Search Results (464)

Poly(vinyl chloride) (PVC) undergoes thermal degradation during processing and operation, which necessitates the use of effective thermal stabilizers. The purpose of this work is to comprehensively evaluate the potential of new hierarchically structured titanium phosphates (TiP) with controlled morphology as thermal stabilizers of plasticized PVC, focusing on the effect of morphology and Ti/P ratio on their stabilizing efficiency. The thermal stability of the compositions was studied by thermogravimetric analysis (TGA) in both inert (Ar) and oxidizing (air) atmospheres. The effect of TiP concentration and its synergy with industrial stabilizers was analyzed. An assessment of the key degradation parameters is given: the temperature of degradation onset, the rate of decomposition, exothermic effects, and the carbon residue yield. In an inert environment, TiPMSI/TiPMSII microspheres demonstrated an optimal balance by increasing the temperature of degradation onset and the residual yield while suppressing the rate of decomposition. In an oxidizing environment, TiPR rods and TiPMSII microspheres provided maximum stability, enhancing resistance to degradation onset and reducing the degradation rate by 10–15%. Key factors of effectiveness include ordered morphology (spheres, rods); the Ti-deficient Ti/P ratio (~0.86), which enhances HCl binding; and crystallinity. The stabilization mechanism of titanium phosphates is attributed to their high affinity for hydrogen chloride (HCl), which catalyzes PVC chain scission, a catalyst for the destruction of the PVC chain. The unique microstructure of titanium phosphate provides a high specific surface area and, as a result, greater activity in the HCl neutralization reaction. The formation of a sol–phosphate framework creates a barrier to heat and oxygen. An additional contribution comes from the inhibition of oxidative processes and the possible interaction with unstable chlorallyl groups in PVC macromolecules. Thus, hierarchically structured titanium phosphates have shown high potential as multifunctional PVC thermostabilizers for modern polymer materials. Potential applications include the development of environmentally friendly PVC formulations with partial or complete replacement of toxic stabilizers, the optimization of thermal stabilization for products used in aggressive environments, and the use of hierarchical TiP structures in flame-resistant and halogen-free PVC-based compositions. Full article

Tocopheramines are a class of antioxidants which are distinguished from tocopherols (vitamin E) by the presence of an amino group instead of the phenolic hydroxyl group. α-Tocopheramine is intensively studied for biomedical applications but also as a stabilizer for synthetic and natural polymers, in particular for cellulose solutions and spinning dopes for cellulosic fibers. This study addresses a fundamental difference in the oxidation chemistry of α-tocopheramine and its tocopherol counterpart: while the formation of the ortho-quinone methide (o-QM) involving C-5a is one of the most fundamental reactions of α-tocopherol, the corresponding ortho-iminoquinone methide (o-IQM) derived from α-tocopheramine has been elusive so far. Synthesis of the transient intermediate succeeded initially via 5a-hydroxy-α-tocopheramine, and its occurrence was confirmed by dimerization to the corresponding spiro-dimer and by trapping with ethyl vinyl ether. Eventually, suitable oxidation conditions were found which allowed for the generation of the o-IQM directly from α-tocopheramine. The underlying oxidation chemistry of α-tocopherol and α-tocopheramine is concisely discussed. Full article

This study involved the fabrication of poly (vinyl alcohol) (PVA) nanocomposite films using the solution-casting process, which incorporated strontium-coated silver oxide (Sr-Ag₂O) nanoparticles generated by a plant-extract assisted method. Various characterization techniques, such as XRD, SEM, TEM, UV, and FTIR, showed the formation and uniform distribution of Sr-Ag₂O nanoparticles in the PVA film, which are biocompatible nanocomposite films. The presence of hydroxyl groups leads to appreciable mixing and interaction between the Sr-Ag₂O nanoparticles and the PVA polymer. Mechanical and thermal results suggest enhanced tensile strength and increased thermal stability. In addition, the sample of PVA/Sr-Ag₂O (1.94/0.06 wt. ratio) nanocomposite film showed decreased hydrophilicity, lower hemolysis, non-toxicity, and appreciable cell migration activity, with nearly 19.95% cell migration compared to the standard drug, and the presence of Sr-Ag₂O nanoparticles favored the adhesion and spreading of cells, which triggered the reduction in the gaps. These research findings suggest that PVA/Sr-Ag₂O nanocomposite films with good mechanical, antimicrobial, non-toxic, and biocompatible properties could be applied in biological wound-healing applications. Full article

In civil engineering, with the increasing demand for structural reinforcement and renovation projects, polymer-rich anchoring adhesives have attracted much attention due to their performance advantage of having high strength and have become a key factor in ensuring the safety and durability of buildings. In this study, polymer-rich anchoring adhesives underwent three artificial aging treatments (alkali medium, hygrothermal, and water bath) to evaluate their aging performance. Alkali treatment reduced bending strength by up to 70% (sample 5#) within 500 h before stabilizing, while hygrothermal and water-curing treatments caused reductions of 16–51% and 15–77%, respectively, depending on adhesive composition. Dynamic thermomechanical analysis revealed significant loss factor decreases (e.g., epoxy adhesives dropped from >1.0 to stable lower values after 500 h aging), indicating increased rigidity. Infrared spectroscopy confirmed chemical degradation, including ester group breakage in vinyl ester resins (peak shifts at 1700 cm⁻¹ and 1100 cm⁻¹) and molecular chain scission in unsaturated polyesters. The three test methods consistently demonstrated that 500 h of aging sufficiently captured performance trends, with alkali exposure causing the most severe degradation in sensitive formulations (e.g., samples 5# and 6#). These results can be used to establish quantitative benchmarks for adhesive durability assessment in structural applications. Full article

The interest in macromolecular alkoxysilyl-functionalized hybrids (self-assembling or nanostructured), which could be used as precursors in biomimetic silica precipitation and for the synthesis of hollow spherical silica particles, is growing. Nevertheless, reports on all-organosilicon systems for bioinspired silica precipitation are scarce. Therefore, a new kind of polyalkoxysilane macromonomer–linear polysilsesquioxane (LPSQ) of ladder-like backbone, functionalized in side chains with trimethoxysilyl groups (LPSQ-R-Si(OMe)₃), was designed following this approach. It was obtained by photoinitiated thiol-ene addition of 3-mercaptopropyltrimethoxysilane to the vinyl-functionalized polysilsesquioxane precursor, carried out in situ in tetraethoxysilane (TEOS). The mixture of LPSQ-R-Si(OMe)₃ and TEOS (co-monomers) was used in a sol–gel process conducted under acidic conditions (0.5 M HCl/NaCl) in the presence of Pluronic^® F-127 triblock copolymer as a template. LPSQ-R-Si(OMe)₃ played a key role for the formation of microparticles of a spherical shape that were formed under the applied conditions, while their size (as low as 3–4 µm) was controlled by the stirring rate. The hybrid materials were hydrophobic and showed good thermal and oxidative stability. Introduction of zinc acetate (Zn(OAc)₂) as an additive in the sol–gel process influenced the pH of the reaction medium, which resulted in structural reinforcement of the hybrid microparticles owing to more effective condensation of silanol groups and a relative increase of the content of SiO₂. The proposed method shows directions in designing the properties of hybrid materials and can be translated to other silicon–organic polymers and oligomers that could be used to produce hollow silica particles. The established role of various factors (macromonomer structure, pH, and stirring rate) allows for the modulation of particle morphology. Full article

Anion exchange membranes (AEMs) are vital for electrochemical energy devices such as alkaline fuel cells and water electrolyzers, enabling the use of non-precious metal catalysts despite challenges from alkaline degradation. Hyperbranched polymers (hbPs) with their globular structure, high functional group density, and simple synthesis, offer a promising platform for enhancing transport and stability. In this study, multifunctional hbPs were synthesized from 4-vinylbenzyl chloride (VBC) and 2-hydroxyethyl methacrylate (HEMA) via atom transfer radical self-condensing vinyl polymerization (ATR-SCVP) and crosslinked into polyurethane-based AEMs. Characterization confirmed successful copolymerization and crosslinking, with excellent alkaline stability. Membranes crosslinked with higher molecular weight (MW) and VBC-richer hbPs (e.g., OH-hbP1-PU) exhibited high water uptake (75%) but low ion-exchange capacity (1.54 mmol/g) and conductivity (186 µS/cm), attributed to steric hindrance and insufficient ionic network connectivity. In contrast, OH-hbP2-PU exhibited optimal properties, with the highest OH⁻ conductivity (338 µS/cm) and IEC (2.64 mmol/g), highlighting a balanced structure for efficient ion transport. This work offers a tunable strategy for high-performance AEM development through tailored hbP architecture. Full article

A VOC-contaminated shallow aquifer in an industrial site was investigated to evaluate its potential for natural attenuation. The shallow groundwater aquifer beneath the industrial site has been contaminated by dissolved volatile organic compounds (VOCs) such as trichloroethylene (TCE), cis-1,2-dichloroethylene (cis-DCE), and vinyl chloride (VC) for more than three decades. Monitoring and investigation were implemented during 2011–2024, aiming to propose future groundwater aquifer management strategies. This study included groundwater borehole investigation, well installation monitoring, hydraulic head measurements, slug tests, groundwater samplings, and microbial analyses. Microbial investigations identified the predominant group of microorganisms of Proteobacteria, indicating biodegradation potential, as demonstrated by the presence of cis-DCE and VC. BIOSCREEN was used to evaluate the process of natural attenuation, incorporating site-specific parameters. A two-layer groundwater flow model was developed using MODFLOW with hydraulic conductivities obtained from slug tests. The site has an average hydraulic head of 259.6 m amsl with a hydraulic gradient of 0.026, resulting in an average groundwater flow velocity of 11 m/y. Hydraulic conductivities were estimated during model calibration using the PEST pilot point technique. A reactive transport model, RT3D, was used to simulate dissolved TCE transport over 30 years, which can undergo sorption as well as biodegradation. Model calibration demonstrated a satisfactory fit between observed and simulated groundwater heads with a root mean square error of 0.08 m and a correlation coefficient (r) between measured and simulated heads of 0.81, confirming the validity of the hydraulic conductivity distribution. The TCE plume continuously degraded and gradually migrated southward, generating a cis-DCE plume. The concentrations in both plumes decreased toward the end of the simulation period at Source 1 (located upstream), while BIOSCREEN results confirmed ongoing natural attenuation primarily by biodegradation. The integrated MODFLOW-RT3D-BIOSCREEN approach effectively evaluated VOC attenuation and plume migration. However, future remediation strategies should consider enhanced bioremediation to accelerate contaminant degradation at Source 2 and ensure long-term groundwater quality. Full article

Plastic pollution poses significant environmental challenges due to its persistence and contribution to the microplastic formation, with polyethylene being among the materials more abundantly found. Understanding how different artificial weathering protocols influence the degradation of plastics is crucial for assessing their environmental impact. This study investigates the effects of three distinct artificial weathering protocols—continuous UV-A irradiation (M_L), cyclic UV-dark exposure (M_C[L→D]), and sequential UV-dark phase (M_L→D)—on the physicochemical properties of plastics, using oxo-low-density polyethylene as the model material. Surface oxidation, measured by quantification of the carbonyl index, was most pronounced under the M_C[L→D] protocol despite the shortest time of overall UV exposure, indicating that oxidative reactions continue during the dark phases. Vinyl group formation, however, required continuous or cyclic UV exposure, highlighting the critical role of light in this chemical process. Alterations in the surface hydrophilicity, measured by contact angle, and changes in molecular weight were quantified and found to closely link to the weathering conditions, with increased oxidations enhancing the surface hydrophilicity and the chain scission balanced by crosslinking with extended UV durations. These findings emphasize the importance of weathering protocols when trying to simulate conditions in the lab that are closer to the ones in the environment to understand plastic degradation mechanisms. Biodegradation experiments with Rhodococcus rhodochrous demonstrated that weathered oxo-LDPE samples with higher surface oxidation levels (ΔCI > 1) supported an increased CO₂ production by Rhodococcus rhodochrous, with the M_C[L→D]—360 h protocol yielding the highest biodegradation rates—31–43% higher than the control. Full article

Background/Objectives: Positron emission tomography (PET) and single-photon emission computed tomography (SPECT) are highly sensitive clinical imaging modalities, frequently employed in conjunction with magnetic resonance imaging (MRI) or computed tomography (CT) for diagnosing a wide range of disorders. Efficient and robust radiolabeling methods are needed to accommodate the increasing demand for PET and SPECT tracer development. Copper-mediated radiohalogenation (CMRH) reactions enable rapid late-stage preparation of radiolabeled arenes, yet synthetic challenges and radiolabeling precursors’ instability can limit the applications of CMRH approaches. Methods: A series of aryl-boronic acids were converted into their corresponding aryl-boronic acid 1,1,2,2-tetraethylethylene glycol esters [ArB(Epin)s] and aryl-boronic acid 1,1,2,2-tetrapropylethylene glycol esters [ArB(Ppin)s] as stable and versatile precursor building blocks for radiolabeling via CMRH. General protocols for the preparation of ¹⁸F-labeled and ¹²³I-labeled arenes utilizing CMRH of these substrates were developed and applied. The radiochemical conversions (RCC) were determined by radio-(U)HPLC. Results: Both ArB(Epin)s and ArB(Ppin)s-based radiolabeling precursors were prepared in a one-step synthesis with chemical yields of 49–99%. Radiolabeling of the aryl-boronic esters with fluorine-18 or iodine-123 via CMRH furnished the corresponding radiolabeled arenes with RCC of 7–99% and 10–99%, respectively. Notably, a radiohalogenated prosthetic group containing a vinyl sulfone motif was obtained with an activity yield (AY) of 18 ± 3%, and applied towards the preparation of two clinically relevant PET tracers. Conclusions: This approach enables the synthesis of stable radiolabeling precursors and thus provides increased versatility in the application of CMRH, thereby supporting the development of novel PET and SPECT radiotracers. Full article

A series of water-soluble molecules based on 8-isopropyl-2-methyl-5-nitroquinoline and 1,10-phenanthroline core were designed by introducing a π-conjugated bridge, vinyl unit –CH=CH–. We present the selective conversion of methyl groups located on the C2 and C9 positions in the constitution of selected quinoline or 1,10-phenanthroline derivatives, respectively, into vinyl (or styryl) products by applying Perkin condensation. The two groups of ligands differ in the presence of one or two arms. The structure of the molecule ((1E,1′E)-(1,10-phenanthroline-2,9-diyl)bis(ethene-2,1-diyl))bis(benzene-4,1,3-triyl) tetraacetate was determined by single-crystal X-ray diffraction measurements. The X-ray, NMR, and DFT computational studies indicate the influence of rotation (rotamers) on the physical properties of studied styryl molecules. The results show that the styryl molecules with the vinyl unit –CH=CH– exhibit significant static and dynamic hyperpolarizabilities. Quantum chemical calculations using density functional theory and B3LYP/6-311++G(d,p) with Grimme’s dispersion correction approach predict the existence and relative stability of different spatial cis(Z)- and trans(E)-conformers of styryl derivatives of quinoline and 1,10-phenanthroline, which exhibit different electronic distribution and conjugation within the molecular skeleton, dipole moments, and steric interactions, leading to variations in their photophysical behavior and various applications. Our studies indicate that the rotation and isomerization of aryl groups can significantly influence the electronic and optical properties of π-conjugated systems, such as vinyl units (–CH=CH–). The rotation of aryl groups around the single bond that connects them to the vinyl unit can lead to changes in the effective π-conjugation between the aryl group and the rest of the π-conjugated system. The rotation and isomerization of aryl groups in π-conjugated systems significantly impact their electronic and optical properties. These changes can modify the efficiency of π-conjugation, affecting charge transfer processes, absorption properties, light emission, and electrical conductivity. In designing optoelectronic materials, such as organic dyes, organic semiconductors, or electrochromic materials, controlling the rotation and isomerization of aryl groups can be crucial for optimizing their functionality. Full article

Protein phosphorylation is one of the most common and important post-translational modifications (PTMs) and is highly involved in various biological processes. Ideal adsorbents with high sensitivity and specificity toward phosphopeptides with large coverage are therefore essential for enrichment and mass spectroscopy-based phosphoproteomics analysis. In this study, a newly designed IMAC adsorbent composite was constructed on the graphene matrix coated with mesoporous silica. The outer functional 3D-network layer was prepared by free radical polymerization of the phosphonate-functionalized vinyl imidazolium salt monomer and subsequent metal immobilization. Due to its unique structural feature and high content of Ti⁴⁺ ions, the resulting phosphonate-immobilized adsorbent composite G@mSiO₂@PPFIL-Ti⁴⁺ exhibits excellent performance in phosphopeptide enrichment with a low detection limit (0.1 fmol, tryptic β-casein digest) and superior selectivity (molar ratio of 1:15,000, digest mixture of β-casein and bovine serum albumin). G@mSiO₂@PPFIL-Ti⁴⁺ displays high tolerance to loading and elution conditions and thus can be reused without a marked decrease in enrichment efficacy. The captured phosphopeptides can be released globally, and mono-/multi-phosphopeptides can be isolated stepwise by gradient elution. When applying this material to enrich phosphopeptides from human lung cell lysates, a total of 3268 unique phosphopeptides were identified, corresponding to 1293 phosphoproteins. Furthermore, 2698 phosphorylated peptides were found to be differentially expressed (p < 0.05) between human lung adenocarcinoma cells (SPC-A1) and human normal epithelial cells (Beas-2B), of which 1592 were upregulated and 1106 were downregulated in the cancer group. These results demonstrate the material’s superior enrichment efficiency in complex biological samples. Full article

Current hydrogels used for cartilage tissue engineering often lack the mechanical strength and structural integrity required to mimic native human cartilage. This study addresses this limitation by developing reinforced hydrogels based on a ternary polymer blend of poly(vinyl) alcohol (PVA), gelatin (GL), and chitosan (CH), with gentamicin sulfate (GS) as an antimicrobial agent and a crosslinker. The hydrogels were produced using two crosslinking methods, the freeze/thaw and heated cycles, and reinforced with forcespun polycaprolactone (PCL) nanofiber to improve mechanical performance. Chemical characterization revealed that GS forms weak hydrogen bonds with the ternary polymers, leading to esterification with PVA, and covalent bonds are formed as the result of the free amino group (-NH₂) of chitosan that reacts with the carboxylic acid group (-COOH) of gelatin. SEM images help us to see how the hydrogels are reinforced with polycaprolactone (PCL) fibers produced via force spinning technology, while mechanical properties were evaluated via uniaxial tensile and compressive tests. Water retention measurements were performed to examine the crosslinking process’s influence on the hydrogel’s water retention, while the hydrogel surface roughness was obtained via confocal microscopy images. A constitutive model based on non-Gaussian strain energy density was introduced to predict experimental mechanical behavior data of the hydrogel, considering a non-monotonous softening function. Loading and unloading tests demonstrated that GS enhanced crosslinking without compromising water retention or biocompatibility because of the reaction between the free amino group of CH and the carboxylic group of gelatin. The PCL-reinforced PVA/GL/CH hydrogel shows strong potential for cartilage repair and tissue engineering applications. Full article

Nanostructured drug-delivery systems with enhanced therapeutic potential have gained attention in biomedical applications. Here, flufenamic acid (FFA)-loaded chitosan/poly(vinyl alcohol) (CHS/PVA; CSPA)-based electrospun nanofibers were fabricated and characterized for antibacterial, anticancer, and antioxidant activities. The FFA-loaded CSPA (FCSPA) nanofibers were characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction (XRD), and differential scanning calorimetry to evaluate their formation process, functional group interactions, and crystallinity. Notably, the average diameter of FCSPA nanofibers decreased with increasing CSPA contents (CSPA-1 to CSPA-3), indicating that FFA addition to CSPA-3 significantly decreased its diameter. Additionally, XRD confirmed the dispersion of FFA within the CSPA amorphous matrix, enhancing drug stability. FCSPA nanofibers exhibited a high swelling ratio (significantly higher than that of the CSPA samples). Biodegradation studies revealed that FCSPA exhibited accelerated weight loss after 72 h, indicating its improved degradation compared with those of other formulations. Furthermore, it exhibited a significantly high drug-encapsulation efficiency, ensuring sustained release. FCSPA nanofibers exhibited excellent antibacterial activity, inhibiting Staphylococcus aureus and Escherichia coli. Regarding anticancer activity, FCSPA decreased HCT-116 cell viability, highlighting its controlled drug-delivery potential. Moreover, FCSPA demonstrated superior antioxidation, scavenging DPPH free radicals. These findings highlight FCSPA nanofibers as multifunctional platforms with wound-healing, drug-delivery, and tissue-engineering potential. Full article

A PAAc-PVI(4:1)@MWCNT hybrid was synthesized for the selective electrochemical detection of serotonin. Multi-walled carbon nanotubes (MWCNT) enhanced electrode conductivity, while the hydrophilic polymer Poly(Acrylic Acid-co-Vinyl imidazole) (PAAc-PVI) facilitated serotonin recognition. At pH 7.4, the carboxyl (-COO⁻) groups in PAAc-PVI interacted with the amine (-NH₃⁺) groups of serotonin, enabling oxidation and electron transfer for signal detection. Additionally, π-π interactions between vinylimidazole and MWCNT improved dispersion and stability. The hybrid materials enhanced electron transfer efficiency, increasing sensitivity and reliability. Structural and electrochemical properties were characterized using FT-IR, HR-TEM, TGA, Raman spectroscopy, impedance analysis, and differential pulse voltammetry (DPV). Serotonin detection using the fabricated electrode demonstrated high selectivity (LOD 0.077 μM and LOQ 0.26 μM), reproducibility (%RSD 1X PBS condition (4.63%) and human serum condition (4.81%)), and quantitative capability (dynamic range 1.2 μM to 10.07 μM) without interference (potential shift from +0.40 V to −0.15 V) from blood-based substances, confirming its potential for electrochemical biosensing applications. Full article

Scar formation and delayed wound healing pose significant challenges in treating skin injuries, especially in severe cases like burns and diabetic wounds. This study investigates the effectiveness of novel Poly(vinyl alcohol) (PVA)/Gentamicin (Gent) and PVA/Chitosan (CHI)/Gent hydrogels in promoting healing of second-degree burn wounds in a rat model. Following in vitro testing, these hydrogels were deemed non-toxic and suitable for in vivo analysis. Clinical evaluations were conducted on the 3rd, 7th, 14th, and 21st post-injury days, assessing parameters such as blistering, edema, redness, crust, bleeding, secretion, scar tissue formation, and wound contraction percentage. Histological analyses focused on re-epithelization and dermal evaluation at specific time points. Results showed that both hydrogels significantly reduced inflammation, particularly redness, by the 14th day and improved re-epithelization, with the PVA/CHI/Gent group outperforming on the 14th day and the PVA/Gent group excelling on the 21st day. Histological findings indicated increased fibroblast proliferation and collagen deposition in treated groups, suggesting enhanced dermal healing. The PVA/CHI/Gent hydrogel demonstrated notable antibacterial properties, likely due to the synergistic effects of CHI and Gent, leading to reduced inflammation and edema. Overall, both hydrogels show promise as effective wound dressings, facilitating faster healing and improved tissue recovery in burn injuries. This study supports the use of biomimetic scaffolds for enhanced wound management in clinical practices. Full article