{"title":"Probing the inner structure and dynamics of pH-sensitive block copolymer nanoparticles with nitroxide radicals using scattering and EPR techniques","authors":"Svetlana Lukáš Petrova , Alessandro Jäger , Ewa Pavlova , Martina Vragović , Eliézer Jäger , Miloš Steinhart , Damir Klepac","doi":"10.1016/j.eurpolymj.2024.113473","DOIUrl":"10.1016/j.eurpolymj.2024.113473","url":null,"abstract":"<div><div>This research emphasizes the crucial role of electron paramagnetic resonance (EPR) spectroscopy in nanoparticle analysis, showcasing its distinctive ability to probe molecular-level details. We demonstrate the synthesis and self-assembly of a new class of pH-responsive amphiphilic diblock copolymers, specifically poly[<em>N</em>-(2-hydroxypropyl)-methacrylamide]-<em>block</em>-poly[2-(diisopropylamino)ethyl methacrylate] (PHPMA-<em>b</em>-PDPA), incorporating 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radicals covalently bound to the hydrophilic PHPMA segment. The copolymer synthesis involved a three-step process, combining reversible addition − fragmentation chain transfer (RAFT) polymerization with carbodiimide (DCC) chemistry. TEMPO radical-containing nanoparticles (RNPs) were created using microfluidic (MF) nanoprecipitation, a technique essential for generating uniform nanoparticles with predictable biodistribution and cellular uptake. Adjusting MF protocol parameters allowed fine-tuning of RNP sizes. EPR spectroscopy confirmed the formation of core–shell RNPs, with features aligning closely with those obtained from scattering techniques like dynamic light scattering (DLS), static light scattering (SLS), small-angle X-ray scattering (SAXS), and cryo-transmission electron microscopy (cryo-TEM). EPR spectroscopy emerges as a potent tool for molecular-level analysis of colloidal polymer systems. This study highlights the EPR-spin label method’s efficacy in probing the internal structural features and dynamics of core–shell nanoparticles, especially their response to pH-triggered disassembly. The findings open new avenues for the use of pH-responsive TEMPO-labeled diblock copolymers in controlled drug delivery applications.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"220 ","pages":"Article 113473"},"PeriodicalIF":5.8,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142319865","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tianfeng Zhou , Haotian Duan , Beibei Li , Yuxia Pang , Hongming Lou , Dongjie Yang , Xueqing Qiu
{"title":"Rapid synthesis of solid polycarboxylate superplasticizers via photoinitiated radical polymerization","authors":"Tianfeng Zhou , Haotian Duan , Beibei Li , Yuxia Pang , Hongming Lou , Dongjie Yang , Xueqing Qiu","doi":"10.1016/j.eurpolymj.2024.113474","DOIUrl":"10.1016/j.eurpolymj.2024.113474","url":null,"abstract":"<div><div>The synthesis and performance optimization of solid polycarboxylate superplasticizers (PCEs) present significant challenges. In our study, a rapid synthesis of a solid polycarboxylate superplasticizer (IPCE10) was achieved using photoinitiated free radical polymerization. IPCE10 exhibited good dispersibility and improved compressive strength in concrete. Dynamic light scattering tests and molecular dynamics simulations demonstrated that the adsorption conformation of IPCE10 on the calcium silicate hydrate surface was relatively dispersed, with a thicker adsorption layer. This indicates that IPCE10 has stronger steric hindrance, resulting in superior dispersibility. Additionally, density functional theory calculations of the reaction energy barriers for radical generation by photoinitiated and azo-initiated monomers revealed that the energy barrier in the photoinitiated system was significantly lower than that in the azo-initiated system, indicating that photoinitiated polymerization is more feasible. This study proposes a simple and rapid method for the preparation of solid polycarboxylate superplasticizers, providing valuable insights for the development of high-value-added construction materials.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"220 ","pages":"Article 113474"},"PeriodicalIF":5.8,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142356992","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sen Tong , Shicui Luo , Qiuqiong Yang , Bo Song , Renjie Chang , Junzi Wu
{"title":"Preparation and biological evaluation of a glucose-responsive block copolymer nanoparticle with the ability to ameliorate diabetic kidney damage","authors":"Sen Tong , Shicui Luo , Qiuqiong Yang , Bo Song , Renjie Chang , Junzi Wu","doi":"10.1016/j.eurpolymj.2024.113472","DOIUrl":"10.1016/j.eurpolymj.2024.113472","url":null,"abstract":"<div><div>In this study, a p(AAPBA-<em>b</em>-Daidzein) block copolymer was designed and synthesised using glucose-responsive 3-acrylamidophenylboronic acid (AAPBA) and esterified daidzein as structural units; this copolymer possessed anti-diabetic pharmacological activity. After confirming the chemical structure of the copolymer, nanoparticles of the copolymer were prepared using the water-in-oil method. The results of the <em>in vitro</em> experiments showed that nanoparticles swelled when the pH was >7 or when the glucose concentration exceeded 1.0 mg/mL. Particle size measurements showed that the size of the nanoparticles was kept in the range of 100–300 nm before and after the glucose response, which helped avoid their clearance by the liver and kidneys. As the nanoparticles swelled, insulin and esterified daidzein were continuously released. The nanoparticles subcutaneously injected into mice with streptozotocin-induced diabetes were able to quickly and continuously reduce the blood sugar levels; significantly improve renal pathological damage and reduce renal function damage, inflammatory factors and oxidative stress indicators. In summary, the p(AAPBA-<em>b</em>-Daidzein) glucose-responsive nanoparticles prepared in the current study possess good pH value and glucose sensitivity, can achieve a precise and controlled release of insulin and exert the pharmacological activity of esterified daidzein. Therefore, it shows potential clinical application value in the treatment of diabetes and its complications.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"220 ","pages":"Article 113472"},"PeriodicalIF":5.8,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142323794","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Efficient and facile dual post-polymerization modification using acetoacetate-acrylate Michael addition","authors":"Hongjie Chen, Linlin Wang, Shengyu Feng, Lei Li","doi":"10.1016/j.eurpolymj.2024.113463","DOIUrl":"10.1016/j.eurpolymj.2024.113463","url":null,"abstract":"<div><div>Post-polymerization modification (PPM) is a valuable strategy for achieving diversified functional polymers; nonetheless, the pursuit of achieving mild and efficient dual modification along the polymeric backbone remains as a challenge. In this work, the Michael addition reaction of acetoacetates and acrylates have been demonstrated as a robust PPM technique. The reversible addition-fragmentation chain transfer polymerization of commercially available 2-(acetoacetoxy)ethyl methacrylate provides a polymer scaffold with controlled molecular weight and acetoacetate groups. These pendant groups are capable of undergoing efficient double addition reactions with acrylates, leading to an increased density of functional moieties within the polymeric backbone. This PPM reaction exhibits unique advantages such as mild reaction conditions (at 40 °C), rapid kinetics (completion within 1 h), and high atom economy. Consequently, a series of polymers with tunable thermal stability, glass transition temperature, and hydrophilicity have been successfully synthesized. Applications have been demonstrated for both the synthesis of polymers exhibiting aggregation-induced luminescence and the preparation of luminescent materials with adjustable mechanical properties. This pioneering work unveils a robust post-polymerization modification technique, significantly advancing the synthesis of innovative functional polymers.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"220 ","pages":"Article 113463"},"PeriodicalIF":5.8,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424820","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Fabrication of multi-responsive dynamic poly(ethylene glycol)-iron oxide nanoparticle nanocomposite hydrogels through interfacial boronate-catechol crosslinking","authors":"Chen-Cheng Yu , Yu-Chia Su , Yi-Cheun Yeh","doi":"10.1016/j.eurpolymj.2024.113469","DOIUrl":"10.1016/j.eurpolymj.2024.113469","url":null,"abstract":"<div><div>Poly(ethylene glycol) (PEG)-based nanocomposite (NC) hydrogel with multiple advantageous properties such as high mechanical strength and stimuli-responsiveness have been demonstrated as promising materials across various fields. Here, an innovative type of PEG-based NC hydrogels is fabricated using phenylboronic acid-polyethyleneimine (PBA-PEI)-functionalized iron oxide nanoparticles (PP-IOPs) to crosslink the dopamine-modified 4arm-PEG (DA-4APEG) through boronate-catechol crosslinking. DA-4APEG/PP-IOP NC hydrogels exhibit tunable microstructures (i.e., pore size) and properties (i.e., rheological, mechanical, and swelling behaviors) by changing the number of PP-IOPs in the hydrogel network. With the dynamic crosslinks and magnetic nanoparticles in the network, DA-4APEG/PP-IOP NC hydrogels are self-healable and also responsive to various stimuli, including temperature, pH, glucose, dopamine, hydrogen peroxide, magnetic field, and near-infrared light. Therefore, a versatile PEG-based hydrogel platform has been developed, featuring customizable properties, multiple stimuli-responsiveness, and dynamic characteristics, making it suitable for advanced applications.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"220 ","pages":"Article 113469"},"PeriodicalIF":5.8,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142327407","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Cyclodextrin-activated porphyrin-DNA nanofibers with AS1411/Hemin toehold for enhanced and targeted photodynamic therapy","authors":"Jinyu Gao, Hai Yang, Cheng Deng, Yuting Lv, Simin Liu, Zhiyong Zhao","doi":"10.1016/j.eurpolymj.2024.113466","DOIUrl":"10.1016/j.eurpolymj.2024.113466","url":null,"abstract":"<div><div>Targeted photodynamic therapy is considered superior to conventional photodynamic therapy due to the enhanced uptake of photosensitizers by tumor cells. However, porphyrin-based photodynamic therapy is still limited due to the low hydrophilicity, poor biocompatibility and susceptibility to quenching of photosensitizers. Herein, we report cyclodextrin-activated porphyrin-DNA nanofibers with AS1411/Hemin toeholds, which enable targeted cancer cells recognition and catalytic oxygenation for enhanced photodynamic therapy. The nanofibers are formed through the self-assembly of the host–guest complex of cyclodextrin and porphyrin-DNA amphiphiles, and can be further functionalized on the surface with AS1411/Hemin. AS1411/Hemin can specifically target nucleolin-overexpressing cancer cells and catalyze conversion of excessive H<sub>2</sub>O<sub>2</sub> into O<sub>2</sub> within tumor cells, thereby alleviating tumor hypoxia and further cascaded enhancing PDT efficacy. These results suggest that the programmable and multifunctional nanofiber provided an effective nanoplatform for enhanced and targeted photodynamic therapy.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"220 ","pages":"Article 113466"},"PeriodicalIF":5.8,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142311209","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Wanwanut Chueasupcharoen , Puttinan Meepowpan , Kiattikhun Manokruang , Montira Sriyai , Chawan Manaspon , Brian J. Tighe , Matthew J. Derry , Paul D. Topham , Winita Punyodom
{"title":"Metal-free ring-opening polymerization for the synthesis of biocompatible star-shaped block copolymers with controllable architecture","authors":"Wanwanut Chueasupcharoen , Puttinan Meepowpan , Kiattikhun Manokruang , Montira Sriyai , Chawan Manaspon , Brian J. Tighe , Matthew J. Derry , Paul D. Topham , Winita Punyodom","doi":"10.1016/j.eurpolymj.2024.113471","DOIUrl":"10.1016/j.eurpolymj.2024.113471","url":null,"abstract":"<div><div>Star-shaped block copolymers (SBCs) have sparked interest as efficient cargo carriers due to their high loading capacity, decreased burst effects through sustained release, and maintained stability in dilute aqueous solution. Despite these advantages, the practical usage of SBCs is hindered by their challenging synthesis processes that often utilize metal-based catalysts at high temperatures. Herein we report the tailored synthesis of 3-, 4-, and 6-arm polycaprolactone-<em>b</em>-poly(ethylene glycol), PCL-<em>b</em>-PEG, SBCs using diphenyl phosphate as a friendlier, more sustainable non-metallic catalyst. Nuclear magnetic resonance (NMR) analysis confirms the molecular architecture of SBCs and gel permeation chromatography (GPC) is used to elucidate trends in molar mass when the number of arms within the SBCs is tuned, while dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS) studies provide insights into aggregation behavior. Critical aggregation concentration (CAC) values, as measured by fluorescence spectroscopy, demonstrated that the 4-arm and 6-arm SBCs have greater stability than the 3-arm SBC. Biocompatibility assessment indicated minimal cytotoxicity of the nanoaggregates, even at high concentration, making these PCL-<em>b</em>-PEG SBCs potentially safe and sustainable vehicles for biomedical release applications.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"220 ","pages":"Article 113471"},"PeriodicalIF":5.8,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424848","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Recent trends and applications of nanostructure-based drug delivery in alleviating pulmonary fibrosis","authors":"Lokesh Nagar , Annu Saini , Sachin Kumar Singh , Gaurav Gupta , Ronan MacLoughlin , Dinesh Kumar Chellappan , Parteek Prasher , Amlan Chakraborty , Kamal Dua , Harish Dureja","doi":"10.1016/j.eurpolymj.2024.113467","DOIUrl":"10.1016/j.eurpolymj.2024.113467","url":null,"abstract":"<div><p>Pulmonary fibrosis is an irreversible fatal chronic disease of lungs, characterized by excessive extracellular matrix deposition, epithelial-mesenchymal transition (EMT) imbalance, and scar formation in the lungs, resulting in severe breathing problems, cough, dyspnea, functional failure of the lungs, impaired quality of life and even death. A recent data on pulmonary fibrosis from various countries shows high mortality rates. As of date, there is no effective clinical treatment to completely cure pulmonary fibrosis. However, conventional symptomatic treatment is available. Anti-fibrotic drugs like pirfenidone and nintedanib are available currently as part of the conventional treatment. Novel therapeutic strategies involving targeted drug delivery via nanostructures has been shown to have enormous potential. Based on their unique physical properties, nanostructures have demonstrated the potential to improve the pharmacokinetics of loaded medications. The main goal of this review is to present a complete spectrum of therapeutics based on nanostructures for the treatment and management of pulmonary fibrosis. These include nanoparticles, polymeric nanoparticles, solid-lipid nanoparticles, liposomes, exosomes, and nanoemulsions. This advanced platform may pave a new path to pulmonary fibrosis clinics.</p></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"220 ","pages":"Article 113467"},"PeriodicalIF":5.8,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142274574","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ritu Singhmar , Sumanta Sahoo , Soonmo Choi , Jin Hyeok Choi , Ankur Sood , Sung Soo Han
{"title":"Harnessing potential of microwave-assisted ultrafast synthesis of reduced graphene oxide/Mn3O4 bioactive nanocomposite hydrogel for bone tissue engineering","authors":"Ritu Singhmar , Sumanta Sahoo , Soonmo Choi , Jin Hyeok Choi , Ankur Sood , Sung Soo Han","doi":"10.1016/j.eurpolymj.2024.113462","DOIUrl":"10.1016/j.eurpolymj.2024.113462","url":null,"abstract":"<div><div>The development of functional materials with the potential for bone tissue regeneration along with rapid synthesis and cost-effective approach has been challenging. In this regard, hydrogels have been explored as a potent candidate to behave as a 3D scaffold for bone repair. However, poor mechanical attributes impeded their clinical translation. Enthralling demonstration of the potential of carbon-based nanocomposites in bone tissue engineering has been constantly encouraging the fabrication of advanced nanocomposites. Here, we investigated the fabrication of reduced graphene/manganese (II, III) oxide (RGO/Mn<sub>3</sub>O<sub>4</sub>) nanocomposites by taking advantage of the microwave-assisted synthesis approach for cost effective, and ultrafast synthesis. Mn<sub>3</sub>O<sub>4</sub> nanoparticles with uniform distribution in RGO sheets and ∼ 1.7 nm size was fabricated using the approach. Further, fine-tuning of the structural interaction and mechanical behavior of the GelMA-based hydrogels upon reinforcement with RGO/Mn<sub>3</sub>O<sub>4</sub> nanocomposites was investigated as a function of different concentrations of the nanocomposites where upto 50 % increment in the compressive stress was observed compared to native GelMA hydrogel. The ability of these hydrogels was further investigated for their osteogenic behaviour on MC3T3-E1 preosteoblast cells where constant cell proliferation for up to 10 days was witnessed for the hybrid hydrogel with the highest concentration of the nanofillers.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"220 ","pages":"Article 113462"},"PeriodicalIF":5.8,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142311208","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mai Feng , Chao-qun Wu , Zhu Zeng , Lin Wang , Meng-jie Xiao , De-xiang Sun , Yong Wang
{"title":"Largely enhanced damping performance of nitrile rubber/ethylene–vinyl acetate blends via phenolic resin-induced phase separation","authors":"Mai Feng , Chao-qun Wu , Zhu Zeng , Lin Wang , Meng-jie Xiao , De-xiang Sun , Yong Wang","doi":"10.1016/j.eurpolymj.2024.113446","DOIUrl":"10.1016/j.eurpolymj.2024.113446","url":null,"abstract":"<div><div>The low glass transition temperature (<span><math><mrow><msub><mi>T</mi><mi>g</mi></msub></mrow></math></span>) and narrow effective damping temperature range (EDTR) greatly restrict the application of common vulcanized rubbers in fields relating to high temperature environmental condition due to the greatly reduced damping performances. In this work, phenolic resin (PR) was incorporated into nitrile rubber/ethylene–vinyl acetate (NBR/EVM) blends through melt-compounding processing, and the microstructure and damping performance changes induced by PR were comparatively investigated. The results show that PR induces the phase separation of the blends and most of PR particles selectively locate in the NBR component. Molecular dynamics simulation confirms that more hydrogen bonds form in the ternary blends, and reduced free volume fraction is also achieved. The ternary blends show good high-temperature damping performances, and apparently enhanced <span><math><mrow><msub><mi>T</mi><mi>g</mi></msub></mrow></math></span> (up to 17.7 °C) and EDTR (82.6 °C, from −2.6 to 80 °C) are also achieved. Additionally, the ternary blends exhibit good mechanical properties, including higher ductility and larger fracture energy, and better energy dissipation ability. This work provides an alternative resolution way to enhance the damping performances of the common vulcanized rubbers at high temperatures.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"220 ","pages":"Article 113446"},"PeriodicalIF":5.8,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142311206","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}