batteries (ALIBs) and flow batteries (FBs) incorporating solid charge carriers (so-called solid boosters). This study investigates the electrochemical stability of ethyl cellulose and cross-linked gluten as substitutes for PVDF in LiMn₂O₄ (LMO) cathodes for aqueous Li-ion battery electrodes and solid boosters for FBs. The millimetre-scaled solid booster beads must be easily produced on a large scale, and at the same time, their charging and discharging must be reversible over long durations under electrolyte tank conditions. The binders were tested under standardized conditions for discharge capacity and cycling stability. Our results demonstrate that ethyl cellulose and cross-linked gluten can rival the electrochemical stability of PVDF, maintaining initial discharge capacities near 100 mAh g⁻¹ at 0.2 C for LMO cathodes and exhibiting reasonable capacity retention over hundreds of cycles. This work supports the feasibility of sustainable electrode processing, provides promising directions for scalable, eco-friendly electrode fabrication methods, and highlights promising binder candidates for use in aqueous energy storage systems. Full article

Liquid Crystalline Elastomers (LCEs) are a class of shape-changing polymers with exceptional mechanical properties and potential as artificial muscles/polymer actuators. Much work has been dedicated to expanding the methods available for processing LCEs into various forms using different manufacturing techniques such as 3D printing, film casting, and microfluidic processing. Recently, several works have reported processing LCEs into long fibres and have highlighted the advantages that fibrous LCEs boast over LCE films. However, the development of alternative methods to produce fibrous LCEs is warranted to fully expedite this field of research. In this study, a method for continuous production of disulphide crosslinked LCE fibres via the technique of wet spinning is explored and reported on. Furthermore, the results show that the mechanical properties, actuation force, and actuation strain can be tuned by adjusting how much crosslinker is incorporated into the wet-spinning dope solution. Depending on the given formulation, the reported fibres could repeatedly actuate in response to thermal energy with actuation forces ranging from 0.002 to 0.02 N per fibre and actuation strains ranging from 9.7 to 33%. Full article

This work examines the mechanical behaviour of 3D-printed stochastic lattice structures fabricated using a semi-controlled design. A primary goal is to predict and optimize the mechanical response of these Acrylic Styrene Acrylonitrile (ASA) filament structures when subjected to compressive stress. By transitioning from a purely stochastic method to a semi-controlled tessellation approach within Rhinoceros 7 software, we effectively generated the proposed design models. This methodology results in mechanical responses that are both predictable and reliable. The design parameters, including nodal formation, strut thickness, and lattice generation based on a predefined geometric routine, are associated with the regulation of the relative density. This approach aims to minimize the effect of relative density on the actual stiffness and strength evaluation. Our findings are cantered on the compressive testing of structures, which were generated using a Voronoi population distributed along a parabolic curve. We analyzed their mechanical response to the point of failure by examining stress–strain fluctuations. Three distinct behaviour stages are observed: elastic range, plastic range, and collapse without densification. The influence of crosslink geometry on the elastic responses was highlighted, with parabolic configurations affecting the peak stresses and elastic line slopes. The structures exhibited purely brittle behaviour, characterized by abrupt local cracking and oscillatory plateau formation in the plastic stage. Full article

Reliable DC cable insulation is crucial for photovoltaic (PV) systems and high-voltage DC (HVDC) networks. However, conventional materials such as cross-linked polyethylene (XLPE) and polyvinyl chloride (PVC) face challenges under prolonged DC stress—notably space charge buildup, dielectric losses, and thermal aging. Cross-linked polyolefin (XLPO) has emerged as a halogen-free, thermally stable alternative, but its comparative DC performance remains underreported. Methods: We evaluated the insulations of virgin XLPO, XLPE, and PVC PV cables under ±1 kV DC using time-domain indices (IR, DAR, PI, Loss Index), supported by MATLAB and FTIR. Multi-layer cable geometries were modeled in MATLAB to simulate radial electric field distribution, and Fourier-transform infrared (FTIR) spectroscopy was employed to reveal polymer chemistry and functional groups. Results: XLPO exhibited an IR on the order of 10⁸–10⁹ Ω, and XLPE (IR ~ 10⁸ Ω) and PVC (IR ~ 10⁷ Ω, LI ≥ 1) at 60 s, with favorable polarization indices under both polarities. Notably, they showed high insulation resistance and low-to-moderate loss indices (≈1.3–1.5) under both polarities, indicating controlled relaxation with limited conduction contribution. XLPE showed good initial insulation resistance but revealed polarity-dependent relaxation and higher loss (especially under positive bias) due to trap-forming cross-linking byproducts. PVC had the lowest resistance (GΩ-range) and near-unit DAR/PI, dominated by leakage conduction and dielectric losses. Simulations confirmed a uniform electric field in XLPO insulation with no polarity asymmetry, while FTIR spectra linked XLPO’s low polarity and PVC’s chlorine content to their electrical behavior. Conclusions: XLPO outperforms XLPE and PVC in resisting DC leakage, charge trapping, and thermal stress, underscoring its suitability for long-term PV and HVDC applications. This study provides a comprehensive structure–property understanding to guide the selection of advanced, polarity-resilient cable insulation materials. Full article

Rubber material with high elasticity and viscoelasticity has become the most widely used universal material, and the study of the aging failure mechanism of rubber has been meaningful research in the polymer materials field. Cis-polyisoprene was employed to analyze the mechanism of oxidative degradation under artificial UV irradiation, and the GQDs/g-C₃N₄ photocatalysis with a 2D layered structure prepared by the method of microwave-assisted polymerization enabled to accelerate the degradation procedure. The results showed that the oxidation of cis-polyisoprene occurred during the irradiation for 3 days and the structure of cis-polyisoprene changed. The α-H of the double bond was attacked by oxygen to form hydroperoxide. Then, aldehydes and ketones generated as the addition reaction of double bonds occurred. The content of the hydrogen of C=C reduced, and the oxidative degradation was dominant at the initial aging stage. The crosslinking reaction was dominant at the final aging stage and the average molecular weight decreased from 15.49 × 10⁴ to 8.78 × 10⁴. The GQDs could promote the charge transfer and the photodegradation efficiency and inhibit the electron–hole recombination. The light capture ability of GQDs was improved after compositing with g-C₃N₄. The free radicals ·O₂²⁻ generated after adding GQDs/g-C₃N₄ nanoparticles, and the molecular weight of cis-polyisoprene decreased to 5.79 × 10⁴, with the photocatalytic efficiency increasing by 20%. This work provided academic bases and reference values for the application of photocatalysts in the field of natural rubber degradation and rubber wastewater treatment. Full article

Background/Objectives: Disinfection of removable prostheses is essential for controlling oral infections, yet the methods employed may compromise the mechanical reliability of denture base materials. This study evaluated the effect of microwave irradiation and immersion in 0.2% chlorhexidine solution on the fracture strength of three commonly used acrylic denture bases. Methods: Forty-five standardised maxillary palatal denture bases were fabricated from cross-linked conventional, high-impact, and light-cured acrylic resins. The specimens were divided equally into three treatment groups: water storage (control), immersion in 0.2% chlorhexidine solution for 30 min twice weekly, and microwave disinfection at 650 W for three minutes, each continued for four weeks. Fracture strength was determined by using the Universal testing machine. The data were analysed with one-way ANOVA followed by Bonferroni post hoc testing. Results: Cross-linked and high-impact acrylic resins exhibited significantly greater fracture strength than light-cured acrylics (p < 0.001). The overall ANOVA showed no statistically significant differences among disinfection methods (p = 0.069); however, post hoc comparisons revealed significant reductions in fracture strength within specific material groups following microwave disinfection. This effect was most pronounced in the light-cured group, whereas immersion in chlorhexidine produced no significant changes. Notably, the fracture strength of all groups remained above clinically acceptable thresholds. Conclusions: Microwave disinfection negatively influences the mechanical integrity of acrylic denture bases, particularly those fabricated from light-cured resins. In contrast, immersion in 0.2% chlorhexidine preserves fracture strength, supporting its use as a safe and effective protocol for routine disinfection in dental practice. Full article

Polysiloxanes are unique polymers used in medicine and materials science and are ideal for various modifications. Classic functionalization methods involve a covalent approach, but finer tuning of the properties of the final polymers can also be achieved through sub-sequent noncovalent modifications. This study introduces a fundamentally new approach to polysiloxane functionalization by incorporating cooperative noncovalent interaction centers: selenium-based chalcogen bonding donors and polyfluoroaromatic π-hole acceptors into a single polymer platform. We developed an efficient nucleophilic substitution strategy using poly((3-chloropropyl)methylsiloxane) as a platform for introducing Se-containing groups with polyfluoroaromatic substituents. Three synthetic approaches were evaluated; only direct modification of Cl-PMS-2 proved successful, avoiding catalyst poisoning and crosslinking issues. The optimized methodology utilizes mild conditions and achieved high substitution degrees (74–98%) with isolated yields of 60–79%. Comprehensive characterization using ¹H, ¹³C, ¹⁹F, ⁷⁷Se, and ²⁹Si NMR, TGA, and contact angle measurements revealed significantly enhanced properties. Modified polysiloxanes demonstrated improved thermal stability (up to 37 °C higher decomposition temperatures, 50–60 °C shifts in DTG maxima) and increased hydrophobicity (water contact angles from 69° to 102°). These systems potentially enable chalcogen bonding and arene–perfluoroarene interactions, providing foundations for materials with applications in biomedicine, electronics, and protective coatings. This dual-functionality approach opens pathways toward adaptive materials whose properties can be tuned through supramolecular modification while maintaining the inherent advantages of polysiloxane platforms—flexibility, biocompatibility, and chemical inertness. Full article

Background: Contact lens-assisted corneal cross-linking can be used to treat keratoconus in patients with thin corneas under measuring less than 400 µm. This study compares the long-term clinical and tomographic outcomes between accelerated corneal cross-linking (A-CXL) and accelerated contact lens-assisted corneal cross-linking (A-CACXL). Methods: Patients who underwent either A-CXL or A-CACXL protocol due to progressive keratoconus were enrolled in this retrospective cohort study conducted between January 2015 and December 2018. The control group (patients with minimum corneal thickness of at least 400 µm, comprising 32 eyes of from 32 patients) was treated with A-CXL, whereas the treatment group (patients that had minimum corneal thickness after epithelial removal below 400 µm; 30 eyes of from 30 patients) underwent the A-CACXL protocol. Clinical and tomographic data were obtained from a 3-year follow-up period. Results: At 3 years, both groups represented a significant gain in best-corrected visual acuity (from 0.32 to 0.18 LogMAR units for A-CXL, p = 0.001; from 0.51 to 0.33 LogMAR units for A-CACXL, p = 0.037). Furthermore, postoperative tomographic parameters (Kmax, Kmean, or corneal astigmatism) were comparable between the two protocols. Progression of keratoconus was halted among 87% of eyes in the A-CXL group and among 73% of eyes in the A-CACXL group (p = 0.2). Conclusions: A-CACXL treatment is an effective and safe option for patients with keratoconus and thin corneas, yielding long term outcomes comparable to those of A-CXL treatment for patients with a minimum corneal thickness of 400 µm following a 3-year follow-up. Full article

The escalating issue of water pollution driven by rapid industrialization necessitates the development of advanced remediation technologies. In this study, a novel method for producing chromium (Cr(VI)) ion-imprinted biochar (Cr(VI)-IIP-PEI@NBC) from wheat residue was proposed. After acid-oxidative modifications, polyethyleneimine (PEI) and glutaraldehyde (GA) were employed as the functional monomer and crosslinker, respectively, to enhance the biochar’s selectivity and adsorption capacity. Under optimized conditions (pH 2.0, 55 °C), the adsorbent achieved a maximum Cr(VI) uptake of 212.63 mg/g, which was 2.3 times higher than that of the non-imprinted biochar. The material exhibited exceptional specificity (99.64%) for Cr(VI) and maintained >80% adsorption efficiency after five regeneration cycles, demonstrating excellent reusability. Comprehensive structural characterization via Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric analysis (TGA), Brunner–Emmet–Teller measurements (BET), and Scanning Electron Microscopy (SEM) confirmed successful Cr(VI) imprinting in the biochar and its high thermal stability and mesoporous architecture, elucidating the mechanisms behind its superior performance. This study presents a sustainable and high-performance adsorbent for the efficient treatment of chromium-contaminated wastewater, with significant potential for industrial applications. Full article

Background/Objectives: The synthesis of protein nanoparticles (NPs) using the coacervation method is influenced by critical parameters. The use of glutaraldehyde limits the pharmacological applications of NPs in humans due to the potential toxicity of residual aldehydes that remain after the purification of the nanoparticles. The aim was to assess heat effect as a crosslinking agent for the synthesis of bovine serum albumin (BSA)–capsaicin nanoparticles and its effect on the physicochemical characteristics of nanoparticles. Results: The initial concentrations of BSA and capsaicin in the formulation were directly correlated with the amount of BSA that was transformed into nanoparticles and the loaded capsaicin (r = 0.97, p = 0.0003 and r = 0.95, p = 0.0003), respectively. Furthermore, the morphometric parameters of nanoparticles were affected by the increase in capsaicin concentration, but not by temperature. The nanoparticles increased in dimensions and showed a loss of shape due to coalescence between nanoparticles. The ζ-potential decreased with the increase in the concentration of capsaicin added. This effect compromised the stability of the nanoparticles; on the other hand, molecular interactions were observed between hydrophobic residues of phenylalanine and tyrosine in BSA and the hydrophobic moiety of capsaicin. At the same time, BSA nanoparticles showed a potential for disassembling and delivering the payload capsaicin, which caused an antisteatotic effect in the liver of a murine model. Conclusions: heat (70 °C) can replace crosslinking agents, such as glutaraldehyde. This property is particularly useful when an aldehyde-free synthesis of BSA nanoparticles is needed. Full article

Polyethylene terephthalate (PET) films were modified by direct fluorination using fluorine gas at room temperature and 660 torr for reaction times ranging from 10 min to 5 h. Some of the fluorinated samples were dried at 70 °C for 7 days. FT-IR and XPS analyses confirmed the successful incorporation of fluorine into the PET structure, with the formation of -CHF- and -CF₂- groups. The degree of fluorination increased with the reaction time, but excessive reaction led to the formation and loss of CF₄. Drying further decreased the fluorine content due to the continued CF₄ formation. XRD revealed that fluorination increased the crystallinity of PET owing to increased polarity, whereas drying decreased the crystallinity owing to increased crosslinking. The DSC results showed an increase in the glass transition temperature (T_g) after fluorination and drying, which was attributed to increased polarity and crosslinking, respectively. The surface hydrophilicity of PET increased significantly with fluorination time, and the water contact angle decreased to as low as 3.35°. This was due to the introduction of polar fluorine atoms and the development of a rough and porous surface morphology, as observed by AFM. Interestingly, drying of the fluorinated samples led to an increase in the water contact angle, with a maximum of 85.95°, owing to increased crosslinking and particle formation on the surface. This study demonstrates a simple and effective method for controlling the hydrophilicity and hydrophobicity of PET surfaces via direct fluorination and drying. Full article

Background/Objectives: Understanding the interactions between nanoparticles and mucosal tissues is crucial for the development of advanced drug delivery systems, as the diffusion behavior of nanoparticles through mucus is strongly influenced by their size and surface properties, and the viscoelastic nature of the hydrogel matrix. In this study, we investigated the impact of nanoparticle size, surface charge, and hydrogel crosslinking density on nanoparticle diffusion in a mucus model in vitro. Method: Citrate-stabilized and PEGylated 30 and 100 nm gold nanoparticles were used as a model of nanoparticle and their diffusion through mucus-mimicking mucin-based hydrogels of two different crosslinking densities was assessed. Results: Citrate-stabilized 30 nm nanoparticles demonstrated greater diffusion in hydrogels mimicking native mucus compared to more densely crosslinked ones, reaching approximately 50.3 ± 0.2% diffusion within the first 5 min of the assay. This size-dependent effect was not observed for the 100 nm citrate-stabilized nanoparticles, which showed limited diffusion in both hydrogel types. To confer different surface charge, gold nanoparticles were functionalized by the conjugation of poly(ethylene glycol) (PEG) derivatives of identical molecular weight with different terminal moieties (neutral, and positively and negatively charged) to modulate the surface charge and assess their interaction with the negatively charged mucin matrix. PEGylated particles exhibited significantly greater mobility than their citrate-stabilized counterparts, regardless of size or hydrogel density owing to the muco-penetration effect of PEG. Among PEGylated particles, the neutral and negatively charged 30 nm variants demonstrated higher diffusion than the positively charged ones due to weaker interactions with the negatively charged mucin hydrogel. For the 100 nm particles, the neutral PEGylated nanoparticles exhibited greater diffusion than their positively charged counterparts. Conclusions: Overall findings could provide valuable insights into the more rational design of nanoparticle-based drug delivery systems targeting mucosal tissues. Full article

1,3-butadiene (BD) is a volatile organic pollutant. Upon inhalation, it is metabolically activated to reactive epoxides which alkylate genomic DNA and form potentially mutagenic monoadducts and DNA–DNA crosslinks including N7-(1-hydroxyl-3-buten-1-yl)guanine (EB-GII) and 1,4-bis-(guan-7-yl)-2,3-butanediol (bis-N7G-BD). While metabolic activation resulting in mutagenicity is a well-established mode of action for 1,3-butadiene, characterization of the extent of inter-individual variability in response to BD exposure is a gap in our knowledge. Previous studies showed that population-wide mouse models can be used to evaluate variability in 1,3-butadiene DNA adducts; therefore, we hypothesized that this approach can be used to also study variability in the formation and loss of BD DNA adducts across tissues and between sexes. To test this hypothesis, female and male mice from five genetically diverse Collaborative Cross (CC) strains were exposed to filtered air or 1,3-butadiene (600 ppm, 6 h/day, 5 days/week for 2 weeks) by inhalation. Some animals were kept for two additional weeks after exposure to study DNA adduct persistence. EB-GII and bis-N7G-BD adducts were quantified in liver, lungs and kidney using established isotope dilution ESI-MS/MS methods. We observed strain- and sex-specific effects on both the accumulation and loss of both DNA adducts, indicating that both factors play important roles in the mutagenicity of 1,3-butadiene. In addition, we quantified the intra-species variability for each adduct and found that for most tissues/adducts, variability values across strains were modest compared to default uncertainty factors. Full article