Ondrej Kopilec, Jan Svoboda, Radoslava Sivkova, Ondrej Sedlacek, Ognen Pop-Georgievski
{"title":"Effect of Side Groups on the Surface Parameters and Antifouling Properties of Poly(N-Alkyl Acrylamide)-Coated Surfaces","authors":"Ondrej Kopilec, Jan Svoboda, Radoslava Sivkova, Ondrej Sedlacek, Ognen Pop-Georgievski","doi":"10.1002/macp.202400481","DOIUrl":"https://doi.org/10.1002/macp.202400481","url":null,"abstract":"<p>Understanding the origins of antifouling properties in polymer materials is essential for improving their biocompatibility. In this work, the effect of side groups in poly(<i>N</i>-alkyl acrylamide)s on their resistance to non-specific interactions with blood proteins is studied. Using reversible addition-fragmentation chain transfer (RAFT) polymerization protocol, a library of acrylamide-based polymers is synthesized, including poly((<i>N</i>-propyl)acrylamide) (pPAM), poly((<i>N</i>-ethyl)acrylamide) (pEAM), poly(<i>N</i>-(2-fluoroethyl)acrylamide) (pFEAM) and poly(<i>N</i>-(2-hydroxyethyl)acrylamide) (pHEAM), with four distinct chain lengths, i.e. degrees of polymerization (<i>DP</i> = 25, 50, 75, and 100). The polymer chains are attached to gold substrates under the most widely used “grafting to” approach through the trithiocarbonate chain end groups. The physical properties of the resulting polymer coatings are studied and evaluated their antifouling properties against blood plasma. While the of pPAM and pEAM reduced the fouling to a certain extent, semi-fluorinated pFEAM and pHEAM coatings showed improved fouling resistance with increasing <i>DP</i> and enhanced brush-like character. Notably, pFEAM and pHEAM coatings of nominal <i>DP</i> = 100 manage to reduce the fouling by more than 90% when compared to bare gold surfaces. These findings highlight the critical role of polymer side groups and chain length in designing antifouling coatings.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 14","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/macp.202400481","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144657564","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Autoxidation-Induced Curing of 6-Hydroxycatechol-Containing Adhesive","authors":"Zhongtian Zhang, Bruce P. Lee","doi":"10.1002/macp.202500010","DOIUrl":"https://doi.org/10.1002/macp.202500010","url":null,"abstract":"<p>Catechol is an oft-used crosslinking precursor and adhesive molecule for designing in situ curable biomaterials and adhesives and the addition of chemical or enzymatic oxidants is required to initiate fast curing. Here, the feasibility for 6-hydroxydopamine (6-OHDA)-modified 8-armed polyethylene glycol (PEG) (8-arm PEG-DA-OH) to cure through autoxidation is evaluated. The modification of catechol side chain with an electron-donating hydroxyl group at the six-position drastically increased the rate of oxidation and the adhesive cured in just over 1 min through autoxidation. The cure time is decreased to under 40 s with the addition of branched polyethyleneimine (PEI). UV–vis spectra revealed that the deprotonated quinone of 6-OHDA is a key oxidation intermediate for chemical crosslinking between 6-OHDA and with primary amine. PEG functionalized with unmodified catechol do not solidify through autoxidation, which highlights the contribution of the electron-donating hydroxyl group in promoting fast oxidation and crosslinking. Eight-arm PEG-DA-OH and PEI mixture also demonstrated significantly higher adhesion strength to pericardium tissues when compared to a commercial PEG-based adhesive, DuraSeal. This report highlights 6-OHDA as an effective crosslinking precursor and adhesive molecule for designing injectable adhesives that do not require externally added oxidants and the adhesive is activated by simple dissolution in an aqueous solution.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 14","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144657565","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Emulsion-Templated Preparation of Protein-Encapsulated Hydrophilic Polymeric Nanocapsules","authors":"Akifumi Kawamura, Miyu Shimizu, Rika Hirabayashi, Takashi Miyata","doi":"10.1002/macp.202500022","DOIUrl":"https://doi.org/10.1002/macp.202500022","url":null,"abstract":"<p>Encapsulation of biomacromolecules, such as proteins, enzymes, and nucleic acids, is of great interest for applications in drug delivery systems and nanobioreactors, because it protects biomacromolecules from degradation by protease. This paper describes the facile preparation of protein-encapsulated hydrophilic polymeric nanocapsules using an emulsion-templated approach. A water-soluble block copolymer emulsifier, poly(2-methacryloyloxyethyl phosphorylcholine)-<i>b</i>-poly[oligo(ethylene glycol)methacrylate] (PMPC-<i>b</i>-POEGMA), is synthesized via reversible addition fragmentation chain transfer polymerization. The PMPC-<i>b</i>-POEGMA emulsifier stabilizes the water-chloroform interface in water-in-oil emulsions. Nanocapsules are prepared by cross-linking the POEGMA blocks of the emulsifier located on the surface of the water droplets using divinyl sulfone (DVS). The resulting nanocapsules have a cross-linked POEGMA membrane and are stably dispersed in aqueous media without further modification. Peroxidase is encapsulated in nanocapsules by dissolving it in the water phase prior to emulsification and cross-linking. The cross-linking density of the capsule membrane can be tuned by varying the DVS to hydroxy group ratio, which affects the encapsulation efficiency. The nearly complete encapsulation of peroxidase is achieved when the DVS to hydroxy group ratio ranges from 0.1 to 1.0. This emulsion-templated strategy provides a facile route to protein-loaded hydrophilic nanocapsules, which have potential applications in nanobioreactors, drug delivery systems, and diagnostic systems.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 14","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144657563","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jin Xie, Mengxue Zhou, Hongyu Ren, Rui Dou, Jiayu Zhang, Yi Hu, Jun Ouyang, Jun Chen
{"title":"Engineering a Tumor-Acidity-Responsive PEG-Sheddable Nanoassembly for Combating Drug Resistance","authors":"Jin Xie, Mengxue Zhou, Hongyu Ren, Rui Dou, Jiayu Zhang, Yi Hu, Jun Ouyang, Jun Chen","doi":"10.1002/macp.202400505","DOIUrl":"https://doi.org/10.1002/macp.202400505","url":null,"abstract":"<p>This study presents a simple strategy to develop a tumor-acidity responsive core-crosslinked micellar nanoassembly capable of delivering multiple drugs to combat drug resistance. Paclitaxel (PTX) nanocrystals are prepared using D-α-tocopherol polyethylene glycol 1000 succinate (TPGS) as an emulsifier and cross-linked with poly(β-cyclodextrin) (PCD) to form the core. An acid-labile prodrug, poly(ethylene glycol)-doxorubicin (mPEG-DOX), is utilized as the shell, forming a core-shell nanoassembly (CSNA) via supramolecular interactions. The CSNA demonstrated high stability in aqueous and serum environments, with triggered shell-detachment in response to tumor acidity. The nanomedicine exhibited superior inhibition of drug-resistant cancer cell line MCF-7/ADR compared to DOX or PTX alone, offering potential to overcome drug resistance in chemotherapy.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 13","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558116","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"The Effects of Polymer Molecular Weight on Morphology and the Device Efficiency: Progress and Prospects for Organic Solar Cells","authors":"Muhammad Ismail Saqib, Xipeng Yin, Zefeng Liu, Manqi Zhao, Meiyan Cheng, Yubiao Li, Chunpeng Song, Qiuju Liang, Jingming Xin, Zongcheng Miao, Jiangang Liu","doi":"10.1002/macp.202500031","DOIUrl":"https://doi.org/10.1002/macp.202500031","url":null,"abstract":"<p>Organic solar cells (OSCs) are developing as a crucial technology for sustainable energy, attaining power conversion efficiencies (PCEs) of over 20%. The morphology of the active layer is essential in influencing PCE, but its exact manipulation is difficult because of the complex interactions between donor and acceptor molecules. The molecular weight (<i>M</i><sub>w</sub>) of polymers is a crucial parameter that significantly affects morphological development, including domain size, purity, crystallinity, and molecular orientation. Here the trade-offs of <i>M</i><sub>w</sub> regulation are examined, emphasizing that high-<i>M</i><sub>w</sub> polymers improve stability and crystallinity but may hinder phase separation. In contrast, low-<i>M</i><sub>w</sub> polymers promote finer phase separation at the cost of mechanical integrity. Moreover, current achievements are synthesized to clarify methodologies for optimizing <i>M</i><sub>w</sub> to achieve balanced morphological features, to enhance active layer design, and maximize the potential of OSCs. These insights facilitate the resolution of existing difficulties and promote the advancements of OSCs toward useful and sustainable applications.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 13","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558187","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Controlling Porosity and Multifunctionality in Electrospun Polymeric Fibers by Nanoscale Phase Separations: Flory–Huggins Interaction Parameters Revisited","authors":"Debmalya Roy, Subhash Mandal, Karan Chandrakar, Mayank Dwivedi","doi":"10.1002/macp.202500046","DOIUrl":"https://doi.org/10.1002/macp.202500046","url":null,"abstract":"<p>Polymeric fibers with multifunctional properties and controlled porosity serve as an ideal platform for creating adaptive scaffolds in regenerative tissue engineering and wearable sensors for biomedical applications. The phase separation in polymeric blends and solutions has been extensively studied using Flory–Huggins polymer–solvent interaction parameter, which is considered a crucial factor in achieving desired morphologies. A detailed outlook of microstructural insight into the polymeric rich and lean phases under the external stimuli, such as an electric field, has been discussed in this paper. The effects of electrospinning parameters on the geometry and physical properties of polymeric nanofibers are explored to understand the role of interactions in the ternary system of polymer–solvent–filler, which contribute to the enthalpy of mixing during electrospun process. The presence of an immiscible filler phase in polymer and solvent systems leads to hierarchical nanoscale phase segregation, where the dimensions and physicochemical properties of the fillers play a crucial role. A well-defined structure–property relationship is established in composite polymeric electrospun fibers, showing that these fibers can be designed to exhibit specific mechanical, chemical, and biological properties by controlling the interaction dynamics within the polymer–filler–solvent ternary system, where the Flory–Huggins isotherm serves as a crucial theoretical framework.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 13","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558111","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"S-S Vitrimer Composites via Simplified Fabrication: Recyclable Graphite Flakes Simultaneously Enhance Mechanical-Thermal Properties and Suppress Disulfide Exchange","authors":"Xin Wu, Chao Yan, Ying Hu, Junlei Tang, Xiuli Zhao, Mao Chen","doi":"10.1002/macp.202500094","DOIUrl":"https://doi.org/10.1002/macp.202500094","url":null,"abstract":"<p>Vitrimers are covalently crosslinked networks with dynamic bond exchange, where their dynamic behavior is typically regulated by adjusting network structures or incorporating fillers. This study introduces graphite flakes (GFs) into sulfur-containing. Vitrimers to investigate their effects on mechanical properties, stress relaxation, and thermal conductivity. The results demonstrate that adding 10 wt.% GFs increases tensile strength by 4.37% compared to pure epoxy vitrimer, while higher filler content reduces toughness and decelerates stress relaxation. At 160 °C, the characteristic relaxation time rises from 15.35 s (pure vitrimer) to 108.85 s (40 wt% GFs composite). The Arrhenius prefactor (<i>τ₀</i>) decreases with GFs loading, whereas the activation energy (<i>E<sub>a</sub></i>) remains nearly unaffected. Additionally, 40 wt.% GFs enhance thermal diffusivity by 110.17% due to oriented phonon transport channels. Chemical recycling via DTT solution achieves complete matrix degradation and filler recovery without damaging GFs. This study provided valuable insights for optimizing vitrimer composites, particularly in enhancing thermal conductivity and modulating dynamic properties.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 13","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558027","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Synthesis and Characterization of Biodegradable Poly(1,8-octanediol-co-citrate)/Poly(ε-caprolactone) Copolyester with Robust Resilience and Low Hysteresis","authors":"Xuemei Chu, Bing Han, Minxuan Kuang, Sitong Hou, Hongyang Zhao, Qian Xu, Xiuqin Zhang","doi":"10.1002/macp.202500038","DOIUrl":"https://doi.org/10.1002/macp.202500038","url":null,"abstract":"<p>The extensive application of polymer materials has caused environmental pollution. Biodegradable polymers, especially biodegradable elastomers, show great potential in biomedical and other fields. Poly(1,8-octanediol-co-citrate) (POC) is a well-known biodegradable elastomer with good properties but limited by poor mechanical properties. To address this issue, a new biodegradable poly(1,8-octanediolco-citrate)/poly(ε-caprolactone) copolyester (POCC) is synthesized. The results show that PCL chains are successfully incorporated into the POCC network. POCC exhibits excellent mechanical properties with a high elongation at break, remarkable cyclic tensile recovery rate, and low hysteresis. It also has good transparency and can be degraded in PBS buffer solution. POCC presents great potential for applications in biomedicine, environmental protection, and electronics, providing new possibilities for the development of related fields.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 13","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558081","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}