Reactive & Functional Polymers最新文献

{"title":"Bio-based dicoumarin-containing benzoxazine resin: Synthesis, photo-thermal polymerization and thermal stability","authors":"Lei Chen,&nbsp;Yin Lu,&nbsp;Kan Zhang","doi":"10.1016/j.reactfunctpolym.2025.106396","DOIUrl":"10.1016/j.reactfunctpolym.2025.106396","url":null,"abstract":"<div><div>With the increasing awareness of environmental protection, considerable efforts are now devoted into bio-derived material fabrication. Through utilization of renewable biomass aligning with green chemistry principles, various sustainable materials have been prepared. In the current study, an innovative benzoxazine monomer containing dual coumarin moieties was successfully prepared through Mannich condensation using 4-methylumbelliferone (bio-phenolic precursor) and 7-amino-4-methylcoumarin (bio-amine component). The molecular architecture integrates photoreactive coumarin moieties, enabling dual photo-thermal curing capability. Structural validation via ¹H/¹³C NMR and FT-IR spectroscopy confirmed the monomer integrity. Real-time UV–Vis spectroscopy monitoring indicated an 81 % conversion of the [2π + 2π] cycloaddition reaction following 2 h of UV irradiation (λ = 365 nm). The photopolymerized benzoxazine precursor shows a 5.4 °C curing temperature depression comparing to unphotopolymerized monomer. Complementary in-situ FT-IR analyses and DSC elucidated thermal-initiated ring-opening polymerization, demonstrating temperature-dependent conversion profiles. The polybenzoxazine prepared through photo-thermal polymerization shows higher thermal stability than solely thermal polymerized one. Through molecular design, this work realizes photo-thermal synergistic curing of bio-based benzoxazine resins, proposing an innovative approach to develop thermosetting materials that integrate low-energy processing, high heat resistance, and environmental sustainability.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"216 ","pages":"Article 106396"},"PeriodicalIF":4.5,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144535938","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}

{"title":"Reactive and non-reactive compatibilization of polyethylene terephthalate glycol/thermoplastic polyurethane (PETG/TPU) blends for 3D/4D printing applications","authors":"Válmer Azevedo de Sousa Filho ,&nbsp;Marcela Cristine de Alencar Lira ,&nbsp;Ryan Lucas Pereira Bonfim ,&nbsp;Rafael Braga da Cunha ,&nbsp;Shirley Nóbrega Cavalcanti ,&nbsp;Louise Brasileiro Quirino Brito ,&nbsp;Pankaj Agrawal ,&nbsp;Gustavo de Figueiredo Brito ,&nbsp;Tomás Jeferson Alves de Mélo","doi":"10.1016/j.reactfunctpolym.2025.106393","DOIUrl":"10.1016/j.reactfunctpolym.2025.106393","url":null,"abstract":"<div><div>In recent years, research on 3D and 4D printing has experienced rapid growth due to its vast potential for applications across multiple fields. Polymer blends of polyethylene terephthalate glycol (PETG) and thermoplastic polyurethane (TPU) have emerged as promising candidates for such applications. PETG offers good shape fixity but limited recovery capability, whereas TPU, as an elastomer, provides excellent shape recovery but poor fixity. Therefore, blending PETG with TPU presents a strategic approach to balancing these complementary shape memory characteristics. However, the immiscibility between PETG and TPU can limit the overall performance of their blends. To address this, compatibilizers can be employed to enhance interfacial adhesion and stabilize blend morphology. This study explores reactive and non-reactive compatibilization strategies for PETG and polycaprolactone-based TPU blends, aiming for 3D/4D printing applications. Three compatibilizers were evaluated: styrene-ethylene-butylene-styrene (SEBS), maleic anhydride-functionalized SEBS (SEBS-MA), and ethylene-glycidyl methacrylate (<em>E</em>-GMA). The blends were prepared via melt blending, extruded into filaments, and used to print test specimens. Comprehensive analyses were conducted to assess shape memory behavior, as well as chemical, rheological, morphological, and mechanical properties. The results demonstrated that all compatibilizers enhanced both the shape memory effect and mechanical performance of PETG/TPU blends. Notably, reactive compatibilization using <em>E</em>-GMA yielded the most significant improvements. Compared to uncompatibilized blends, the E-GMA system exhibited a ∼ 12.7 % increase in shape recovery, along with enhancements in mechanical properties: Young's modulus increased by ∼20 %, tensile strength by ∼37 %, elongation at break by ∼550 %, and impact strength by ∼70 %, reaching values exceeding 650 J/m, characteristic of supertough polymers. These improvements were attributed to reduced interfacial tension, enhanced phase adhesion, and improved morphological stability in the compatibilized blends, resulting in superior printing quality. Overall, this study highlights the effectiveness of compatibilization, particularly reactive compatibilization, in improving the performance of immiscible polymer blends for advanced 3D/4D printing applications, paving the way for the development of high-performance material systems.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"215 ","pages":"Article 106393"},"PeriodicalIF":4.5,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144522993","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}

{"title":"Controlling the solvent, surfactant and ion-regulated swelling and elastic response of anionically-modified poly(N-isopropylacrylamide)-based hybrids through simultaneous macromolecular crowding","authors":"Birgul Kalkan ,&nbsp;Nermin Orakdogen","doi":"10.1016/j.reactfunctpolym.2025.106394","DOIUrl":"10.1016/j.reactfunctpolym.2025.106394","url":null,"abstract":"<div><div>An investigation is presented on how the ion specificities of anionically-modified thermosensitive hybrid systems formed by covalently cross-linked chains in presence of macromolecular crowding agent are affected by ion-pairing interactions. The effects of divalent and monovalent cations on poly(N-isopropylacrylamide-<em>co</em>-methacrylic acid)/polyacrylamide gels having controlled physical/mechanical properties were quantitatively investigated. A systematic investigation on solvent-composition induced transition of thermosensitive hybrids was performed in water–organic solvent (acetone, methanol, ethanol, and 2-propanol) mixtures. The volume fraction of solvent at which swelling of hybrids is minimum in co-nonsolvency zone varied and based on hydrophobicity and carbon chain length of alcohol, the swelling followed decreasing order; methanol &gt; ethanol &gt;2-propanol. The increase in both salt concentration and PAAm content in the precursor solution resulted in “salting out” behavior. The swelling was higher in presence of Cl⁻ anions compared to SO₄²⁻ anions and followed decreasing order for cations: Na⁺ &gt; K⁺ &gt; Mg²⁺. Salt-treatment caused significant changes in elasticity and swelling, while the elasticity of hybrids was correlated with alteration of salt concentration upon swelling in presence of kosmotropic ions. Surfactants interacted with hybrid system strongly enough to change the macroscopic properties. The swelling was lowest in cationic cetyl trimethylammonium bromide and cetyltrimethylammonium chloride solutions, while a greater swelling was observed in anionic sodium dodecylsulfonate solutions. A perspective for the molecular-specific nature of anionically modified poly(N-alkylacrylamide)-based hybrids is presented for potential applications to evaluate a wide range of surfactant, solvent and salt interactions.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"215 ","pages":"Article 106394"},"PeriodicalIF":4.5,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144517375","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}

{"title":"Stretchable, compressible, and thermo-responsive hydrogel for hot work in oil pipelines","authors":"Ziteng Yang ,&nbsp;Ruixuan Ni ,&nbsp;Jie Qi ,&nbsp;Yong Zhang ,&nbsp;Xingyu Lin ,&nbsp;Li Wang ,&nbsp;Zheng Zhang ,&nbsp;Hongsheng Lu","doi":"10.1016/j.reactfunctpolym.2025.106395","DOIUrl":"10.1016/j.reactfunctpolym.2025.106395","url":null,"abstract":"<div><div>Hydrogels can temporarily plug oil pipelines, ensuring the safety of hot work. However, hydrogels are prone to fragmentation during the injection, and the chemical hydrogels are often difficult to completely remove from the oil pipeline. Herein, we prepared a stretchable, compressible, and thermo-responsive hydrogel through the 6-aminouracil-modified copolymerization of acrylamide acrylic acid (AUP) with melamine (MEL). The rheological results indicate the hydrogel exhibits tunable mechanical strength and self-recovery. The maximum tensile strength and elongation of the hydrogel containing 25 g/L MEL are 5.19 kPa and 237.6 %, respectively. Moreover, the tensile Young's modulus and the toughness of the hydrogel are measured at 3.30 kPa and 7.07 kJ/m³, respectively. The thermo-responsive properties of the hydrogel indicate that they can easily dissolve due to the hydrogen bonds. The hydrogel demonstrates exceptional flame-retardant properties, ensuring the safety of hot work. When the plugging length of hydrogel in the simulated pipeline reached 50 cm, the maximum resistance pressure was 117.3 kPa, indicating an effective plugging capability. Furthermore, the hydrogel injected into the oil-coated pipeline can displace the residual oil, significantly reducing the residual oil content in the plugging area, thereby further ensuring the safety of hot work. The hydrogel with a plugging length of 20 cm was completely removed in approximately 40 min with 70 °C hot water. The stretchable, compressible, and thermo-responsive hydrogel can effectively plug oil pipelines and can be rapidly removed by injecting hot water, thereby ensuring the implementation of hot work and enhancing the efficiency of pipeline repair and replacement.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"215 ","pages":"Article 106395"},"PeriodicalIF":4.5,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144517376","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}

{"title":"Molecularly imprinted polymer systems for the controlled release of naphthoquinone derivatives with antimicrobial activity","authors":"Vanessa Galván-Romero ,&nbsp;Fernando Gonzalez-Salazar ,&nbsp;Karla Vargas-Berrones ,&nbsp;Francisco Castro Flores ,&nbsp;Blanca Nohemí Zamora Mendoza ,&nbsp;Denisse Atenea de Loera Carrera ,&nbsp;Fidel Martínez Gutiérrez ,&nbsp;Luz Eugenia Alcántara-Quintana ,&nbsp;Rogelio Flores-Ramírez","doi":"10.1016/j.reactfunctpolym.2025.106388","DOIUrl":"10.1016/j.reactfunctpolym.2025.106388","url":null,"abstract":"<div><div>This study aimed to synthesize, characterize, and evaluate molecularly imprinted polymers (MIPs) as drug delivery systems for naphthoquinone (NQ) derivatives. MIPs were synthesized using non-covalent bulk and <em>co</em>-precipitation polymerization methods, employing lactic acid (LA) and methacrylic acid (MA) as functional monomers and ethylene glycol dimethacrylate as a crosslinker. The quantification of 3-chloro-2-tyrosine-1,4-naphthoquinone (Cl-NQ-TYR) and 2-tyrosine-1,4-naphthoquinone (NQ-TYR) was performed using liquid chromatography with a diode array detector. The method demonstrated excellent linearity (R² = 0.99) within the working range (0.5–10 mg L⁻¹) and acceptable precision, with intra-day (CV: 0.62–2.14 % and 1–4.27 %) and inter-day (CV: 0.18–1.76 % and 0.62–5.46 %) variation for Cl-NQ-TYR and NQ-TYR, respectively. MIPs synthesized with MA exhibited the highest retention rates (99.53 % and 98.58 %). Electrostatic interactions influenced drug release properties, with zero charge points of 3.8 and 4.7, indicating that polymer ionization at higher pH values enhances drug release. All MIPs achieved imprinting factors above one (1.18–1.89), indicating that the molecular imprinting process was successful. The release profile showed an initial burst followed by sustained release over 24 h, with Cl-NQ-TYR MIP (MA, bulk) exhibiting the highest release rate, fitting best with the Korsmeyer-Peppas model. Antimicrobial activity against <em>Escherichia coli</em> (minimum inhibitory concentration, MIC: 12.5 μg mL ⁻¹) and <em>Staphylococcus aureus</em> (MIC: 3.12 μg mL⁻¹) was attributed to released NQ derivatives. MIPs demonstrated biocompatibility with dermal fibroblasts, highlighting their suitability for medical applications. These results position MIPs as a promising platform for the safe and effective delivery of therapeutic agents in biomedical applications.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"215 ","pages":"Article 106388"},"PeriodicalIF":4.5,"publicationDate":"2025-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144490910","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}

{"title":"Heterocyclic self-curing phthalonitrile resins","authors":"Loren C. Brown ,&nbsp;Cole R. Davis ,&nbsp;Andrew T. Kerr ,&nbsp;Matthew Laskoski","doi":"10.1016/j.reactfunctpolym.2025.106383","DOIUrl":"10.1016/j.reactfunctpolym.2025.106383","url":null,"abstract":"<div><div>A new class of self-curing phthalonitrile (PN) resins composed of various heterocycles is detailed. The heterocyclic-imine PN (HIPN) resins were synthesized utilizing methanol at ambient temperature and polar aprotic solvents acetone or dimethyl sulfoxide. Characterization of the resins was conducted via proton (¹H) and carbon (¹³C) nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), mechanical analysis (torsion), single crystal X-ray diffraction (SCXRD), and rheometry. The HIPN resins were self-curing due to the heterocycle, imine, and PN moieties present and displayed a range of viscosities from 146 to 1295 cP at 200 °C. The resulting HIPN polymers were prepared by post-curing to 380 °C and exhibited excellent thermal stability up to a 76 % char yield at 1000 °C. The cured HIPN polymers displayed improved mechanical performance in comparison to rival PN systems with storage moduli near 1600 MPa. This combination of properties suggests the HIPN resins are excellent materials for thermomechanical applications.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"215 ","pages":"Article 106383"},"PeriodicalIF":4.5,"publicationDate":"2025-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144523159","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}

{"title":"Modified polystyrene waste in the adsorptive removal of crystal violet and Cu (II) ion from aqueous medium – Groundwater applicability, modelling and characterization studies","authors":"Nadjib Dahdouh ,&nbsp;Bouallouche Rachida ,&nbsp;V. Sivasankar ,&nbsp;T. Chaabane ,&nbsp;Kiyoshi Omine ,&nbsp;Mohammed Azzaz ,&nbsp;Ramon Murillo","doi":"10.1016/j.reactfunctpolym.2025.106385","DOIUrl":"10.1016/j.reactfunctpolym.2025.106385","url":null,"abstract":"<div><div>The waste polystyrene in the sulfonated form was utilized as an adsorbent material for the exclusion of a crystal violet and copper (II) ion from synthetic solution and groundwater. The adsorptive removal of CV and Cu (II) ion as a function of time, pH, SPS dose, initial concentration and temperature was studied. The maximum uptake of CV and Cu (II) of 812 ± 6 mg/g (pH 3–10.5) and 257.3 mg/g (pH 6.03) was observed respectively at an equilibrium time of 60 min. An exothermic nature of sorption (− ΔH°) decreased the removal efficiency by 11 % and 16.5 ± 3.5 % for CV and Cu (II) respectively. The spontaneity of adsorption was reflected from the negative ΔG° values with decreasing randomness (− ΔS°) upon increasing the temperature. The adsorption kinetics (pseudo – first – order, pseudo – second – order, intra – particle diffusion and Elovich) and isotherms models (Langmuir, Freundlich and DKR) in compliance with the present (CV and Cu²⁺) adsorption systems were checked. The stability and efficiency for successive regeneration cycles (uptake of CV ≥ 78 % up to six cycles) inferred that SPS was superior for CV than that of Cu (II) ion. Conspicuously, the removal of 98 % of CV from groundwater was achieved, nonetheless, the Cu (II) ion removal was 56 % due to competing Ca²⁺ and Mg²⁺ ions in groundwater. The signature of copper oxides on the SPS was corroborated from the XRD patterns along with the expansion and contraction of SPS crystallites during the adsorption and regeneration processes respectively. The SEM and FTIR studies described the morphological and vibrational modifications of virgin and CV/Cu (II) laden SPS adsorbent. The twin application of SPS in CV and Cu (II) removal has been detailed with a plausible mechanism in this paper.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"215 ","pages":"Article 106385"},"PeriodicalIF":4.5,"publicationDate":"2025-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144490967","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}

{"title":"Redox/pH dual-responsive sodium alginate/cassava starch composite hydrogel beads for slow release of insecticides","authors":"Dandan Yan ,&nbsp;Yuanfeng Pan ,&nbsp;Pingxiong Cai ,&nbsp;Huining Xiao","doi":"10.1016/j.reactfunctpolym.2025.106389","DOIUrl":"10.1016/j.reactfunctpolym.2025.106389","url":null,"abstract":"<div><div>Insecticides play a crucial role in promoting crop growth and boosting crop yields. However, they also contribute to environmental pollution and pose risk to human health. To increase the utilization rate of insecticides and minimize their pollution of the soil and water environment, it is imperative to develop a green material or carrier for the controlled-release of agrochemicals including insecticides. In this study, composite hydrogel beads were successfully prepared using dialdehyde starch and sodium alginate as green-based raw materials, cystamine dihydrochloride as a cross-linking agent, and meanwhile sodium alginate was ionic cross-linked with calcium ions. As-prepared composite hydrogel beads possess pH/redox dual-responsive properties, enabling the controlled release of the insecticide dinotefuran (DIN). The properties, structure and morphology of the hydrogel beads were comprehensively characterized using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and X-ray diffraction (XRD). Additionally, the release behavior of DIN from the composite hydrogel beads under various conditions was extensively investigated. The results showed that the incorporation of dialdehyde starch significantly enhanced the encapsulation efficiency of DIN within the hydrogel bead. Moreover, the cumulative release of DIN can be precisely modulated by adjusting the release conditions or environmental stimuli; the release kinetics align with the Korsmeyer-Peppas model well. Specially, DIN release is accelerated under neutral conditions and in the presence of the reducing agent glutathione (GSH). The findings of this work are anticipated to exert a positive influence on agricultural production while also contributing to the alleviation of insecticide-related adverse environmental impacts.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"215 ","pages":"Article 106389"},"PeriodicalIF":4.5,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144523160","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}

{"title":"Versatile crosslinked poly(ionic liquid) gel nanocomposites for environmental remediation, sustainable energy generation and antibacterial applications","authors":"Oscar Ramírez ,&nbsp;Romina Ramírez ,&nbsp;Belén Olivares ,&nbsp;Sebastián Bonardd ,&nbsp;César Saldías ,&nbsp;David Díaz Díaz ,&nbsp;Angel Leiva","doi":"10.1016/j.reactfunctpolym.2025.106392","DOIUrl":"10.1016/j.reactfunctpolym.2025.106392","url":null,"abstract":"<div><div>A series of PIL gel-based nanocomposites were obtained, characterized and evaluated for relevant applications such as environmental remediation, sustainable energy generation and antibacterial applications. The materials consisted of poly(4-vinyl pyridine) crosslinked by dibrominated PEG or PCL, leaving IL-like moieties that act as crosslinking nodes within the gel network. Afterwards, the materials were employed as supports for the synthesis of Au and Pt nanoparticles (NPs) via an adsorption/reduction approach. The hybrid materials were characterized by FT-IR, TGA, DSC, NMR and HRTEM techniques. The selection of the crosslinker showed a considerable effect on the swelling and adsorption properties of the materials. Compared with the PIL-PCL gels, the PIL-PEG systems presented higher swelling ratios and faster metal uptake because of the hydrophilicity of PEG. AuNPs/PIL-based materials can remove 4NP from water sources, via adsorption and conversion into 4-aminophenol, a reaction used as an environmental remediation model. The process took place with yields above 82 % in successive runs, also exhibiting a remarkable recyclability, with no desorption of catalytic entities from the support. On the other hand, nanocomposites bearing PtNPs were capable of hydrolysing ammonia borane into hydrogen, as a model reaction for the generation of energy vector molecules, conserving the properties revealed during 4NP removal, like high effectiveness (conversion into hydrogen above 95 %), proper reusability and stability during three reaction cycles. Finally, the presence of ionizable units in the gel endows the material with antimicrobial properties, allowing a significant reduction in bacterial viability, enhancing system durability in the environments where it may be applied.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"215 ","pages":"Article 106392"},"PeriodicalIF":4.5,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144480273","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}

{"title":"Molecular mobility and calorimetric investigation in renewable polymeric systems based on polylactide blocks in situ built on Pluronic (poloxamer 188)","authors":"Nikolaos D. Bikiaris ,&nbsp;Evi Christodoulou ,&nbsp;Panagiotis Barmpalexis ,&nbsp;Apostolos Kyritsis ,&nbsp;Panagiotis A. Klonos","doi":"10.1016/j.reactfunctpolym.2025.106390","DOIUrl":"10.1016/j.reactfunctpolym.2025.106390","url":null,"abstract":"<div><div>In this work, we study a newly synthesized series of renewable block copolymers based on poly(lactic acid), PLA, blocks built in situ onto the two terminal sites of pluronic at quite small amounts (poloxamer 188, 0.05–0.20 wt%), i.e., PLA-<em>b</em>-Pluronic-<em>b</em>-PLA. The investigation involves mainly calorimetry and dielectric spectroscopy, supplemented by other techniques for the structure. The local and segmental dynamics mapping for the said systems is performed here for the first time. The direct effects of the copolymer structure on the thermodynamical properties are assessed mainly in the amorphous PLA state. Useful conclusions are obtained by directly comparing with neat linear PLAs of various molecular weights, <em>M</em>_n. Interestingly, Pluronic seems to play a <em>co</em>-initiator role within the ring opening polymerization of lactides. The successful copolymer synthesis is partially confirmed here by the systematic decrease of the copolymer chain lengths (<em>M</em>_n), the corresponding acceleration of molecular mobility (<em>T</em>_g drop) and the decreasing fragility, with the increasing of the amount of Pluronic. Compatible with the above results are also the recorded effects on crystallizability of PLA, being mainly suppressed in the PLA/Pluronic systems, in terms of both nucleation and crystalline fraction. The dominant parameters on molecular dynamics were the <em>M</em>_n, the alternations in the free volume and chain-chain associations, in addition to the existence of dynamical heterogeneities in the copolymers, always comparing with neat PLAs of various <em>M</em>_n [<em>Polymer</em> 305 (2024) 127177]. The PLA/Pluronic systems are envisaged for biomedical application, as are considered to exhibit the so-called thermo-responsive transition in aqueous environments. In this frame, the plethora of alternations recorded, herein, e.g., on the <em>T</em>_g and semi-crystallinity of PLA/Pluronic, comparing with neat PLAs, set these systems interesting for further study regarding the applications.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"215 ","pages":"Article 106390"},"PeriodicalIF":4.5,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144471665","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}