Pub Date : 2026-01-27DOI: 10.1016/j.reactfunctpolym.2026.106665
Alexander O. Malakhov , Stepan E. Sokolov , Evgenia A. Grushevenko , Stepan D. Bazhenov , Anton L. Maksimov
Sorption and permeation properties of membrane based on polycetylmethylsiloxane (PCMS) were described for the first time. The sorption of methane and butane was studied using the gravimetric method over the temperature range of 5–45 °C. Gas permeability was measured using the constant-volume/variable-pressure technique. DSC and density measurements revealed that the PCMS membrane has a melting transition due to side chain crystallization at near-room temperature. The effects of temperature and pressure on solubility and permeability for methane and n-butane are explored and discussed. It was found that the sorption selectivity of n-butane over methane increases as the temperature decreases, both for amorphous and semi-crystalline states of the polymer. The n-butane/methane ideal perm-selectivity exhibits an extremal temperature dependence. The maximum perm-selectivity α increases and shifts towards lower temperatures as the transmembrane pressure increases. The value of α increases from 12 to 200 as the feed pressure of n-butane increases from 0 to 1 bar at 20 °C. The achieved n-butane/methane perm-selectivity is an order of magnitude higher than previously reported values for polymer membranes, including polyalkylmethylsiloxanes.
{"title":"Sorption and permeation properties of polycetylmethylsiloxane to methane and n-butane","authors":"Alexander O. Malakhov , Stepan E. Sokolov , Evgenia A. Grushevenko , Stepan D. Bazhenov , Anton L. Maksimov","doi":"10.1016/j.reactfunctpolym.2026.106665","DOIUrl":"10.1016/j.reactfunctpolym.2026.106665","url":null,"abstract":"<div><div>Sorption and permeation properties of membrane based on polycetylmethylsiloxane (PCMS) were described for the first time. The sorption of methane and butane was studied using the gravimetric method over the temperature range of 5–45 °C. Gas permeability was measured using the constant-volume/variable-pressure technique. DSC and density measurements revealed that the PCMS membrane has a melting transition due to side chain crystallization at near-room temperature. The effects of temperature and pressure on solubility and permeability for methane and <em>n</em>-butane are explored and discussed. It was found that the sorption selectivity of <em>n</em>-butane over methane increases as the temperature decreases, both for amorphous and semi-crystalline states of the polymer. The <em>n</em>-butane/methane ideal perm-selectivity exhibits an extremal temperature dependence. The maximum perm-selectivity <em>α</em> increases and shifts towards lower temperatures as the transmembrane pressure increases. The value of <em>α</em> increases from 12 to 200 as the feed pressure of <em>n</em>-butane increases from 0 to 1 bar at 20 °C. The achieved <em>n</em>-butane/methane perm-selectivity is an order of magnitude higher than previously reported values for polymer membranes, including polyalkylmethylsiloxanes.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"222 ","pages":"Article 106665"},"PeriodicalIF":5.1,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146096030","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-27DOI: 10.1016/j.reactfunctpolym.2026.106666
Shuai Yang , Guxia Wang , Tingxuan Dong , Dan Li , Ning Wu , Zhiyi Wu , Liyang Ding , Shengwei Guo , Yen Wei
To address the issues of flammability and inadequate UV resistance of low-density polyethylene (LDPE) in outdoor cable applications, we encapsulated ammonium polyphosphate (APP) surface with polysiloxane to mitigate its antagonistic impact (Si-APP), and grafted 4-amino-2,2,6,6-tetramethylpiperidine (TEMP) onto Si-APP by reacting with melamine (ME) and benzylamine (Bn), resulting in the formation of TEMP-ME@Si-APP and TEMP-Bn@Si-APP, which were then combined with tris(2-hydroxyethyl) isocyanurate (THEIC) and incorporated into LDPE. The resulting LDPE/TEMP-ME@Si-APP/THEIC composites demonstrated a carbonyl index of 10.45, reflecting substantial UV resistance. Compared with pure LDPE, the composites exhibited a limiting oxygen index (LOI) of 31.0%, along with a reduction of 75.8% in peak heat release rate (pHRR), a 59.9% decrease in smoke release rate (pSPR), and a 49.7% reduction in peak carbon monoxide production (pCOP). After 100 h of UV aging, the samples retained an LOI of 30.3% and achieved UL-94 V-0 rating. The tensile strength and elongation at break decreased by only 2.06% and 2.29%, respectively, which was significantly lower than that observed in control samples. This study confirms that the combination of polysiloxane encapsulation and amine salt grafting effectively enhances the UV stability, flame retardancy, and mechanical properties of LDPE.
{"title":"A robust strategy for enhanced UV stability and flame retardancy of LDPE via synergistic polysiloxane encapsulation and amine grafting","authors":"Shuai Yang , Guxia Wang , Tingxuan Dong , Dan Li , Ning Wu , Zhiyi Wu , Liyang Ding , Shengwei Guo , Yen Wei","doi":"10.1016/j.reactfunctpolym.2026.106666","DOIUrl":"10.1016/j.reactfunctpolym.2026.106666","url":null,"abstract":"<div><div>To address the issues of flammability and inadequate UV resistance of low-density polyethylene (LDPE) in outdoor cable applications, we encapsulated ammonium polyphosphate (APP) surface with polysiloxane to mitigate its antagonistic impact (Si-APP), and grafted 4-amino-2,2,6,6-tetramethylpiperidine (TEMP) onto Si-APP by reacting with melamine (ME) and benzylamine (Bn), resulting in the formation of TEMP-ME@Si-APP and TEMP-Bn@Si-APP, which were then combined with tris(2-hydroxyethyl) isocyanurate (THEIC) and incorporated into LDPE. The resulting LDPE/TEMP-ME@Si-APP/THEIC composites demonstrated a carbonyl index of 10.45, reflecting substantial UV resistance. Compared with pure LDPE, the composites exhibited a limiting oxygen index (LOI) of 31.0%, along with a reduction of 75.8% in peak heat release rate (pHRR), a 59.9% decrease in smoke release rate (pSPR), and a 49.7% reduction in peak carbon monoxide production (pCOP). After 100 h of UV aging, the samples retained an LOI of 30.3% and achieved UL-94 V-0 rating. The tensile strength and elongation at break decreased by only 2.06% and 2.29%, respectively, which was significantly lower than that observed in control samples. This study confirms that the combination of polysiloxane encapsulation and amine salt grafting effectively enhances the UV stability, flame retardancy, and mechanical properties of LDPE.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106666"},"PeriodicalIF":5.1,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146079072","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-27DOI: 10.1016/j.reactfunctpolym.2026.106667
Jessica Borges-Vilches , Tuuli Virkkala , Valentina Guccini , Marko Crivaro , Thaddeus Maloney , Tekla Tammelin , Eero Kontturi
Stimuli-responsive hydrogels are interesting, particularly in the realm of biomedicals, but often the fundamental response of their key physical properties is not simultaneously monitored. Here, we investigated the pH response on the porosity, rheological behavior, mechanical performance, and molecular diffusivity of a hydrogel system composed of two bio-based components: gelatin and rod-like cellulose nanocrystals (CNCs). By leveraging the pH-responsive nature of gelatin, we systematically examined the structural properties of these hydrogels formed under three pH conditions: below (pH 5), above (pH 11), and at the isoelectric point (pH 8) of type A gelatin. All hydrogels exhibited a distinct cellular architecture, characterized by micron-scale tubular pores with embedded mesopores. Increasing pH upon the hydrogel crosslinking promoted the formation of more porous structures with significantly enhanced mechanical performance. The effect on the Young's modulus was significant: with a 3-fold increase compared to its counterparts, the hydrogel fabricated at pH 11 exhibited the stiffest structure. This improvement in hydrogel stiffness with pH further restricted the molecular diffusivity within the hydrogels to some extent, as evidenced by Fluorescence Recovery After Photobleaching analysis using fluorescein isothiocyanate-dextran as a diffusion probe. Overall, this study presents a straightforward and effective strategy for fabricating pH-tunable hydrogels, providing valuable insights for the design of responsive biomaterials with potential applications in soft tissue engineering and drug delivery.
{"title":"Tuning physical performance of gelatin-cellulose nanocrystals hydrogels","authors":"Jessica Borges-Vilches , Tuuli Virkkala , Valentina Guccini , Marko Crivaro , Thaddeus Maloney , Tekla Tammelin , Eero Kontturi","doi":"10.1016/j.reactfunctpolym.2026.106667","DOIUrl":"10.1016/j.reactfunctpolym.2026.106667","url":null,"abstract":"<div><div>Stimuli-responsive hydrogels are interesting, particularly in the realm of biomedicals, but often the fundamental response of their key physical properties is not simultaneously monitored. Here, we investigated the pH response on the porosity, rheological behavior, mechanical performance, and molecular diffusivity of a hydrogel system composed of two bio-based components: gelatin and rod-like cellulose nanocrystals (CNCs). By leveraging the pH-responsive nature of gelatin, we systematically examined the structural properties of these hydrogels formed under three pH conditions: below (pH 5), above (pH 11), and at the isoelectric point (pH 8) of type A gelatin. All hydrogels exhibited a distinct cellular architecture, characterized by micron-scale tubular pores with embedded mesopores. Increasing pH upon the hydrogel crosslinking promoted the formation of more porous structures with significantly enhanced mechanical performance. The effect on the Young's modulus was significant: with a 3-fold increase compared to its counterparts, the hydrogel fabricated at pH 11 exhibited the stiffest structure. This improvement in hydrogel stiffness with pH further restricted the molecular diffusivity within the hydrogels to some extent, as evidenced by Fluorescence Recovery After Photobleaching analysis using fluorescein isothiocyanate-dextran as a diffusion probe. Overall, this study presents a straightforward and effective strategy for fabricating pH-tunable hydrogels, providing valuable insights for the design of responsive biomaterials with potential applications in soft tissue engineering and drug delivery.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106667"},"PeriodicalIF":5.1,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146079068","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-26DOI: 10.1016/j.reactfunctpolym.2026.106664
Maksims Jurinovs , Nikolass Rukavisnikovs , Sabine Greivule , Olesja Starkova , Andrejs Kovalovs , Jānis Brunāvs , Jan Macutkevič , Inna Juhnevica , Oskars Platnieks , Sergejs Gaidukovs
High-performance coatings require rapid and sustainable processing, robust mechanical properties, and long-term durability. However, conventional epoxy systems rely on slow and energy-intensive thermal curing. Here, we develop UV-curable epoxy-acrylate systems optimized through three sequential stages: neat UV-cured epoxy, interpenetrating epoxy-acrylate networks, and nanoclay-reinforced IPN composites. The formulations cure into ∼300 μm films under 2 min of UV exposure, removing the need for thermal treatment. The epoxy-acrylate networks exhibit a markedly increased hardness (up to 38% increase) and improved water-barrier performance compared to neat UV-cured epoxy. The incorporation of nanoclay platelets yields nanostructure-reinforced epoxy-acrylate composite coating and further enhances materials' thermal stability, reduces water uptake (by up to 46%), and improves stiffness (by up to 50%). Mechanical property predictions from finite-element analysis (FEA), derived from experimentally measured hardness and modulus values, confirmed the formation of efficiently reinforced and mechanically stable networks across the optimized compositions. Moisture transport was quantified using Fickian sorption models, establishing clear correlations between polymer network architecture, platelet alignment, and material stiffness with water barrier behavior. Together, these results demonstrate a predictable and tunable route to rapidly and sustainably produce high-performance UV-curable epoxy-acrylate coatings for marine environment applications, combining the speed of photopolymerization with the durability of nanoparticle-reinforced thermoset composites.
{"title":"Nanostructure-reinforced epoxy-acrylate interpenetrated networks for UV-curable high-performance coatings","authors":"Maksims Jurinovs , Nikolass Rukavisnikovs , Sabine Greivule , Olesja Starkova , Andrejs Kovalovs , Jānis Brunāvs , Jan Macutkevič , Inna Juhnevica , Oskars Platnieks , Sergejs Gaidukovs","doi":"10.1016/j.reactfunctpolym.2026.106664","DOIUrl":"10.1016/j.reactfunctpolym.2026.106664","url":null,"abstract":"<div><div>High-performance coatings require rapid and sustainable processing, robust mechanical properties, and long-term durability. However, conventional epoxy systems rely on slow and energy-intensive thermal curing. Here, we develop UV-curable epoxy-acrylate systems optimized through three sequential stages: neat UV-cured epoxy, interpenetrating epoxy-acrylate networks, and nanoclay-reinforced IPN composites. The formulations cure into ∼300 μm films under 2 min of UV exposure, removing the need for thermal treatment. The epoxy-acrylate networks exhibit a markedly increased hardness (up to 38% increase) and improved water-barrier performance compared to neat UV-cured epoxy. The incorporation of nanoclay platelets yields nanostructure-reinforced epoxy-acrylate composite coating and further enhances materials' thermal stability, reduces water uptake (by up to 46%), and improves stiffness (by up to 50%). Mechanical property predictions from finite-element analysis (FEA), derived from experimentally measured hardness and modulus values, confirmed the formation of efficiently reinforced and mechanically stable networks across the optimized compositions. Moisture transport was quantified using Fickian sorption models, establishing clear correlations between polymer network architecture, platelet alignment, and material stiffness with water barrier behavior. Together, these results demonstrate a predictable and tunable route to rapidly and sustainably produce high-performance UV-curable epoxy-acrylate coatings for marine environment applications, combining the speed of photopolymerization with the durability of nanoparticle-reinforced thermoset composites.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106664"},"PeriodicalIF":5.1,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146079073","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-22DOI: 10.1016/j.reactfunctpolym.2026.106663
Haitao Liu , Hengde Li , Saman Hamidi , Xi Chen , Mohsen Adeli , Angelo H. All
Targeted therapy for the central nervous system (CNS) has traditionally relied on intravenous injections or direct intracerebroventricular delivery. Recently, neuronal transport-mediated delivery from the periphery to the CNS, such as intranasal, has emerged as a promising alternative. The rabies virus is capable of efficiently entering the CNS via the neuromuscular junction, intra-axonal retrograde transport and synaptic cleft crossing, thus bypassing the restrictive blood-brain barrier (BBB). RVG29, a peptide derived from the rabies virus glycoprotein, exhibits excellent neurotropic properties. Inspired by this concept, we designed a novel brain-targeted system, PAA-PEG-RVG29, consisting of poly(amido amine)s (PAAs) functionalized with poly(ethylene glycol) (PEG) to reduce cytotoxicity and aggregation, and conjugated with RVG29 to enhance neuronal transport capability. Moreover, Rhodamine B (RhB) was loaded into this system as a model cargo by intermolecular hydrogen bonding, and its efficiency for intra- and inter-neuronal distribution was evaluated. PAA-PEG-RVG29 (RhB) exhibited a hydrodynamic radius of 29.9 nm, a zeta potential of +25 mV, and a RhB loading capacity of 36.4 μg/mg. Cytotoxicity and cellular uptake studies demonstrated promising biocompatibility and efficient internalization in Neuro2a, NSC34, and primary neurons. Furthermore, patch-clamp electrophysiology confirmed that there was no significant alteration effect on primary spinal neuronal action potential generation and propagation. In a two-compartment microfluidic chamber, PAA-PEG-RVG29 (RhB) exhibited effective retrograde axonal transport. A three-compartment chamber further showed progressive trans-synaptic delivery to neighboring neuronal somas. These results highlight the potential of PAA-PEG-RVG29 (RhB) for neuronal transport and synaptic cleft crossing, offering a promising strategy for neuronal delivery, bioimaging, and tracking.
{"title":"RVG29-modified PAA-PEG nanocarriers enable synaptic cleft crossing and neuronal delivery","authors":"Haitao Liu , Hengde Li , Saman Hamidi , Xi Chen , Mohsen Adeli , Angelo H. All","doi":"10.1016/j.reactfunctpolym.2026.106663","DOIUrl":"10.1016/j.reactfunctpolym.2026.106663","url":null,"abstract":"<div><div>Targeted therapy for the central nervous system (CNS) has traditionally relied on intravenous injections or direct intracerebroventricular delivery. Recently, neuronal transport-mediated delivery from the periphery to the CNS, such as intranasal, has emerged as a promising alternative. The rabies virus is capable of efficiently entering the CNS <em>via</em> the neuromuscular junction, intra-axonal retrograde transport and synaptic cleft crossing, thus bypassing the restrictive blood-brain barrier (BBB). RVG29, a peptide derived from the rabies virus glycoprotein, exhibits excellent neurotropic properties. Inspired by this concept, we designed a novel brain-targeted system, PAA-PEG-RVG29, consisting of poly(amido amine)s (PAAs) functionalized with poly(ethylene glycol) (PEG) to reduce cytotoxicity and aggregation, and conjugated with RVG29 to enhance neuronal transport capability. Moreover, Rhodamine B (RhB) was loaded into this system as a model cargo by intermolecular hydrogen bonding, and its efficiency for intra- and inter-neuronal distribution was evaluated. PAA-PEG-RVG29 (RhB) exhibited a hydrodynamic radius of 29.9 nm, a zeta potential of +25 mV, and a RhB loading capacity of 36.4 μg/mg. Cytotoxicity and cellular uptake studies demonstrated promising biocompatibility and efficient internalization in Neuro2a, NSC34, and primary neurons. Furthermore, patch-clamp electrophysiology confirmed that there was no significant alteration effect on primary spinal neuronal action potential generation and propagation. In a two-compartment microfluidic chamber, PAA-PEG-RVG29 (RhB) exhibited effective retrograde axonal transport. A three-compartment chamber further showed progressive trans-synaptic delivery to neighboring neuronal somas. These results highlight the potential of PAA-PEG-RVG29 (RhB) for neuronal transport and synaptic cleft crossing, offering a promising strategy for neuronal delivery, bioimaging, and tracking.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106663"},"PeriodicalIF":5.1,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146079083","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Cellulose nanofibers (CNFs) containing ammonium carboxylate groups are possibly converted to CNFs with protonated carboxy groups via simple thermal decomposition. The CNF-COOH structures in films and composites can form intra- and inter-fibrillar hydrogen bonds, which are expected to enhance mechanical, thermal, and gas-barrier properties. In this study, CNF pellets and films containing ammonium carboxylate groups were first prepared and subjected to dry thermal, humid thermal, and hydrothermal treatments to clarify the convertibility of ammonium carboxylate groups to protonated ones, considering simple thermal processes to improve CNF properties. The ratios of ammonium carboxylate or protonated carboxy groups in the heated samples were determined from their infrared spectra. Freeze-dried pellets-COONH4 and cast/dried CNF-COONH4 films contained 81–82% ammonium carboxylate group ratios before heating; however, complete formation of ammonium carboxylate groups in the pellet and film samples could not be achieved. Heating at 90 °C and 90% RH for 240 min was required for the CNF-COONH4 films to reduce the ammonium carboxylate ratio from 81% to 8%. These results indicate that the ammonium carboxylate groups in the film samples exhibited high resistance to the formation of protonated carboxy groups under the thermal conditions applied. Consequently, it is not plausible that CNF-COONH4 films were mostly converted to CNF-COOH structures under the heating conditions used in this study over a short time. Nevertheless, partial conversions of CNF-COONH4 groups to CNF-COOH ones by thermal treatment under suitable conditions are regarded as simple processes to change the structures of counterions of carboxy groups and resultant film properties.
{"title":"Stability of ammonium carboxylate structures in TEMPO-oxidized cellulose to dry thermal, humid thermal, and hydrothermal treatments","authors":"Runqing Hou, Pavitra Thevi Arnandan, Korawit Chitbanyong, Izumi Shibata, Akira Isogai","doi":"10.1016/j.reactfunctpolym.2026.106657","DOIUrl":"10.1016/j.reactfunctpolym.2026.106657","url":null,"abstract":"<div><div>Cellulose nanofibers (CNFs) containing ammonium carboxylate groups are possibly converted to CNFs with protonated carboxy groups via simple thermal decomposition. The CNF-COOH structures in films and composites can form intra- and inter-fibrillar hydrogen bonds, which are expected to enhance mechanical, thermal, and gas-barrier properties. In this study, CNF pellets and films containing ammonium carboxylate groups were first prepared and subjected to dry thermal, humid thermal, and hydrothermal treatments to clarify the convertibility of ammonium carboxylate groups to protonated ones, considering simple thermal processes to improve CNF properties. The ratios of ammonium carboxylate or protonated carboxy groups in the heated samples were determined from their infrared spectra. Freeze-dried pellets-COONH<sub>4</sub> and cast/dried CNF-COONH<sub>4</sub> films contained 81–82% ammonium carboxylate group ratios before heating; however, complete formation of ammonium carboxylate groups in the pellet and film samples could not be achieved. Heating at 90 °C and 90% RH for 240 min was required for the CNF-COONH<sub>4</sub> films to reduce the ammonium carboxylate ratio from 81% to 8%. These results indicate that the ammonium carboxylate groups in the film samples exhibited high resistance to the formation of protonated carboxy groups under the thermal conditions applied. Consequently, it is not plausible that CNF-COONH<sub>4</sub> films were mostly converted to CNF-COOH structures under the heating conditions used in this study over a short time. Nevertheless, partial conversions of CNF-COONH<sub>4</sub> groups to CNF-COOH ones by thermal treatment under suitable conditions are regarded as simple processes to change the structures of counterions of carboxy groups and resultant film properties.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106657"},"PeriodicalIF":5.1,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146079173","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-22DOI: 10.1016/j.reactfunctpolym.2026.106661
Jie Zhang , Yuhao Zhao , Jianze Cao , Yongfei Liu , Haiyan Zhao
Traditional bone defect repair faces challenges such as donor scarcity and immune rejection. In this study, we developed a chitosan hydrogel embedded with Dexamethasone-loaded nanoparticles (Dex-CS-NPs) to synergistically enhance bone regeneration through immunomodulation and osteogenic stimulation. The Dex-CS-NPs, synthesized via ionic crosslinking, exhibited an average diameter of 41.10 ± 7.31 nm, an encapsulation efficiency of 65.62%, and a drug loading capacity of 22.33%. These nanoparticles were then uniformly integrated into a chitosan hydrogel matrix. In vitro, the Dex-CS-NPs-loaded hydrogel demonstrated sustained release of Dexamethasone, which promoted macrophage polarization towards the anti-inflammatory M2 phenotype and enhanced the osteogenic differentiation of MC3T3-E1 pre-osteoblasts. In a rat tibial critical-size defect model, implantation of the NPs-hydrogel significantly improved bone regeneration outcomes and facilitated integration with the host tissue. Histological analysis confirmed upregulation of RUNX2 expression and increased osteoblast activity at the defect site, without inducing systemic toxicity. This dual-functional biomaterial not only modulates the local immune microenvironment via M2 polarization but also directly stimulates osteogenesis, offering a promising strategy to address clinical challenges in bone repair.
{"title":"Chitosan hydrogel loaded with dexamethasone nanoparticles enhances osteogenesis and bone regeneration via macrophage polarization","authors":"Jie Zhang , Yuhao Zhao , Jianze Cao , Yongfei Liu , Haiyan Zhao","doi":"10.1016/j.reactfunctpolym.2026.106661","DOIUrl":"10.1016/j.reactfunctpolym.2026.106661","url":null,"abstract":"<div><div>Traditional bone defect repair faces challenges such as donor scarcity and immune rejection. In this study, we developed a chitosan hydrogel embedded with Dexamethasone-loaded nanoparticles (Dex-CS-NPs) to synergistically enhance bone regeneration through immunomodulation and osteogenic stimulation. The Dex-CS-NPs, synthesized via ionic crosslinking, exhibited an average diameter of 41.10 ± 7.31 nm, an encapsulation efficiency of 65.62%, and a drug loading capacity of 22.33%. These nanoparticles were then uniformly integrated into a chitosan hydrogel matrix. In vitro, the Dex-CS-NPs-loaded hydrogel demonstrated sustained release of Dexamethasone, which promoted macrophage polarization towards the anti-inflammatory M2 phenotype and enhanced the osteogenic differentiation of MC3T3-E1 pre-osteoblasts. In a rat tibial critical-size defect model, implantation of the NPs-hydrogel significantly improved bone regeneration outcomes and facilitated integration with the host tissue. Histological analysis confirmed upregulation of RUNX2 expression and increased osteoblast activity at the defect site, without inducing systemic toxicity. This dual-functional biomaterial not only modulates the local immune microenvironment via M2 polarization but also directly stimulates osteogenesis, offering a promising strategy to address clinical challenges in bone repair.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106661"},"PeriodicalIF":5.1,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146079082","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-21DOI: 10.1016/j.reactfunctpolym.2026.106658
Junyi Lin , Chuanzhuang Zhao , Li Zhang
Mechanical fragility under liquid-saturated conditions remains a critical limitation of conventional porous oil sorbents, including many polyvinyl formal (PVF) sponges that primarily rely on surface wettability optimization. In this work, a mechanically reinforced and highly hydrophobic PVF sponge is developed through a chemically integrated two-step modification strategy. First, a secondary glutaraldehyde-induced acetal crosslinking process is employed to densify the PVF network and substantially enhance structural rigidity. Subsequently, covalent grafting of dodecyltrimethoxysilane introduces low-surface-energy alkyl chains and hierarchical micro/nanoscale surface roughness, yielding stable hydrophobicity with a water contact angle of 131°, maintained under acidic, alkaline, and saline environments. The resulting sponge exhibits selective adsorption toward a broad range of organic solvents both on and beneath the water surface, with an adsorption capacity of up to 9.1 g g−1. Notably, the material retains a high compressive strength of 3.38 MPa even in the saturated state, effectively preventing structural collapse and secondary leakage during oil recovery. In emulsion separation, the sponge achieves an ultrahigh oil flux of 2.9 × 104 L m−2 h−1 bar−1 for water-in-oil emulsions and maintains over 94% removal efficiency for oil-in-water emulsions across 10 consecutive cycles. By directly addressing the mechanical instability of conventional PVF sorbents through covalent network reinforcement, this study offers a robust design strategy for developing durable functional polymer sponges for oil–water separation applications.
液体饱和条件下的机械脆弱性仍然是传统多孔吸油剂的一个关键限制，包括许多主要依赖于表面润湿性优化的聚乙烯醇（PVF）海绵。在这项工作中，通过化学集成的两步改性策略，开发了一种机械增强和高度疏水性的PVF海绵。首先，采用二次戊二醛诱导缩醛交联工艺使PVF网络致密化，并大大提高结构刚度。随后，十二烷基三甲氧基硅烷的共价接枝引入了低表面能烷基链和分层微/纳米级表面粗糙度，产生了稳定的疏水性，水接触角为131°，在酸性、碱性和盐水环境下都能保持。所得海绵对各种有机溶剂均有选择性吸附，吸附量高达9.1 g g−1。值得注意的是，即使在饱和状态下，该材料也保持了3.38 MPa的高抗压强度，有效地防止了采油过程中的结构坍塌和二次泄漏。在乳状液分离中，海绵对油包水乳状液的油通量达到2.9 × 104 L m−2 h−1 bar−1，在连续10个循环中对油包水乳状液的去除率保持在94%以上。通过共价网络增强直接解决传统PVF吸附剂的机械不稳定性问题，该研究为开发用于油水分离的耐用功能聚合物海绵提供了强大的设计策略。
{"title":"Rigid highly hydrophobic polyvinyl formal sponges via dual glutaraldehyde crosslinking and silane grafting for high-performance oil sorption","authors":"Junyi Lin , Chuanzhuang Zhao , Li Zhang","doi":"10.1016/j.reactfunctpolym.2026.106658","DOIUrl":"10.1016/j.reactfunctpolym.2026.106658","url":null,"abstract":"<div><div>Mechanical fragility under liquid-saturated conditions remains a critical limitation of conventional porous oil sorbents, including many polyvinyl formal (PVF) sponges that primarily rely on surface wettability optimization. In this work, a mechanically reinforced and highly hydrophobic PVF sponge is developed through a chemically integrated two-step modification strategy. First, a secondary glutaraldehyde-induced acetal crosslinking process is employed to densify the PVF network and substantially enhance structural rigidity. Subsequently, covalent grafting of dodecyltrimethoxysilane introduces low-surface-energy alkyl chains and hierarchical micro/nanoscale surface roughness, yielding stable hydrophobicity with a water contact angle of 131°, maintained under acidic, alkaline, and saline environments. The resulting sponge exhibits selective adsorption toward a broad range of organic solvents both on and beneath the water surface, with an adsorption capacity of up to 9.1 g g<sup>−1</sup>. Notably, the material retains a high compressive strength of 3.38 MPa even in the saturated state, effectively preventing structural collapse and secondary leakage during oil recovery. In emulsion separation, the sponge achieves an ultrahigh oil flux of 2.9 × 10<sup>4</sup> L m<sup>−2</sup> h<sup>−1</sup> bar<sup>−1</sup> for water-in-oil emulsions and maintains over 94% removal efficiency for oil-in-water emulsions across 10 consecutive cycles. By directly addressing the mechanical instability of conventional PVF sorbents through covalent network reinforcement, this study offers a robust design strategy for developing durable functional polymer sponges for oil–water separation applications.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106658"},"PeriodicalIF":5.1,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146079071","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-20DOI: 10.1016/j.reactfunctpolym.2026.106659
Xiyuan Guo , Yuanfeng Pan , Yuanjian Xie , Pingxiong Cai
Pesticides are essential for agricultural production; however, their improper application can result in ecological damage and potential threats to human health. Therefore, the development of pesticide-controlled-release systems is crucial for the sustainable progress of agriculture and society. This work presents a novel strategy for fabricating a polyelectrolyte hydrogel bead-based pesticide-controlled-release system. The process involves blending a sodium alginate/carboxymethyl chitosan (SA/CMCS) solution with cystine dihydrochloride (CYS), followed by introducing the mixture into a citric acid (CA) solution. The abundant protonated amino groups (-NH3+) and carboxylate anions (-COO-) within the system facilitate the formation of CMCS/SA-CYS/CA composite hydrogel beads (CHGB), subsequently loaded with thiamethoxam (TMX) to create TMX-loaded CHGB (TCHGB) for investigations into drug loading and responsive release. The CHGB exhibits remarkable swelling properties (up to 4200%), along with pH and redox sensitivity. And the release of TMX from TCHGB displays favorable responsiveness to pH and redox stimuli. Under alkaline conditions (pH 9.0) and reductive surroundings (containing glutathione), the cumulative release ratio of TMX surpasses 95%. Furthermore, it has been demonstrated that the release kinetics of TMX comply with Fickian diffusion described by the Korsmeyer-Peppas model. The discoveries of this study hold considerable research and practical value in the domain of controlled-release agricultural chemicals.
{"title":"Sodium alginate/carboxymethyl chitosan composite hydrogel beads for pH/redox dual-responsive pesticide release","authors":"Xiyuan Guo , Yuanfeng Pan , Yuanjian Xie , Pingxiong Cai","doi":"10.1016/j.reactfunctpolym.2026.106659","DOIUrl":"10.1016/j.reactfunctpolym.2026.106659","url":null,"abstract":"<div><div>Pesticides are essential for agricultural production; however, their improper application can result in ecological damage and potential threats to human health. Therefore, the development of pesticide-controlled-release systems is crucial for the sustainable progress of agriculture and society. This work presents a novel strategy for fabricating a polyelectrolyte hydrogel bead-based pesticide-controlled-release system. The process involves blending a sodium alginate/carboxymethyl chitosan (SA/CMCS) solution with cystine dihydrochloride (CYS), followed by introducing the mixture into a citric acid (CA) solution. The abundant protonated amino groups (-NH<sup>3+</sup>) and carboxylate anions (-COO-) within the system facilitate the formation of CMCS/SA-CYS/CA composite hydrogel beads (CHGB), subsequently loaded with thiamethoxam (TMX) to create TMX-loaded CHGB (TCHGB) for investigations into drug loading and responsive release. The CHGB exhibits remarkable swelling properties (up to 4200%), along with pH and redox sensitivity. And the release of TMX from TCHGB displays favorable responsiveness to pH and redox stimuli. Under alkaline conditions (pH 9.0) and reductive surroundings (containing glutathione), the cumulative release ratio of TMX surpasses 95%. Furthermore, it has been demonstrated that the release kinetics of TMX comply with Fickian diffusion described by the Korsmeyer-Peppas model. The discoveries of this study hold considerable research and practical value in the domain of controlled-release agricultural chemicals.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106659"},"PeriodicalIF":5.1,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146079069","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-19DOI: 10.1016/j.reactfunctpolym.2026.106656
Lifang Lin , Wei Cao , Hongbo Liu , Zhaoxi Zhou , Haopeng Wang , Qiming Chen , Xiaowen Pu , Dhandapani Kuzhandaivel , Zixiang Weng , Lixin Wu
The widespread adoption of vat photopolymerization (VPP) 3D printing for creating functional load-bearing components is often constrained by the inherent brittleness of photocurable stereolithography resins (SLRs), which typically exhibit high rigidity but low fracture toughness. To overcome this limitation, we designed and synthesized a novel low-molecular-weight aromatic copolyester, poly(adipic acid-co-phthalic acid)-co-(1,4-butanediol-co-neopentyl glycol) (PABN), which serves as a multifunctional toughening modifier. The PABN architecture was strategically engineered to incorporate rigid aromatic segments for enhanced thermal and mechanical properties, methyl-functionalized side chains to inhibit crystallization and promote chain mobility, and terminal carboxyl groups to form covalent bonds with the epoxy matrix, ensuring robust interfacial adhesion. This polyester was synthesized via melt polycondensation and incorporated into a commercial SLR formulation to create a series of SLR/PABN hybrid systems with varying polyester contents. Remarkably, the hybrid system containing 10 wt% PABN achieved a superior balance of properties, exhibiting simultaneous and significant enhancements in toughness, stiffness, and strength. Specifically, it increased the fracture toughness (KIC), elongation at break, elastic modulus, and hardness by approximately 18.2%, 70.0%, 65.2%, and 80.6%, respectively, compared to the unmodified resin. Furthermore, the hybrid resin maintained a suitable viscosity for processing and exhibited good stability. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) analyses revealed a phase-separated morphology that facilitated effective energy dissipation in the device. This study validates a sophisticated molecular-level design strategy for aromatic polyesters, providing a viable pathway for developing high-performance, toughened, photocurable resins for demanding industrial applications in additive manufacturing.
{"title":"Synthesis of an aromatic polyester for enhanced mechanical properties of stereolithography resins","authors":"Lifang Lin , Wei Cao , Hongbo Liu , Zhaoxi Zhou , Haopeng Wang , Qiming Chen , Xiaowen Pu , Dhandapani Kuzhandaivel , Zixiang Weng , Lixin Wu","doi":"10.1016/j.reactfunctpolym.2026.106656","DOIUrl":"10.1016/j.reactfunctpolym.2026.106656","url":null,"abstract":"<div><div>The widespread adoption of vat photopolymerization (VPP) 3D printing for creating functional load-bearing components is often constrained by the inherent brittleness of photocurable stereolithography resins (SLRs), which typically exhibit high rigidity but low fracture toughness. To overcome this limitation, we designed and synthesized a novel low-molecular-weight aromatic copolyester, poly(adipic acid-<em>co</em>-phthalic acid)-<em>co</em>-(1,4-butanediol-<em>co</em>-neopentyl glycol) (PABN), which serves as a multifunctional toughening modifier. The PABN architecture was strategically engineered to incorporate rigid aromatic segments for enhanced thermal and mechanical properties, methyl-functionalized side chains to inhibit crystallization and promote chain mobility, and terminal carboxyl groups to form covalent bonds with the epoxy matrix, ensuring robust interfacial adhesion. This polyester was synthesized via melt polycondensation and incorporated into a commercial SLR formulation to create a series of SLR/PABN hybrid systems with varying polyester contents. Remarkably, the hybrid system containing 10 wt% PABN achieved a superior balance of properties, exhibiting simultaneous and significant enhancements in toughness, stiffness, and strength. Specifically, it increased the fracture toughness (K<sub>IC</sub>), elongation at break, elastic modulus, and hardness by approximately 18.2%, 70.0%, 65.2%, and 80.6%, respectively, compared to the unmodified resin. Furthermore, the hybrid resin maintained a suitable viscosity for processing and exhibited good stability. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) analyses revealed a phase-separated morphology that facilitated effective energy dissipation in the device. This study validates a sophisticated molecular-level design strategy for aromatic polyesters, providing a viable pathway for developing high-performance, toughened, photocurable resins for demanding industrial applications in additive manufacturing.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"221 ","pages":"Article 106656"},"PeriodicalIF":5.1,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146038462","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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