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Waterborne polyurethane (WPU) often suffers from poor water resistance and mechanical properties due to hydrophilic emulsifiers. To address these issues, this study introduces glycidyl carbamate (GC) as a crosslinker to improve WPU performance. Three types of GC were synthesized using aliphatic, cycloaliphatic, and aromatic isocyanates, respectively. The crosslinked network was established through a reaction between the epoxide group of GC and the carboxylic acid and amine groups of WPU. Among these, the WPU film utilizing aromatic isocyanate-based GC exhibited the highest crosslink density, modulus, hardness, and water resistance, due to the rigidity of the aromatic molecular structure. However, the film displayed excessive brittleness, resulting in reduced tensile strength, along with yellowing typically associated with aromatic compounds. The WPU crosslinked with cycloaliphatic GC demonstrated the next best mechanical properties and water resistance, with a 2.7-fold increase in tensile strength, a 1.5-fold increase in hardness, and a 66% reduction in the water swelling ratio compared to neat WPU. This study presents a novel and effective strategy to enhance the water resistance and mechanical properties of WPU films, making them suitable for advanced coating applications.

Environment-friendly polymer blends of poly(lactic acid) (PLA) and itaconic acid (IA), poly(itaconic acid) (PIA), poly(itaconic acid)- co -poly(methyl itaconate) (Cop-IA), and net- poly(itaconic acid)- ν -triethylene glycol dimethacrylate (Net-IA) were performed via melt blending. The compositions studied were 0.1, 1, 3, and 10 wt% of the diverse chemical architectures. The research aims to study and understand the effect of IA and its different architectures on the mechanical, rheological, and thermal properties of PLA. The PLA/IA, PLA/PIA, PLA/Cop-IA, and PLA/Net-IA blends were characterized by dynamic mechanical thermal analysis, rotational rheometer (RR), thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, and scanning electron microscopy. The complex viscosity, storage module, and loss module for the RR properties were observed in the following order: PLA/Cop-IA, PLA/Net-IA, and PLA/PIA > PLA > PLA/IA. Thermal stability improved with increasing concentrations of Cop-IA and Net-IA. In the same way, the mechanical properties were enhanced. In addition, the micrographs illustrated the formation of fibrillar structures for all blends. The crystallinity degree displayed higher values for the blends that contain Net-IA > Cop-IA than IA > PIA. Therefore, IA and its architectures can influence these studied properties, which have potential applications in disposable food packing.

Increasing of rubber content in isotactic polypropylene/ethylene-propylene rubber (iPP/EPR) alloys can extend the applications of this kind of polyolefin. The EPR content and phase structure of isotactic polypropylene multicomponents have great effect on the viscoelasticity and mechanical properties. iPP/EPR in-reactor alloys with a high EPR content were obtained through the in situ crosslinking of EPR chains with α,ω-diene. The morphological observation results indicate that the crosslinked iPP/EPR in-reactor alloys have a good spherical shape with clean and rough external surfaces. The high EPR content is finely dispersed in the crosslinked iPP/EPR alloys in areas ranging in size from tens of nanometers to several micrometers, which implies that a sufficient crosslinking degree of EPR chains can effectively prevent their aggregation and restrict macro-phase separation. The rheological results show a clear plateau in the terminal region, which reveals an entangled polymer chain network in the crosslinked iPP/EPR alloys. The well-dispersed EPR and the bi-continuous phase structure have a great effect on the mechanical properties of the isotactic polypropylene multicomponent which were assessed.

Collagen nanofibrous materials have become integral to tissue engineering due to their exceptional properties and biocompatibility. Dehydrothermal crosslinking (DHT) enhances stability and maintains structural integrity without the formation of toxic residues. The study involved the crosslinking of electrospun collagen, applying DHT with access to air and under vacuum conditions. Various DHT exposure times of up to 72 h were applied to examine the time dependance of the DHT process. The DHT crosslinked collagen was subsequently chemically crosslinked using carbodiimides. The material crosslinked in this way evinced elevated Young's modulus values and ultimate tensile strength values, a lower swelling rate and lower shrinkage ratio during crosslinking, and a higher degree of resistance to degradation than the material crosslinked solely with DHT or carbodiimides. It was shown that the crosslinking mechanism using DHT occupies different binding sites than those using chemical crosslinking. Access to air for 12 h or less did not exert a significant impact on the material properties compared to DHT under vacuum conditions. However, concerning longer exposure times, it was determined that access to air results in the deterioration of the properties of the material and that reactions take place that occupy the free bonding sites, which subsequently reduces the effectiveness of chemical crosslinking using carbodiimides.

Molecular dynamics simulation (MD) technology can be used to simulate and study the physicochemical properties of polymer materials on the basis of material data obtained in traditional experiments. In this study, we use MD to construct models of crosslinked carbon nanotubes/epichlorohydrin rubber composites with different carbon nanotube diameters and study the effect of CNT tube diameter on crosslinked ECO. The results show that with the increase in CNT tube diameter, the contact area between the CNTs and rubber matrix increases, the interaction force is enhanced, the free volume fraction of rubber matrix decreases by 21.36%, the glass transition temperature increases by 6.5%, the mean square displacement decreases, the radius of gyration decreases by 3.18 Å, and the radial distribution function of the C-atom group and the H-atom group in the system gradually decreases. The binding energy between the two is elevated, which in turn verifies the enhancement of the interaction force.

This study investigates the crosslinking dynamics and swelling properties of pH-responsive poly(ethylene glycol) (PEG)/poly(acrylic acid) (PAA) interpenetrating polymer network (IPN) hydrogels. These hydrogels feature denser crosslinked networks compared to PEG single network (SN) hydrogels. Fabrication involved a two-step UV curing process: First, forming PEG-SN hydrogels using poly(ethylene glycol) diacrylate (PEGDA) through UV-induced free radical polymerization and crosslinking reactions, then immersing them in PAA solutions with two different molar ratios of acrylic acid (AA) monomer and poly(ethylene glycol) dimethacrylate (PEGDMA) crosslinker. A subsequent UV curing step created PAA networks within the pre-fabricated PEG hydrogels. The incorporation of AA with ionizable functional groups imparted pH sensitivity to the hydrogels, allowing the swelling ratio to respond to environmental pH changes. Rheological analysis showed that PEG/PAA IPN hydrogels had a higher storage modulus ( G ') than PEG-SN hydrogels, with PEG/PAA-IPN5 exhibiting the highest modulus. Thermal analysis via thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) indicated increased thermal stability for PEG/PAA-IPN5 compared to PEG/PAA-IPN1, due to higher crosslinking density from increased PEGDMA content. Consistent with the storage modulus trend, PEG/PAA-IPN hydrogels demonstrated superior mechanical properties compared to PEG-SN hydrogels. The tighter network structure led to reduced water uptake and a higher gel modulus in swollen IPN hydrogels, attributed to the increased density of active network strands. Below the p K a (4.3) of acrylic acid, hydrogen bonds between PEG and PAA chains caused the IPN hydrogels to contract. Above the p Ka , ionization of PAA chains induced electrostatic repulsion and osmotic forces, increasing water absorption. Adjusting the crosslinking density of the PAA network enabled fine-tuning of the IPN hydrogels' properties, allowing comprehensive comparison of single network and IPN characteristics.

Anti-inflammatory wound healing involves targeted drug delivery to the wound site using hydrogel materials to prolong drug effectiveness. In this work, hydrogel films were fabricated using carboxymethyl cellulose (CMC) and poly(vinyl alcohol) (PVA) crosslinked with citric acid (CA) and glutaraldehyde (GA) at different concentrations. The crosslinker densities were optimized with various CA (2-10% w / v ) and GA (1-5% v / v ) concentrations. The optimized crosslink densities in the hydrogel exhibited additional functional group peaks in the FT-IR spectra at 1740 cm -1 for the C=O stretching of the ester linkage in CA and at 1060 cm -1 for the C-O-C stretching of the ether group in GA. Significantly, the internal porous structures of hydrogel composite films improved density, swelling capacities, solubility percentage reduction, and decreased water retention capacities with optimized crosslinker densities. Therefore, these hydrogel composite films were utilized as drug carriers for controlled drug release within 24 h during medical treatment. Moreover, the hydrogel films demonstrated increased triamcinolone acetonide (TAA) absorption with higher crosslinker density, resulting in delayed drug release and improved TAA efficiency in anti-inflammatory activity. As a result, the modified hydrogel showed the capability of being an alternative material with enhanced anti-inflammatory efficiency with hydrogel films.

The high demand for lithium (Li) relates to clean, renewable storage devices and the advent of electric vehicles (EVs). The extraction of Li ions from aqueous media calls for efficient adsorbent materials with various characteristics, such as good adsorption capacity, good selectivity, easy isolation of the Li-loaded adsorbents, and good recovery of the adsorbed Li ions. The widespread use of metal-based adsorbent materials for Li ions extraction relates to various factors: (i) the ease of preparation via inexpensive and facile templation techniques, (ii) excellent selectivity for Li ions in a matrix, (iii) high recovery of the adsorbed ions, and (iv) good cycling performance of the adsorbents. However, the use of nano-sized metal-based Lithium-ion sieves (LISs) is limited due to challenges associated with isolating the loaded adsorbent material from the aqueous media. The adsorbent granulation process employing various binding agents (e.g., biopolymers, synthetic polymers, and inorganic materials) affords composite functional particles with modified morphological and surface properties that support easy isolation from the aqueous phase upon adsorption of Li ions. Biomaterials (e.g., chitosan, cellulose, alginate, and agar) are of particular interest because their structural diversity renders them amenable to coordination interactions with metal-based LISs to form three-dimensional bio-composite materials. The current review highlights recent progress in the use of biopolymer binding agents for the granulation of metal-based LISs, along with various crosslinking strategies employed to improve the mechanical stability of the granules. The study reviews the effects of granulation and crosslinking on adsorption capacity, selectivity, isolation, recovery, cycling performance, and the stability of the LISs. Adsorbent granulation using biopolymer binders has been reported to modify the uptake properties of the resulting composite materials to varying degrees in accordance with the surface and textural properties of the binding agent. The review further highlights the importance of granulation and crosslinking for improving the extraction process of Li ions from aqueous media. This review contributes to manifold areas related to industrial application of LISs, as follows: (1) to highlight recent progress in the granulation and crosslinking of metal-based adsorbents for Li ions recovery, (2) to highlight the advantages, challenges, and knowledge gaps of using biopolymer-based binders for granulation of LISs, and finally, (3) to catalyze further research interest into the use of biopolymer binders and various crosslinking strategies to engineer functional composite materials for application in Li extraction industry. Properly engineered extractants for Li ions are expected to offer various cost benefits in terms of capital expenditure, percent Li recovery, and reduced environmental footprint.

Polypropylene-based aerogels with high surface area have been developed for the first time. By chemical crosslinking of polypropylene with oligomeric capped-end amino compounds, followed by dissolution, thermally induced phase separation, and the supercritical CO 2 drying process or freeze-drying method, the aerogels exhibit high specific surface areas up to 200 m 2 /g. Moreover, the silica-cage multi-amino compound was utilized in a similar vein for forming hybrid polypropylene aerogels. According to the SEM, the developed polypropylene-based aerogels exhibit highly porous morphology with micro-nanoscale structural features that can be controlled by processing conditions. Our simple and inexpensive synthetic strategy results in a low-cost, chemically resistant, and highly porous material that can be tailored according to end-use applications.

Acellular fish swim bladders (AFSBs) are a promising biomaterial in tissue engineering, however, they may suffer from rapid degradation due to enzyme invasion. In this work, natural polyphenols, including epigallocatechin gallate (EGCG), proanthocyanidin (PC), tannic acid (TA) and protocatechuic acid (PCA), were utilized to improve the properties of AFSBs through crosslinking modifications. Fourier transform infrared (FTIR) results indicate that the triple helix of the collagen in AFSBs is well preserved after crosslinking. The differential scanning calorimetry (DSC), water contact angle (WCA) and in vitro degradation tests indicate that the polyphenol-crosslinked AFSBs exhibit improved thermal stability, enzymatic stability, hydrophilicity and mechanical properties. Among them, EGCG with multiple phenolic hydroxyl groups and low potential resistance is more favorable for the improvement of the mechanical properties and enzymatic stability of AFSBs, as well as their biocompatibility and integrity with the collagen triple helix. Moreover, the crosslinking mechanism was demonstrated to be due to the hydrogen bonds between polyphenols and AFSBs, and was affected by the molecular size, molecular weight and the hydroxyl groups activity of polyphenol molecules, as clarified by molecular dynamic (MD) simulations. The approach presented in this work paves a path for improving the properties of collagen materials., Competing Interests: There are no conflicts of interest to declare.

Polypropylene-based multiphase compositions with a disperse elastomer phase provide superior impact strength. Making this property indifferent to processing steps requires stabilization of the morphology of these materials. Various approaches have been tested over time, each of which shows limitations in terms of performance or applicability. Using polyethylene (PE) homo- and copolymers capable of silane-based crosslinking as modifiers was explored in the present study, which allows decoupling of the mixing and crosslinking processes. Commercial silane-copolymerized low-density PE (LD-PEX) from a high-pressure process and silane-grafted high-density PE (HD-PEX) were studied as impact modifiers for different types of PP copolymers, including non-modified reference PE grades, LDPE and HDPE. Blends based on ethylene-propylene random copolymers (PPR) and based on impact- (PPI) and random-impact (PPRI) copolymers show improvements of the stiffness-impact balance; however, to different degrees. While the absolute softest and most ductile compositions are achieved with the already soft PPRI copolymer base, the strongest relative effects are found for the PPR based blends. Modifiers with lower density are clearly superior in the toughening effect, with the LD-PEX including acrylate as second comonomer sticking out due to its glass transition around -40 °C. The impact strength improvement found in most compositions (except at very high content) results, however, not from the expected phase stabilization. For comparable systems, particle sizes are normally higher with crosslinking, probably because the process already starts during mixing. Thermoplastic processability could be retained in all cases, but the drop in melt flow rate limits the practical applicability of such systems.

Silk fibroin (SF) hydrogels have garnered extensive attention in biomedical materials, owing to their superior biological properties. However, the challenges facing the targeted silk fibroin hydrogels involve chemical agents and shortfalls in performance. In this study, the silk fibroin hydrogels were prepared in different ways: sonication induction, chemical crosslinking, photopolymerization, and enzyme-catalyzed crosslinking. The SF hydrogels derived from photopolymerization exhibited higher compressive properties, with 124 Kpa fracture compressive stress and breaks at about 46% compression. The chemical crosslinking and enzyme-catalyzed silk fibroin hydrogels showed superior toughness, yet sonication-induced hydrogels showed brittle performance resulting from an increase in silk II crystals. The chemical-crosslinked hydrogel demonstrated lower thermostability due to the weaker crosslinking degree. In vitro, all silk fibroin hydrogels supported the growth of human umbilical vein endothelial cells, as the cell viability of hydrogels without chemical agents was relatively higher. This study provides insights into the formation process of silk fibroin hydrogels and optimizes their design strategy for biomedical applications.

In this investigation, we systematically explored the intricate relationship between the structural attributes of polyvinyl alcohol (PVA) membranes and their multifaceted properties relevant to fuel cell applications, encompassing diverse crosslinking conditions. Employing the solution casting technique, we fabricated crosslinked PVA membranes by utilizing phosphoric acid (PA) as the crosslinking agent, modulating the crosslinking temperature across a range of values. This comprehensive approach aimed to optimize the selection of crosslinking parameters for the advancement of crosslinked polymer materials tailored for fuel cell contexts. A series of meticulously tailored crosslinked PVA membranes were synthesized, each varying in PBTCA content (5-30 wt.%) to establish a systematic framework for elucidating chemical interactions, morphological transformations, and physicochemical attributes pertinent to fuel cell utilization. The manipulation of crosslinking agent concentration and crosslinking temperature engendered a discernible impact on the crosslinking degree, leading to a concomitant reduction in crystallinity. Time-resolved attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) was harnessed to evaluate the dynamics of liquid water adsorption and ionomer swelling kinetics within the array of fabricated PVA films. Notably, the diffusion of water within the PVA membranes adhered faithfully to Fick's law, with discernible sensitivity to the crosslinking conditions being implemented. Within the evaluated membranes, proton conductivities exhibited a span of between 10 -3 and 10 -2 S/cm, while methanol permeabilities ranged from 10 -8 to 10 -7 cm 2 /s. A remarkable revelation surfaced during the course of this study, as it became evident that the structural attributes and properties of the PVA films, under the influence of distinct crosslinking conditions, underwent coherent modifications. These changes were intrinsically linked to alterations in crosslinking degree and crystallinity, reinforcing the interdependence of these parameters in shaping the characteristics of PVA films intended for diverse fuel cell applications.

When applying electron or gamma irradiation to poly-3-hydroxybutyrate (P3HB), main chain scissions are the dominant material reactions. Though propositions have been made that crosslinking in the amorphous phase of P3HB occurs under irradiation, a conclusive method to achieve controlled additive free irradiation crosslinking has not been shown and no mechanism has been derived to the best of our knowledge. By applying irradiation in a molten state at 195 °C and doses above 200 kGy, we were able to initiate crosslink reactions and achieved gel formation of up to 16%. The gel dose D gel was determined to be 200 kGy and a range of the G values, the number of scissions and crosslinks for 100 eV energy deposition, is given. Rheology measurements, as well as size exclusion chromatography (SEC), showed indications for branching at doses from 100 to 250 kGy. Thermal analysis showed the development of a bimodal peak with a decrease in the peak melt temperature and an increase in peak width. In combination with an increase in the thermal degradation temperature for a dose of 200 kGy compared to 100 kGy, thermal analysis also showed phenomena attributed to branching and crosslinking.

Tailored porous structures of poly(2-hydroxyethyl methacrylate) (PHEMA) and silk sericin (SS) were used to create porous hydrogel scaffolds using two distinct crosslinking systems. These structures were designed to closely mimic the porous nature of the native extracellular matrix. Conventional free radical polymerization of 2-hydroxyethyl methacrylate (HEMA) was performed in the presence of different concentrations of SS (1.25, 2.50, 5.00% w / v ) with two crosslinking systems. A chemical crosslinking system with N ' N -methylene bisacrylamide (MBAAm) and a physical crosslinking system with dimethylurea (DMU) were used: C-PHEMA/SS (crosslinked using MBAAm) and C-PHEMA/pC-SS (crosslinked using MBAAm and DMU). The focus of this study was on investigating the impact of these crosslinking methods on various properties of the scaffolds, including pore size, pore characteristics, polymerization time, morphology, molecular interaction, in vitro degradation, thermal properties, and in vitro cytotoxicity. The various crosslinked networks were found to appreciably influence the properties of the scaffolds, especially the pore sizes, in which smaller sizes and higher numbers of pores with high regularity were seen in C-PHEMA/1.25 pC-SS (17 ± 2 μm) than in C-PHEMA/1.25 SS (34 ± 3 μm). Semi-interpenetrating networks were created by crosslinking PHEMA-MBAAm-PHEMA while incorporating free protein molecules of SS within the networks. The additional crosslinking step involving DMU occurred through hydrogen bonding of the -C=O and -N-H groups with the SS, resulting in the simultaneous incorporation of DMU and SS within the PHEMA networks. As a consequence of this process, the scaffold C-PHEMA/pC-SS exhibited smaller pore sizes compared to scaffolds without DMU crosslinking. Moreover, the incorporation of higher loadings of SS led to even smaller pore sizes. Additionally, the gelation time of C-PHEMA/pC-SS was delayed due to the presence of DMU in the crosslinking system. Both porous hydrogel scaffolds, C-PHEMA/pC-SS and PHEMA, were found to be non-cytotoxic to the normal human skin dermal fibroblast cell line (NHDF cells). This promising result indicates that these hydrogel scaffolds have potential for use in tissue engineering applications.

Objective: Sound, natural dentin collagen can be stabilized against enzymatic degradation through exogenous crosslinking treatment for durable bonding; however, the effect on denatured dentin (DD) collagen is unknown. Hence, the ability of different crosslinkers to enhance/restore the properties of DD collagen was assessed., Methods: Demineralized natural and DD collagen films (7 mm × 7 mm × 7 µm) and beams (0.8 mm × 0.8 mm × 7 mm) were prepared. DD collagen was experimentally produced by heat or acid exposure, which was then assessed by various techniques. All specimens were then treated with 1 wt% of chemical crosslinker 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/n-hydroxysuccinimide (EDC/NHS) and two structurally different flavonoids-theaflavins (TF) from black tea and type-A proanthocyanidins from cranberry juice (CR) for either 30 s or 1 h. The controls were untreated. Dentin films were assessed for chemical interaction and cross-linking effect by FTIR, biostability against exogenous collagenase by weight loss (WL) and hydroxyproline release (HYP), and endogenous matrix metalloproteinases (MMPs) activity by confocal laser microscopy. Dentin beams were evaluated for tensile properties. Data were analyzed using ANOVA and Tukey's test (α = 0.05)., Results: Compared with natural collagen, DD collagen showed pronounced structural changes, altered biostability and decreased mechanical properties, which were then improved to various degrees that were dependent on the crosslinkers used, with EDC/NHS being the least effective. Surprisingly, the well-known MMP inhibitor EDC/NHS showed negligible effect on or even increased MMP activity in DD collagen. As compared with control, cross-linking induced by TF and CR significantly increased collagen biostability (reduced WL and HYP release, p < 0.05), MMP inhibition ( p < 0.001) and mechanical properties ( p < 0.05), regardless of denaturation., Conclusions: DD collagen cannot or can only minimally be stabilized via EDC/NHS crosslinking; however, the challenging substrate of DD collagen can be enhanced or restored using the promising flavonoids TF and CR.

This comprehensive review begins by tracing the historical development and progress of cold plasma technology as an innovative approach to polymer engineering. The study emphasizes the versatility of cold plasma derived from a variety of sources including low-pressure glow discharges (e.g., radiofrequency capacitively coupled plasmas) and atmospheric pressure plasmas (e.g., dielectric barrier devices, piezoelectric plasmas). It critically examines key operational parameters such as reduced electric field, pressure, discharge type, gas type and flow rate, substrate temperature, gap, and how these variables affect the properties of the synthesized or modified polymers. This review also discusses the application of cold plasma in polymer surface modification, underscoring how changes in surface properties (e.g., wettability, adhesion, biocompatibility) can be achieved by controlling various surface processes (etching, roughening, crosslinking, functionalization, crystallinity). A detailed examination of Plasma-Enhanced Chemical Vapor Deposition (PECVD) reveals its efficacy in producing thin polymeric films from an array of precursors. Yasuda's models, Rapid Step-Growth Polymerization (RSGP) and Competitive Ablation Polymerization (CAP), are explained as fundamental mechanisms underpinning plasma-assisted deposition and polymerization processes. Then, the wide array of applications of cold plasma technology is explored, from the biomedical field, where it is used in creating smart drug delivery systems and biodegradable polymer implants, to its role in enhancing the performance of membrane-based filtration systems crucial for water purification, gas separation, and energy production. It investigates the potential for improving the properties of bioplastics and the exciting prospects for developing self-healing materials using this technology.

Industrial polyureas are typically synthesized using diisocyanates via two possible alternative pathways: the extremely quick and highly exothermal diamine-diisocyanate pathway and the relatively slow and mild water-diisocyanate pathway. Although polyurea synthesis via the water-diisocyanate pathway is known and has been industrially applied for many decades, there is surprisingly very little analytical information in the literature in relation to the type and extent of the occurring side reactions and the resulting chemical structures following this synthesis pathway. The synthesis of polyureas exhibiting very high concentrations of carbonyl-containing groups resulted in strong and accurate diagnostic analytical signals of combined FTIR and solid-state 13 C NMR analysis. Despite the strictly linear theoretical chemical structure designed, the syntheses resulted in highly nonlinear and crosslinked polymers. It was analytically found that the water-diisocyanate pathway preferentially produced highly dominant and almost equal contents of both biuret structures and tertiary oligo-uret structures, with a very small occurrence of urea groups. This is in strong contrast with the chemical structures previously obtained via the diamine-diisocyanate polyurea synthesis pathway, which almost exclusively resulted in biuret structures. The much slower reaction and crosslinking rate of the water-diisocyanate synthesis pathway enabled the further access of isocyanate groups to the already-formed secondary nitrogens, thus facilitating the formation of complex hierarchical tertiary oligo-uret structures.

Preparing strong and flexible atelocollagen-based materials for biomedical applications is still a challenging task. To address this challenge, this study describes the synthesis and characterization of water-soluble polyrotaxanes (PRs) with different coverage ratios and molecular weights of axle polymers, and their potential applications for PR-reinforced atelocollagen threads (PRATs). A novel method was established for the syntheses of PRs with relatively low coverage ratio at the sub-gram scale, in which the aldehyde groups were employed as crosslinking sites for preparing the PRATs via reductive amination. The aldehyde groups were successfully quantified by 1 H nuclear magnetic resonance spectroscopy using 1,1-dimethylhydrazine as an aldehyde marker. Fourier-transform infrared and thermogravimetric analysis measurements supported the characterization of the PRs. Interestingly, tensile testing demonstrated that coverage ratio affected the mechanical properties of the PRATs more strongly than molecular weight. The insights obtained in this study would facilitate the development of soft materials based on atelocollagens and PRs.

This work aimed to evaluate the properties of butylene adipate-co-terephthalate (PBAT) degraded after 1800 days of storage (DPBAT) by preparing blends (films) with crosslinked starch (Cm) through extrusion and thermocompression. Different ratios of DPBAT:Cm (70:30, 60:40, and 50:50 m/m) were prepared. The incorporation of Cm into DPBAT significantly changed the properties of the films by making them stiffer (increasing Young's modulus by up to 50%) and increasing the thermal resistance of DPBAT. The presence of crosslinked starch in the films made them less hydrophobic (with decreased contact angle and increased moisture content), but these parameters did not vary linearly with changes in the content of crosslinked starch in the blend (DPBAT:Cm). The microscopic images show an inhomogeneous distribution of Cm granules in the DPBAT matrix. Thus, the films prepared with PBAT show a significant decrease in their mechanical parameters and heat resistance after long-term storage. However, the preparation of blends of degraded DPBAT with crosslinked starch promoted changes in the properties of the films prepared by thermocompression, which could be useful for disposable packaging.

Green tea polyphenol (TP) was encapsulated in zein and fabricated into a gelatin-zein composite film by complex coacervation. Transglutaminase (TG) crosslinking was employed to obtain a compact structural orientation of the film to prolong the release of bioactive compounds. The encapsulation efficiency of zein and the TP release rate from the composite film were investigated. The retention rate was over 30% and 80% after film fabrication and storage, respectively. Crosslinking decreased the diffusion coefficient by half, thus improving the release of TP from the film. The antioxidant properties were satisfactory after discharge from the film detected by DPPH/ABTS scavenging. The value of crosslinking degree (~60%) and increased molecular weight of the protein were investigated by SDS-PAGE, indicating the compatibility of TP and TG treatment. According to physicomechanical findings, the TG2TP1 film exhibited the best characteristics. Tensile strength and water solubility properties were ameliorated by the TG treatment of TP-encapsulated films compared to the control film. TG and TP-loaded gelatin-zein composite film had better thermal stability than the control film. Moreover, the TP loading reduced the transparency value and improved the light-barrier properties of the film. The films showed significant antimicrobial activities against two food-borne bacteria, including Staphylococcus aureus BCTC13962 and Escherichia coli BCRC10675. The result obtained shows that the encapsulation of TP and TG treatment may be used to fabricate gelatin-zein composite film with controlled release of phenolic compounds for active packaging applications.

This work proposes the development of a polymer film made up of affordable components for its use as a healthcare material. Chitosan, itaconic acid, and Randia capitata fruit extract (Mexican variation) are the unique ingredients of this biomaterial prospect. Chitosan (from crustacean chitin) is crosslinked with itaconic acid, and in situ added R. capitata fruit extract in a one-pot reaction carried out in water as the sole solvent. Structurally, the film formed is an ionically crosslinked composite characterized by IR spectroscopy and thermal analysis (DSC and TGA); cell viability was also performed in vitro using fibroblasts BALB/3T3. Dry and swollen films were analyzed to determine affinity and stability in water. This chitosan-based hydrogel is designed as a wound dressing due to the combined properties of the chitosan with R. capitata fruit extract, which has potential as bioactive material due to its properties in epithelial regeneration.

Chitosan is one of the most commonly employed natural polymers for biomedical applications. However, in order to obtain stable chitosan biomaterials with appropriate strength properties, it is necessary to subject it to crosslinking or stabilization. Composites based on chitosan and bioglass were prepared using the lyophilization method. In the experimental design, six different methods were used to obtain stable, porous chitosan/bioglass biocomposite materials. This study compared the crosslinking/stabilization of chitosan/bioglass composites with ethanol, thermal dehydration, sodium tripolyphosphate, vanillin, genipin, and sodium β-glycerophosphate. The physicochemical, mechanical, and biological properties of the obtained materials were compared. The results showed that all the selected crosslinking methods allow the production of stable, non-cytotoxic porous composites of chitosan/bioglass. The composite with genipin stood out with the best of the compared properties, taking into account biological and mechanical characteristics. The composite stabilized with ethanol is distinct in terms of its thermal properties and swelling stability, and it also promotes cell proliferation. Regarding the specific surface area, the highest value exposes the composite stabilized by the thermal dehydration method.

Starch oleate (degree of substitution = 2.2) films were cast and crosslinked in the presence of air using UV curing (UVC) or heat curing (HC). A commercial photoinitiator (CPI, Irgacure 184) and a natural photoinitiator (NPI, a mixture of biobased 3-hydroxyflavone and n-phenylglycine) were used for UVC. No initiator was used during HC. Isothermal gravimetric analyses, Fourier Transform Infrared (FTIR) measurements, and gel content measurements revealed that all three methods were effective in crosslinking, with HC being the most efficient. All methods increased the maximum strengths of film, with HC causing the largest increase (from 4.14 to 7.37 MPa). This is consistent with a higher degree of crosslinking occurring with HC. DSC analyses showed that the T g signal flattened as film crosslink densities increased, even disappearing in the case of HC and UVC with CPI. Thermal gravimetric analyses (TGA) indicated that films cured with NPI were least affected by degradation during curing. These results suggest that cured starch oleate films could be suitable for replacing the fossil-fuel-derived plastics currently used in mulch films or packaging applications., Competing Interests: The authors declare no conflicts of interest.

Although keratin can effectively repair hair fibres and enhance their moisture content and flexibility, it has a relatively low affinity for hair. In this study, the effects of transglutaminase (TGase)-commonly used to catalyse crosslinking of proteins or amino acids-in crosslinking serine and hydrolysed wool keratin to repair damaged hair and protect healthy hair were studied. Treatment with a repair solution containing hydrolysed wool keratin, serine, and TGase improved the physical and chemical properties of damaged hair samples. The alkali solubility of damaged hair samples decreased by 50.53%, fracture stress increased from 1.031 to 1.806 N, and fracture strain increased from 9.51 to 19.88 mm. Fourier transform infrared spectroscopy and X-ray analysis showed that amide bonds increased in damaged hair samples treated with the repair solution and hair crystallinity increased. Differential scanning calorimetry showed that the repair solution improved the thermal stability of damaged hair. After five cycles of washing, the effects of the repair solution were still apparent in damaged hair samples. The enzymatic solution had stronger repair effects than general hair care products and reduced water loss rates in damaged hair samples; repaired hair samples were also softer and brighter. The repair solution was effective in protecting healthy hair samples against chemical damage. The materials used to prepare the repair solution are all bio-based, and treatment with this product is safer and longer lasting.

To address the increasing demand for biobased materials, lignin-derived ferulic acid (FA) is a promising candidate. In this study, an FA-derived styrene-like monomer, referred to as 2-methoxy-4-vinylphenol (MVP), was used as the platform to prepare functional monomers for radical polymerizations. Hydrophobic biobased monomers derived from MVP were polymerized via solution and emulsion polymerization resulting in homo- and copolymers with a wide range of thermal properties, thus showcasing their potential in thermoplastic applications. Moreover, divinylbenzene (DVB)-like monomers were prepared from MVP by varying the aliphatic chain length between the MVP units. These biobased monomers were thermally crosslinked with thiol-bearing reagents to produce thermosets with different crosslinking densities in order to demonstrate their thermosetting applications. The results of this study expand the scope of MVP-derived monomers that can be used in free-radical polymerizations toward the preparation of new biobased and functional materials from lignin.

To assist in bone defect repair, ideal bone regeneration scaffolds should exhibit good osteoconductivity and osteoinductivity, but for load-bearing applications, they should also have mechanical properties that emulate those of native bone. The use of biomimetic processing methods for the mineralization of collagen fibrils has resulted in interpenetrating composites that mimic the nanostructure of native bone; however, closely matching the mechanical properties of bone on a larger scale is something that is still yet to be achieved. In this study, four different collagen crosslinking methods (EDC-NHS, quercetin, methacrylated collagen, and riboflavin) are compared and combined with biomimetic mineralization via the polymer-induced liquid-precursor (PILP) process, to obtain bone-like collagen-hydroxyapatite composites. Densified fibrillar collagen scaffolds were fabricated, crosslinked, and biomimetically mineralized using the PILP process, and the effect of each crosslinking method on the degree of mineralization, tensile strength, and modulus of the mineralized scaffolds were analyzed and compared. Improved modulus and tensile strength values were obtained using EDC-NHS and riboflavin crosslinking methods, while quercetin and methacrylated collagen resulted in little to no increase in mechanical properties. Decreased mineral contents appear to be necessary for retaining tensile strength, suggesting that mineral content should be kept below a percolation threshold to optimize properties of these interpenetrating nanocomposites. This work supports the premise that a combination of collagen crosslinking and biomimetic mineralization methods may provide solutions for fabricating robust bone-like composites on a larger scale.

Herein the synthesis, characterization, and study of spectroscopic, thermal, and thermo-mechanical properties of polymeric composites are presented. The composites were obtained in special molds (8 × 10 cm) based on the commercially available epoxy resin Epidian ® 601 cross-linked by 10% w / w triethylenetetramine (TETA). To improve the thermal and mechanical properties of the synthetic epoxy resins, natural fillers in the form of minerals from the silicate cluster kaolinite (KA) or clinoptilolite (CL) were added to the composites. The structures of the materials obtained were confirmed by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR/FTIR). The thermal properties of the resins were investigated by differential scanning calorimetry (DSC) and dynamic-mechanical analysis (DMA) in an inert atmosphere. The hardness of the crosslinked products was determined using the Shore D method. Moreover, strength tests were performed on the 3PB (three-point bending) specimen, with the analysis of tensile strains conducted using the Digital Image Correlation (DIC) technique.