Search Results (583)

Asphalt pavement cracking is an important factor affecting its service life. Under certain conditions, the self-healing behavior of asphalt itself can repair pavement cracks. However, the self-healing ability of asphalt itself is limited. In order to strengthen the self-healing ability of asphalt, the microcapsule wrapped with a repair agent is pre-mixed into the asphalt mixture. When the crack occurs and spreads to the surface of the microcapsule, the microcapsule ruptures and the healing agent flows out to realize the self-healing of the crack. Current microcapsules are mostly prepared with healing agents and bio-oil as core materials, and their high-temperature resistance to rutting is poor. While the epoxy resin contains a three-membered cyclic ether, it can undergo ring-opening polymerization to bond and repair the asphalt matrix. In addition, research on microcapsules mainly focuses on the self-healing properties of microcapsule-modified asphalt. In fact, before adding microcapsules to asphalt to improve its self-healing performance, it is necessary to ensure that the asphalt has a good road performance. On this basis, the self-healing performance of asphalt is improved, thereby extending the service life of asphalt pavement. Therefore, two-component epoxy self-healing microcapsules (E-mic and G-mic) were first prepared in this paper. Then, a temperature scanning test, rheological test of bending beams, and linear amplitude scanning test were, respectively, conducted for the microcapsule/asphalt to evaluate its road performance, including the high-temperature performance, low-temperature crack resistance, and fatigue performance. Finally, the self-healing performance of microcapsules/asphalt was tested. The results showed that the self-developed epoxy self-healing microcapsules were well encapsulated and presented as spherical micron-sized particles. The average particle size of the E-mic was approximately 23.582 μm, while the average particle size of the G-mic was approximately 22.440 μm, exhibiting a good normal distribution. In addition, they can remain intact and unbroken under high-temperature conditions. The results of road performance tests indicated that the microcapsule/asphalt mixture exhibits an excellent high-temperature resistance to permanent deformation, low-temperature crack resistance, and fatigue resistance. The self-healing test demonstrated that the microcapsule/asphalt exhibited an excellent self-healing performance. When the microcapsule content was 4%, the self-healing rate reached its optimal level of 67.8%, which was 149.2% higher than that of the base asphalt. Full article

Polylactic acid (PLA) is a renewable biopolymer that has attracted considerable interest due to its ability to replace petroleum-based synthetic polymers, thereby offering a more sustainable alternative to global environmental concerns. This study focused on evaluating the effect of catalyst concentration and reaction time on the efficiency of PLA synthesis via the Ring-Opening Polymerization (ROP) technique. The process involved a lactic acid esterification stage (using 88% lactic acid) to obtain lactide, employing 40% and 60% (v/v) sulfuric acid concentrations, followed by polymerization at various reaction times (10, 15, 20, and 30 min). Analysis of variance (ANOVA) results revealed that the 40% catalyst concentration had a statistically significant effect on polymer yield (p = 0.032), whereas reaction time showed no statistical significance (p = 0.196), although the highest yields were recorded at 10 and 15 min. Fourier Transform Infrared Spectroscopy (FTIR) confirmed the presence of the characteristic functional groups of PLA, and Differential Scanning Calorimetry (DSC) revealed a semi-crystalline structure with a high melting temperature, indicating good thermal stability. These results validate the viability of PLA as a functional and sustainable biopolymer. Full article

This study discloses the noncovalent immobilization of a bienzyme cascade composed of glucose oxidase (GOx) and horseradish peroxidase (HRP) onto magnetically responsive polyamide microparticles (PA MPs). Porous PA6, PA4, and PA12 MPs containing iron fillers were synthesized via activated anionic ring-opening polymerization in suspension, alongside neat PA6 MPs used as a reference. Four hybrid catalytic systems (GOx/HRP@PA) were prepared through sequential adsorption of HRP and GOx onto the various PA MP supports. The initial morphologies of the supports and the hybrid biocatalysts were characterized by SEM, followed by evaluation of the catalytic performance using a two-step glucose oxidation cascade process. Among all systems, the GOx/HRP@PA4-Fe complex exhibited the highest activity, being approximately 1.5 times greater than the native enzyme dyad, followed by the PA6-supported system with slightly inferior performance. All systems obeyed Michaelis–Menten kinetics, with the immobilized cascades displaying higher Kₘ and Vₘₐₓ values than the non-immobilized enzyme pair while maintaining comparable catalytic efficiencies, CE (CE = k_cat/Kₘ). Subsequently, the immobilized and native enzyme systems were employed for the polymerization of aniline. According to UV–VIS, complete monomer conversion was achieved within 24 h for selected catalysts, and FTIR analysis confirmed the formation of polyaniline in the emeraldine base form without the use of template molecules. These findings highlight the potential of Fe-containing polyamide microparticles as efficient supports for the sustainable, enzyme-mediated synthesis of intrinsically conductive aromatic polymers. Full article

The polymerization of norbornene can occur via ring-opening metathesis polymerization (ROMP) or vinyl-addition pathways, each yielding polynorbornene with distinct structures and properties. This study reports on the synthesis and catalytic application of a new class of vanadium(III) and nickel(II) complexes bearing N-heterocyclic carbene ligands, based on the IPr* framework, for the polymerization of norbornene. The vanadium(III) complexes, activated by diethylaluminum chloride and in the presence of ethyl trichloroacetate, showed activity in ROMP. In contrast, the nickel(II) complexes, activated by methylaluminoxane, exhibited catalytic activity toward vinyl-addition polymerization. Characterization by GPC, NMR, and FTIR confirmed the formation of both ring-opening metathesis polymerization and vinyl-type-derived polynorbornenes, with vinyl-type polymers showing significantly higher molecular weights. Structural variations in the N-heterocyclic carbene ligands, particularly the linker length between imidazole donors, were found to strongly influence polymer molecular weight and the morphology of polynorbornenes. Full article

The synthesis of novel biodegradable polymers as non-viral vectors remains one of the challenging tasks in the field of gene delivery. In this study, the synthesis of the polysaccharide-g-polypeptide copolymers, namely, hyaluronic acid-g-polylysine (HA-g-PLys), using a copper-free strain-promoted azide-alkyne cycloaddition reaction was proposed. For this purpose, hyaluronic acid was modified with dibenzocyclooctyne moieties, and poly-L-lysine with a terminal azido group was obtained using ring-opening polymerization of N-carboxyanhydride of the corresponding protected amino acid, initiated with the amino group azido-PEG₃-amine. Two HA-g-PLys samples with different degrees of grafting were synthesized, and the structures of all modified and synthesized polymers were confirmed using ¹H NMR and FTIR spectroscopy. The HA-g-PLys samples obtained were able to form nanoparticles in aqueous media due to self-assembly driven by electrostatic interactions. The binding of DNA and model siRNA by copolymers to form polyplexes was analyzed using ethidium bromide, agarose gel electrophoresis, and SybrGreen I assays. The hydrodynamic diameter of polyplexes was ˂300 nm (polydispersity index, PDI ˂ 0.3). The release of a model fluorescently-labeled oligonucleotide in the complex biological medium was significantly higher in the case of HA-g-PLys as compared to that in the case of PLys-based polyplexes. In addition, the cytotoxicity in normal and cancer cells, as well as the ability of HA-g-PLys to facilitate intracellular delivery of anti-GFP siRNA to NIH-3T3/GFP+ cells, were evaluated. Full article

To address the challenges of cotton cellulose materials being susceptible to environmental humidity and pollutant erosion, a strategy for constructing superhydrophobic functional coatings with biomimetic micro–nano composite structures was proposed. Through surface silanization modification, diatomite (DEM) and Fe₃O₄ nanoparticles were functionalized with octyltriethoxysilane (OTS) to prepare superhydrophobic diatomite flakes (ODEM) and OFe₃O₄ nanoparticles. Following the multi-scale composite principle, ODEM and OFe₃O₄ nanoparticles were blended and crosslinked via the hydroxyl-initiated ring-opening polymerization of epoxy resin (EP), resulting in an EP/ODEM@OFe₃O₄ composite coating with hierarchical roughness. Microstructural characterization revealed that the micrometer-scale porous structure of ODEM and the nanoscale protrusions of OFe₃O₄ form a hierarchical micro–nano topography. The special topography combined with the low surface energy property leads to a contact angle of 158°. Additionally, the narrow bandgap semiconductor characteristic of OFe₃O₄ induces the localized surface plasmon resonance effect. This enables the coating to attain 80% light absorption across the 350–2500 nm spectrum, and rapidly heat to 45.8 °C within 60 s under 0.5 sun, thereby demonstrating excellent deicing performance. This work provides a theoretical foundation for developing environmentally tolerant superhydrophobic photothermal coatings, which exhibit significant application potential in the field of anti-icing and anti-fouling. Full article

Polymeric nanoparticles based on poly(ethyl cyanoacrylate) (PECA) and poly(ε-caprolactone) (PCL) were synthesized via semicontinuous microemulsion polymerization for potential biomedical applications. A systematic evaluation of four surfactants (Tween 80, Alkonat L70, Genapol LRO, and Brij-20) was carried out to determine their effects on micelle formation and particle size. Brij-20 enabled the formation of nanoparticles under 100 nm, with optimal conditions identified at 4% surfactant concentration and pH 1.75. The polymerization process included acid-catalyzed ring-opening of ε-caprolactone, followed by the semicontinuous addition of ethyl-2-cyanoacrylate under an inert atmosphere. Copolymerization was confirmed through FT-IR spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and differential scanning calorimetry, revealing a glass transition temperature (T_g) of 110.9 °C, indicating PECA as the dominant phase. Thermogravimetric analysis showed two decomposition events corresponding to each polymer. Transmission electron microscope analysis revealed nanoparticles averaging 51.74 nm in diameter. These findings demonstrate the feasibility of producing PECA-PCL nanoparticles with controlled size and composition, suitable for drug delivery and other biomedical uses. Full article

In this study, poly-DL-lactic acid (PDLLA) was synthesized via ring-opening polymerization (ROP) to develop a biomedical scaffold for tissue engineering. A rotary evaporator with a two-stage vacuum pump under an inert atmosphere and constant stirring was used. A factorial design with three factors (oligomerization time, ROP time, and catalyst concentration) at two levels was applied. Polymers were characterized by FTIR, capillary viscometry, ¹H-NMR, DSC, and TGA. The kinetic study revealed a first-order model, indicating that the polymerization rate depends linearly on monomer concentration. The activation energy (70.5 kJ/mol) suggests a moderate energy requirement, consistent with ring-opening polymerization, while the high pre-exponential factor (6.93 × 10⁶ min⁻¹) reflects a significant frequency of molecular collisions. The scaffold was fabricated via extrusion and 3D printing, and its morphology, porosity, mechanical properties, and contact angle were studied. The highest molecular weight PDLLA was obtained with 6 h of oligomerization, 4 h of ROP, and 1% catalyst concentration. The samples exhibited thermal stability below 40 °C, while the scaffold reached 71.6% porosity, an 85.97° contact angle, and a compressive strength of 4.24 MPa with an elastic modulus of 51.7 MPa. These findings demonstrate the scaffold’s potential for biomedical applications. Full article

Glycopolypeptoids were synthesized and showed effective antifreeze activity, demonstrating their potential as novel antifreeze agents for cryopreservation. These polypeptide analogs offer improved stability and tunability compared with natural antifreeze glycoproteins (AFGPs) and existing synthetic mimics. Using the ring-opening polymerization of N-substituted N-carboxyanhydride monomers followed by click chemistry, glycopolypeptoids with controlled polymerization degrees and varied structures were designed and prepared. Their antifreeze performance was assessed via nanoliter osmometry and ice recrystallization inhibition assays, revealing a strong correlation between the molecular structure and antifreeze activity. The findings highlight glycopolypeptoids as a promising, cost-effective alternative to natural AFGPs, providing new insights into the development of biomimetic cryoprotectants. This study expands the understanding of synthetic antifreeze materials and offers a practical approach for improving cryopreservation efficiency in biomedical and industrial applications. Full article

Recent advances in zinc complexes for stereoselective ring-opening polymerization (ROP) and copolymerization (ROCOP) highlight their pivotal role in synthesizing biodegradable aliphatic polyesters and polycarbonates. These materials address the urgent demand for sustainable alternatives to petroleum-based plastics, with stereochemical control directly impacting polymer crystallinity, thermal stability, and degradability. Zinc catalysts, leveraging low toxicity and versatile coordination chemistry, enable precise stereoregulation, whose performance is modulated by ligand steric/electronic effects, coordination geometry, and reaction conditions. This review summarizes the recent developments in zinc complexes for stereoselective ROP and ROCOP, focusing on ligand design strategies to enhance catalytic performance. Full article

Bacterially produced poly[(R)-3-hydroxybutyrate] (P3HB) was subjected to an alcoholysis reaction to produce low-molecular-weight (M_n ≈ 10,000 g mol⁻¹) hydroxy-terminated P3HB (LMPHB). Using diethyl zinc as a catalyst, LMPHB was reacted with the cyclic monomers ε-caprolactone and l-lactide in separate ring-opening polymerization (ROP) reactions to produce PHB-b-PCL (PHBCL) and PHB-b-PLA (PHBLA) AB-type crystalline–crystalline diblock copolymers with varying PCL and PLA block lengths. ¹H NMR and GPC were used to confirm the structure of the polymers. DSC was used to measure the thermal properties as well as assessing crystallization. A single-shifting T_g for PHBLA showed the two blocks to be miscible in the melt. The TGA results indicate enhanced thermal stability over the homopolymer P3HB. A study of the crystallization was undertaken by combining WAXD, a second DSC heating regime, and POM. POM showed that the crystallization in PHBCL to be dependent on the crystallization temperature more so than PHBLA, whose composition appeared to be the more definitive factor determining the spherulitic morphology. The results informed the crystallization temperatures used in the production of the melt-crystallized thin films that were imaged using AFM. AFM images showed unique surface morphologies dependent on the diblock copolymer composition, block length, and crystallization temperature. Finally, the enzymatic degradation studies showed these unique surface morphologies to influence how these block copolymers were degraded by enzymes. Full article

Bio-based polyurethane (PU) is synthesized either via the prepolymerization or addition polymerization of bio-based polyols and isocyanates. PU synthesized from vegetable-oil-based polyols has excellent properties for various application needs. Bio-based PU coatings from renewable vegetable oil show good degradability in soil while controlling the nutrient release process. Castor oil, soybean oil, palm oil, olive oil, linseed oil, rapeseed oil, cottonseed oil, and recycled oil have been explored in the study of bio-based PU coatings for controlled nutrient release. Castor oil as a natural polyol has been widely studied. Generally, the epoxidation ring opening method is preferred to prepare bio-based polyols. Almost all of these studies used a drum coating machine to complete the coating process. To obtain better controlled release performance, a vegetable-oil-based PU (VPU) coating was modified by increasing the degrees of crosslinking and hydrophobicity and improving the coating uniformity. The nutrient release duration of the modified castor-oil-based PU-coated fertilizer reached 200 days. VPU-coated fertilizers, in contrast to traditional fertilizers, effectively reduce the detrimental impact on the environment. Although the preparation of VPU-coated fertilizers is still at the laboratory scale, application research has been carried out in field crops. Full article

We report the synthesis of highly enantiopure perdeuterated poly-L-lactic acid and poly-D-lactic acid polymers with well-defined molecular weight by polymerization of perdeuterated lactides. Enantiopure D- and L-lactic acid-d₄ monomers were synthesized from sodium pyruvate-d₃ using D- and L-lactate dehydrogenase enzymes (D-LDH and L-LDH) as biocatalysts. The reduced form of the co-enzyme nicotinamide adenine dinucleotide-d₁ (NADH-d₁) was generated in situ from the oxidized form nicotinamide adenine dinucleotide (NAD⁺) by formate dehydrogenase (FDH)-catalyzed oxidation of sodium formate-d₁ to carbon dioxide with concerted reduction of NAD⁺ to NADH-d₁. For the conversion of the perdeuterated lactic acid monomers to the corresponding lactide dimers, we developed a process for generating these compounds in the high purity needed for the final anionic ring-opening polymerization step. This method enabled the generation of a range of perdeuterated polylactic acid polymers that are highly suitable for the characterization of polymer structure and dynamics using neutron scattering, infrared and nuclear magnetic resonance spectroscopy methods that are sensitive to deuterium. Furthermore, these deuterium-labeled polymers are well-suited to the study of the biodegradation of PLA-based plastics. Full article

Unsaturated macrolactones (UMs) have long attracted researchers’ attention due to a combination of a reactive ester fragment and C=C bond in their structures. UMs of natural origin are comparatively few in number, and the task of developing synthetic approaches to new UMs is relevant. Recent advances in the synthesis of UMs cannot be dissociated from the progress in design of metathesis catalysts, since this catalytic approach is an atom-economy alternative to conventional organochemical methods. In the present review, we summarized and discussed the use of ring-closing metathesis, catalyzed by Ru and Group 6 metal complexes, in the synthesis of Ums and the advantages and shortcomings of the catalytic approach to UMs in comparison with organochemical methods. In a separate section, the use of UMs in the synthesis of unsaturated polyesters, the functionalization of these (co)polymers, and the prospects for practical use of the material obtained are also presented. It is essential that the actual approaches to UMs are often based on the use of renewable feedstocks, thereby meeting Green Chemistry principles. Full article

Benzoxazines are a kind of high-performance thermosetting resin that can undergo ring-opening polymerization to generate cross-linking structures. Here, two benzoxazine monomers, bisphenol A/aniline type (BA-a) and bisphenol A/tert-butylamine type (BA-tb), were synthesized and mixed with three tertiary amine catalysts like 2-methylimidazole (2MI), 1,2-dimethylimidazole (12MI), 4-dimethylaminopyridine (DMAP). Differential scanning calorimetry (DSC) was performed to study the curing behaviors and the curing kinetics of two benzoxazine/catalyst systems. The results indicated that all amines had a catalytic effect on the polymerization of both benzoxazines, and the BA-a/catalyst systems showed relatively higher activity. In addition, Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectra were procured to analyze structural changes in the benzoxazine/catalyst systems during the curing process. The presence of the catalysts promoted the progress of the ring-opening reactions and the formation of the phenolic units in the cross-linking structures, and these evolutions were more obvious for the BA-a/catalyst system than the BA-tb/catalyst system. Furthermore, a thermogravimetric analysis (TGA) was conducted to analyze the thermal stability of the cured systems. Finally, possible curing reaction mechanisms were proposed for these benzoxazine/amine systems. Full article