Search Results (5,009)

In this work, we demonstrate a functional and previously insufficiently explored route for converting cyclic olefin copolymer (COC) TOPAS^® thin films into antibacterial hybrid materials through a combination of solvent casting, plasma activation, noble-metal sputtering, and subsequent thermal or laser treatment. While COC is already well-known as a transparent, chemically resistant material for pharmaceutical and optical applications, its coupling with post-treated noble-metal nanostructures for antibacterial functionality has not been systematically described. The main contribution of this study lies in showing that COC can serve not only as a passive packaging substrate, but also as an active platform for the formation of biologically relevant surface nanostructures. Compared with previously reported metal/polymer systems, the present work provides clear evidence that noble-metal layers on COC undergo substantial structural evolution after thermal and excimer-laser treatment, resulting in regular nanoclustered morphologies. A particularly important finding is the detection of Au particle implantation below the COC surface during sputtering, as revealed by Rutherford backscattering spectrometry, which distinguishes this system from conventional surface-only metal coatings. Furthermore, we show that laser and thermal processing do not merely reshape the deposited layer, but significantly influence the final biological response of the material. Ag-based structures showed strong bactericidal behavior against both Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus. The prepared samples were comprehensively characterized by AFM, DSC, RBS, SEM, and TGA, and their roughness and wettability were also evaluated, enabling direct correlation between physicochemical changes and antibacterial performance. These results introduce a new strategy for upgrading conventionally used pharmaceutical COC materials into multifunctional surfaces with added antibacterial value. Full article

Background: The combination of photodynamic therapy (PDT) and immunotherapy has been explored as an innovative approach to enhance efficacy against tumors. However, PDT shows limited effectiveness in treating deep-seated tumors, as light and lasers do not sufficiently penetrate tissue. Methods: Herein, we introduced a nanocarrier (NP_VR) via self-assembly, using an amphiphilic copolymer to co-deliver the hydrophobic photosensitizer verteporfin (VP) and the immunoadjuvant imiquimod (R837). Results: Our X-ray-induced photodynamic therapy (X-PDT) mechanism induced NP_VR to generate a large amount of cytotoxic reactive oxygen species (ROS), which directly killed cancer cells. Moreover, the released R837 facilitated immunogenic cell death following the X-PDT process and promoted the maturation of dendritic cells (DCs), thereby eliciting immune responses against malignant triple-negative breast cancer (TNBC). In animal experiments, the combined therapy using NP_VR showed a tumor growth inhibition rate of ~70%. Conclusions: This novel strategy opens new avenues to designing next-generation nanomedicines for use in immunotherapy and other combination therapies. Full article

To address the prominent problem of early rutting distress in asphalt pavements under heavy-load traffic in China, this study proposes a composite modifier consisting of direct coal liquefaction residue (DCLR), styrene–butadiene–styrene block copolymer (SBS), and styrene–butadiene rubber (SBR). The preparation process and formula were optimized through single-factor experiments and orthogonal tests. Systematic investigations were conducted on its conventional performance, water damage resistance, aging resistance, fatigue performance, rheological properties, and microscopic mechanism, with comparisons made against base asphalt, single DCLR-modified asphalt, SBS-modified asphalt, and SBS/SBR-modified asphalt. The results indicate that the optimal preparation process for the novel composite high-modulus modified asphalt is as follows: DCLR particle size of 0.3 mm, addition in molten state, shear temperature of 170 °C, shear rate of 5000 r·min⁻¹, shear time of 50 min. The optimal formula is 10% DCLR + 3% SBS + 2% SBR + 3% compatibilizer, with the addition sequence of “DCLR → SBS + compatibilizer → SBR”. This asphalt exhibits a softening point of 77.8 ± 2.1 °C, a Brookfield viscosity at 135 °C of 1.928 ± 0.105 Pa·s, and a grading of 5 for adhesion to aggregates; the rutting factor at 64 °C reaches 10.8 ± 0.9 kPa (6.43 times that of the base asphalt), the creep stiffness at −12 °C is 136 ± 12.5 MPa, and the low-temperature limit temperature is −17 °C; the freeze–thaw splitting strength ratio (TSR) is 94.6 ± 1.8%, and both aging resistance and water damage resistance are significantly superior to those of the control group asphalts (p < 0.05). The novel composite high-modulus modified asphalt showed improved overall laboratory performance and may be suitable for heavy-load traffic and complex climatic conditions, however, field validation is needed. Full article

Droplet size is a key factor in minimizing spray drift. Different types of adjuvants and sprayer operating pressures can affect the droplet size distribution in various ways. This study aimed to evaluate the effects of commercial adjuvants, namely, acids and surfactant (AS), silicone surfactant (SS), organosilicone surfactant (OS), mineral oil (MO and MO₂), and copolymer (CP) adjuvants, on the droplet spectra and physicochemical properties of aqueous solutions. Hydrogen potential (pH), volumetric mass ($VM$), electrical conductivity (EC), surface tension (ST), contact angle (CA), and droplet spectra were measured. The droplet spectrum variables, including volumetric diameters ($D_{v0.1}$, $D_{v0.5}$, and $D_{v0.9}$), the Relative Span Factor ($RSF$), and percentages of the total volume of droplets with a diameter smaller than 100 µm (V100) and larger than 500 µm (V500), were determined using a laser diffraction particle analyzer (Malvern Spraytec). Spraying tests were carried out using the AXI 11003 flat fan nozzle at pressures of (0.1, 0.2, 0.3, 0.4, and 0.5) MPa. The increase in pressure increased the V100 and the $RSF$, with greater sensitivity observed for SS. Adjuvants such as AS, MO₂ and OS showed a more balanced trend, with a smaller increase in fine droplets and a greater reduction in coarse droplets. The principal component analysis (PCA) revealed that the droplet spectrum variables were the ones that best explained the variation among the solutions. A negative correlation was identified between EC and other physicochemical properties, such as pH, ST, and CA. Therefore, these properties alone did not determine the atomization pattern. The study demonstrates that optimizing spray quality and minimizing drift require a combined consideration of adjuvant physicochemical properties and their interaction with operational pressure. Full article

The conducted study was focused on the development of a new type of polymer blends intended for additive manufacturing applications, in particular, the material extrusion method (MEX). The developed materials were prepared from recycled poly(ethylene terephthalate) and amorphous copolymers poly(ethylene terephthalate-glycol) (PETG), and poly(cyclohexylenedimethyl terephthalate-glycol) (PCTG). The basic blend systems were additionally modified with POE-g-GMA impact modifier (IM) during the reactive extrusion process. The main aim of the work was to assess the effectiveness of using composite additives and their influence on the mechanical and thermomechanical parameters of the tested systems. To prepare the composites, selected polymer blends were modified with 10% of talc (T) and carbon fibers (CF). The properties evaluation includes the mechanical/thermomechanical testing, thermal analysis and structural observations. The accuracy of printing was measured using optical scanning methods. The test results indicate that even the relatively small amount of the CF filler could lead to a significant increase in tensile modulus from reference 1.6 GPa to 2.9 GPa; the same improvement applies to strength values, where the CF-modified materials reached 45 MPa, compared to the reference 31 MPa. The heat deflection tests (0.455 MPa) after annealing revealed the maximum HDT of around 170 °C for both types of CF-modified materials. The Vicat test results were also favorable for annealed materials. Considering that the Vicat/HDT results after the 3D-printing process usually reach around 70 °C, the performed heat treatment strongly enhanced the heat resistance for most of the prepared blends. The performed studies revealed that for most of the prepared materials, the brittleness was a common drawback for both MEX-printed and injection-molded materials. Full article

This study investigates how the composition and synthesis sequence affect the structure and responsive behavior of single-network (SN) and double-network (DN) hydrogels composed of poly(N,N’-diethylacrylamide) (PDEAAm) and polyacrylamide (PAAm). DN hydrogels were prepared in two configurations, PDEAAm/PAAm and PAAm/PDEAAm, and compared with SN copolymer hydrogels of varying DEAAm/AAm ratios. ¹H NMR spectroscopy revealed that DN hydrogels exhibit significant heterogeneity due to polymer-rich domains, impacting the accuracy of compositional determination and leading to broad NMR signals. Temperature-dependent NMR and gravimetric swelling analyses were used to quantify thermoresponsive behavior, showing that SN copolymer hydrogels exhibit composition-dependent phase transition parameters, while DN hydrogels show relatively constant transition parameters due to heterogeneous structures. NMR relaxation studies of water molecules identified “free” and “bound” molecules whose dynamics differ markedly above the transition temperature, especially in DN systems. Finally, the swelling behavior in water–acetone mixtures was examined, revealing distinct responses depending on hydrogel composition and thermal state. PAAm-rich hydrogels showed abrupt deswelling near 40 vol% acetone, while PDEAAm-based hydrogels responded more gradually. The findings demonstrate that both composition and network formation order critically influence the structural, thermal, and solvent-responsive properties of hydrogels, offering insights for the design of stimuli-responsive materials. Full article

Mechanochromism is a phenomenon in which mechanical stimuli change the optical properties of a material, such as its color and emission properties. Various materials exhibiting this behavior have been intensively studied. Mechanochromic materials that exploit liquid crystals have been previously reported. Using liquid crystals, properties different from those of conventional materials, such as anisotropic response and multicolored luminescence due to intermediate aggregation phase stabilization, can be expected. Recently, we reported the preparation and evaluation of the optical properties of liquid-crystalline mechanochromic dyes with cholesterol terminals. The dyes formed gels in some solvents, changed their emission color, and exhibited a friable response without reaching a crystalline state. In addition, film-forming properties, processability, and responsiveness were improved in thin films mixed with polymers. However, the mechanical and thermal stabilities of the gels were low. In this study, a compound similar to the polymerizable unit was synthesized to produce tougher gels. In addition, triblock polymers with a mechanoresponsive dye in the hard segment were synthesized. The xerogel film prepared from the monomer showed an irreversible blue shift in photoluminescent color by mechanical grinding and also exhibited linearly polarized photoluminescence by uniaxial grinding due to force-induced alignment. On the other hand, the xerogel film prepared from the triblock copolymer showed a blue shift in photoluminescent color that can approximately revert to the initial state by thermal annealing, though it showed no anisotropy by uniaxial grinding, indicating that polymerization partially preserves mechanical responsiveness. Full article

Circularly polarized (CP) organic light-emitting diodes (CP-OLEDs) have attracted considerable attention due to their promising applications in next-generation display systems, optical data transmission, and quantum computing, and their potential roles in medical devices. Achieving efficient and tunable CP emission remains a significant challenge, prompting the development of various strategies that leverage organic semiconductors. Notably, certain classes of materials now consistently deliver CP polarization at levels suitable for technological applications. Among these, conjugated polymers, particularly the copolymer poly(9,9-dialkylfluorene-alt-benzothiadiazole) (PFBT), stand out for their exceptional optoelectronic properties, ease of processing, and adaptability to produce CP emission. PFBT has played diverse roles within CP-OLED devices, enabling innovative architectural solutions. This review explores principal strategies for integrating PFBT into CP-OLED architectures, drawing upon findings from the recent scientific literature. By consolidating current knowledge and identifying unresolved issues, this work aims to inspire further research into the development of solution-processable, high-performance and tunable CP-OLEDs based on PFBT and conjugated polymers in general. Full article

The performance of recycled hot-mix asphalt mixtures (RHAM) is strongly governed by the extent and uniformity of interactions between the aged binder in reclaimed asphalt pavement (RAP) and the virgin binder. However, in current engineering practice, it remains difficult to accurately evaluate the blending degree of aged and virgin asphalt during RHAM production, where the blending degree refers to the extent and uniformity of binder interaction during hot mixing. Moreover, influenced by various construction-related factors, the uniformity of interfacial diffusion between the two asphalt layers is also hard to control, which compromises the durability of RHAM. To address these issues, fluorescence microscopy was used to quantitatively characterize the blending behavior of aged and virgin asphalt, and Fourier transform infrared spectroscopy (FTIR) was employed to investigate the interfacial diffusion process and its evolution under time-temperature coupling conditions from plant production to field paving. The results indicate that, owing to the fluorescent characteristics of the Styrene-butadiene-styrene block copolymer (SBS) modifier in polymer-modified asphalt, the blending behavior during hot mixing can be quantitatively characterized by the fluorescent area and its areal proportion, providing a rapid solution for quantitative evaluation during RHAM production. Increasing the preheating temperature of RAP, extending mixing time, raising mixing temperature, and adopting Mixing Sequence I reduced the proportion of fluorescent area, suggesting improved blending between aged and virgin asphalt. After blending, the interfacial diffusion between aged and virgin asphalt occurs within the RHAM; the uniformity of this diffusion becomes more pronounced as the elapsed duration from production to paving increases. Nevertheless, excessively long duration may induce secondary aging of the blended binder. Accordingly, the duration is recommended to be controlled at approximately 90 min and should not exceed 180 min. By elucidating the blending and diffusion behaviors of aged and virgin asphalt, this study provides practical guidance for contractors in controlling production-process parameters for RHAM. Full article

Background: Co-delivery of two drugs with diverse physicochemical properties and a specific administration sequence holds great importance in cancer theranostics to overcome drug resistance and reduce side effects. Paclitaxel (PTX) and hydroxycamptothecin (HCPT) have long been used clinically as chemotherapeutic agents for Nasopharyn-geal carcinoma (NPC). However, their clinical application is severely restricted by low water solubility, poor stability, and systemic adverse reactions. Nanoparticle-based drug delivery systems provide a promising platform for combination cancer therapy. Methods: In this study, folic acid-modified and dual drug-loaded self-assembled HCPT/PTX@FA@p-PS-SPIONs were successfully fabricated via the emulsification–solvent evaporation method using amphiphilic phosphorylated polystyrene (p-PS). The characterization, cellular uptake, and in vivo pharmacokinetic profiles of the nanoparticles in NPC models were systematically investigated. Result: HCPT/PTX@FA@p-PS-SPIONs were successfully prepared with p-PS as the copolymer backbone. The nanoparticles exhibited a uniform particle size of 196.9 ± 5.5 nm and a zeta potential of −7.3 ± 0.7 mV. The encapsulation efficiency (EE) was 81.4 ± 2.5% for PTX and 67.6 ± 4.1% for HCPT. The drug loading (DL) efficiency was 18.4 ± 1.5% for PTX and 12.2 ± 1.0% for HCPT. HCPT/PTX@FA@p-PS-SPIONs showed favorable biocompatibility. Sustained and sequential release of the two drugs contributed to an enhanced therapeutic effect. Moreover, under magnetic field (MF) guidance, HCPT/PTX@FA@p-PS-SPIONs exhibited stronger inhibitory effects on NPC cells than single-drug, cocktail, or dual-drug groups, demonstrating the superiority of the combined therapy. Pharmacokinetic studies in rats revealed that the half-lives of PTX and HCPT were 3.9 ± 1.2 h and 4.7 ± 1.1 h, respectively, confirming that HCPT/PTX@FA@p-PS-SPIONs could resist rapid metabolism and clearance in vivo. Conclusions: The long-circulating, folic acid-targeted nanoparticles HCPT/PTX@FA@p-PS-SPIONs show great potential for the targeted therapy of nasopharyngeal carcinoma. Full article

The development of durable road sealing materials capable of maintaining performance under combined mechanical and climatic loads remains a critical challenge for modern infrastructure. Conventional bitumen-based sealants exhibit limited resistance to high-temperature deformation, cracking, and adhesion degradation, leading to reduced service life. This study proposes a rheology-oriented approach to the design of polymer-reinforced bituminous sealants based on penetration-grade bitumen 50/70 and 70/100 modified with styrene–butadiene–styrene (SBS) copolymers up to 9 wt.% and reinforced with cellulose fibers. The rheological behavior of the developed composites was investigated using dynamic shear rheometry to determine the complex shear modulus (G*), phase angle (δ), and temperature–frequency dependencies in the range from −20 to +90 °C, while infrared spectroscopy was employed to assess intermolecular interactions. Adhesion performance was evaluated at different temperature. The modified systems demonstrated a 5–10-fold increase in G*/sinδ enhanced high-temperature stability, and improved adhesion and crack resistance compared to base bitumen. Based on the obtained rheological and performance indicators, the developed composition was approved for subsequent pilot-scale testing and field validation as a promising road sealing material. Full article

The reaction of the pyridylalcohol Ph₂C(OH)CH₂-2-py-6-Me (IH) with Me₃Al in refluxing toluene led to the isolation of the dimer [AlMe₂(μ-OC(Me)Ph₂)]₂ (1), whilst at ambient temperature the complex [(I)AlMe₂]·MeCN (2·MeCN) was isolated. Complex 1 is also readily available via the interaction of diphenylethanol and Me₃Al. Similar treatment of iPr₂C(OH)CH₂-2-py-6-Me (IIH) at ambient temperature afforded [(II)AlMe₂] (3). Treatment of IH and IIH with [VO(OiPr)₃] led to oxo-bridged complexes of the type [(VO)(μ₂-O)(I/II)]₂ (I (4·0.67MeCN), II (5)). The molecular structures of 1–5 are reported. These complexes have been employed as catalysts for the ring-opening polymerization (ROP) of the cyclic esters ε-caprolactone (ε-CL) and δ-valerolactone (δ-VL). For aluminium, complex 1/BnOH produced medium- to high-molecular-weight (M_n) PCL at 20 to 110 °C in solution, though some bi-/multi-modal behaviour was observed; for melts the M_n values were toward the lower end. For complexes 2 and 3, far lower M_n values for PCL were observed at 20 °C in solution and as melts, whilst in solution at 110 °C higher M_n values were achieved, though with less control. In general, M_n values for the PCL obtained using the vanadium complexes were low (≤8560 Da for 4, ≤2920 Da for 5). In the case of PVL, 1/BnOH in solution exhibited higher M_n values at lower temperatures with good control, and when employed as a melt, the M_n was toward the higher end (30,830 Da) observed. For 2/BnOH, much lower M_n values (≤2740 Da) were recorded both in solution and as a melt, whilst for 3, high M_n values were only observed in the absence of BnOH. Low M_n values (≤2920 Da) were also observed for the vanadium complexes 4 and 5. Kinetic results (both ε-CL and δ-VL) revealed that the vanadium complexes, particularly 4, outperformed the aluminium complexes. MALDI-ToF spectra revealed the formation of linear PCL polymers with BnO/H end groups for the aluminium/BnOH complexes in solution, and cyclic polymers when employed as melts. For vanadium, cyclic PCL polymers were the major family present. In the case of PVL, linear (BnO/H end groups) and cyclic polymers were observed when employing the Al/BnOH systems, whilst cyclic polymers were observed for vanadium. Copolymerization of ε-CL and δ-VL using 4/BnOH at 110 °C over 24 h led to incomplete conversion and formation of a random-type copolymer. Full article

The use of seven biomaterials was examined in the study: polyethylene (PE), polypropylene (PP), polyurethane (PU), teflon (PTFE), polycaprolactone (PCL), polylactide (PLLA), and a copolymer of poly L-lactide and dibutyryl chitin (PLLA/DBC). The use of these materials has not been discussed in the context of animal reproduction so far. Due to the specific nature of the reproductive system and the high sensitivity of reproductive cells, at the outset the biocompatibility and cytotoxicity of the materials were tested in somatic cell and embryo cultures. Additionally, the material properties of the catheters were determined in terms of the roughness of the internal and external surfaces, the stability of the shape of the catheters, their elasticity, durability, and ductility. Finally, clinical testing of the developed catheters was performed in laparoscopic transplantation of embryos into the uterine tubes of the sows. Significant toxicity of PTFE, PCL and PLLA/DBC towards the embryos was indicated in the cytotoxicity testing. In the materials testing, numerous flaws of the PP, PLLA, and PLLA/DBC catheters were indicated. In the final stage, catheters were developed using PE and PU. In clinical testing, these latter catheters exhibited high effectiveness in transferring embryos. Among the seven biomaterials tested, only polyethylene and polyurethane exhibited high biocompatibility and the material properties mentioned above. There is thus good indication for the introduction of these catheters for embryo transfer in animal reproduction biotechnology. Full article

Solid polymer electrolytes (SPEs) hold great potential in high-safety energy storage but face two key bottlenecks: low room-temperature ionic conductivity and insufficient mechanical strength. This study proposes a synergistic optimization strategy of “long-carbon-chain regulation of polymer microstructure combined with porous polyimide (PI) support”. A linear random copolyester, poly(1,3-propylene-co-1,4-butylene succinate-co-sebacate) (PBPSS), was synthesized via melt polycondensation using 1,3-propanediol, 1,4-butanediol, succinic acid, and sebacic acid as monomers. Subsequently, the PBPSS-75 composite electrolyte was prepared with this copolyester as the matrix and porous PI as support. Results show that long-carbon-chain sebacic acid effectively regulates polymer segment flexibility and free volume, synergistically enhancing ionic conductivity and interfacial mechanical stability with lithium metal. Experimental data indicate that PBPSS-75 composite electrolyte exhibits an ionic conductivity of up to 4.25 × 10⁻⁵ S cm⁻¹ (30 °C), a lithium-ion transference number of 0.81, and an electrochemical stability window of 4.48 V (vs. Li/Li⁺). In LiFePO₄//Li batteries, it maintains nearly 100% capacity retention after 300 cycles at 0.5 C, and achieves stable cycling for over 800 h in lithium symmetric cells. This study confirms that the combined strategy effectively addresses the conductivity-mechanical property trade-off of SPEs, providing theoretical guidance and technical reference for high-performance solid-state battery material design. Full article

Oily substances (oils, greases, lubricants, etc.) are among the most persistent pollutants for water. They mix with water to form emulsions that contaminate large volumes. Therefore, this project evaluated the use of porous systems (polyurethane foam) modified with polydimethylsiloxane-modified silica (SiO₂/DMS) hybrid ceramics as filtration membranes at the laboratory scale for vegetable oil. The polyurethane foam was modified using sol solutions with various SiO₂/PDMS ratios obtained via the sol–gel method. Tetraethyl-orthosilicate (TEOS) was used as the silica precursor. Three different polydimethylsiloxane chains were employed as the organic fragment: polydimethylsiloxane hydroxyl terminated (DMS-CH₃), aminopropyl-terminated polydimethylsiloxane (DMS-N), and copolymer polydiphenylsiloxane-polydimethylsiloxane hydroxyl terminated (PDS). The siloxane chain was added at a concentration of 20–40% w/w. The modification of the porous system was determined using different characterization techniques, including infrared spectroscopy, which was used to observe the main functional groups. Optical microscopy and SEM were used to identify the hybrid ceramic deposited into the pore structure of the polyurethane sponge. Contact angle measurements revealed the hydrophobic character of the modified material. The removal capacity was evaluated by using vegetable oil as a representative oily contaminant, with values ranging from 43.42 to 96.78 g of oil per gram of adsorbent. In the case of gasoline, removal capacities between 27 and 54 g were observed. This study demonstrated the influence of hydrophobicity on vegetable oil removal, confirming that higher hydrophobicity leads to greater adsorption capacity. Nevertheless, the use of a viscous contaminant introduced challenges in the extraction process from the PS/SiO₂-DMS system. Despite this limitation, the material maintained adequate removal performance for up to five reuse cycles. On the other hand, the removal capacity depends on the amount of polysiloxane chain in the ceramic, as well as the functional group, exhibiting the following behavior: DMS-N < DMS-CH₃ < PDS. This study demonstrates that hydrophobicity is a key property for enhancing the removal capacity of oily substances. Moreover, the control of intermolecular interactions further strengthens this effect, as evidenced in the PS/SiO₂–PDS system. Full article