{"title":"From Molecular Structure to Macroscopic Performance: Insights into Polycarbosilane Curing","authors":"Tobias Haupt, Vanessa Koch, Florian Rott, Ricardo Helm, Marcel Dickmann, Torsten Gottschalk-Gaudig, Konstantin Karaghiosoff","doi":"10.1002/marc.70347","DOIUrl":"10.1002/marc.70347","url":null,"abstract":"<div>\u0000 \u0000 <p>Curing protocols critically influence the structure and properties of crosslinked polymer networks, yet their impact on nanoscale structural features remains poorly understood. Here, polycarbosilane (PCS) networks are used as a model system to investigate curing-induced structural evolution across multiple techniques. PCS networks were prepared via Pt-catalyzed hydrosilylation reaction at progressively higher curing temperatures, and their macroscopic properties were correlated with molecular-level changes using a combined experimental-computational approach. Mechanical testing revealed a transition from flexible to brittle behavior with increasing curing temperature, while dynamic mechanical thermal analysis (DMTA) and swelling experiments showed a continuous increase in glass transition temperature (<i>T<sub>g</sub></i>) and crosslink density. Positron annihilation lifetime spectroscopy (PALS) provided direct insight into network development and revealed a redistribution toward larger free-volume populations despite the higher crosslink density. Molecular dynamics (MD) simulations qualitatively supported this trend by demonstrating reduced segmental mobility and the formation of fewer but larger geometric free volume domains at high conversion, thereby explaining both the increase in free volume and the onset of brittleness. This integrated approach highlights the strong influence of curing temperature on both network architecture and macroscopic performance. Beyond PCS, the methodology provides a generalizable framework for analyzing structure-process-property relationships in highly crosslinked polymer networks.</p>\u0000 </div>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":"47 16","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148373996","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yoseph Kim, So Han Kim, Gue Seon Lee, Jeung Gon Kim, Youngjo Kim
{"title":"Temperature-Driven Switching Between Block, Near-Statistical, and Gradient Copolymers Enabled by Multinuclear Aluminum Catalysis","authors":"Yoseph Kim, So Han Kim, Gue Seon Lee, Jeung Gon Kim, Youngjo Kim","doi":"10.1002/marc.70346","DOIUrl":"10.1002/marc.70346","url":null,"abstract":"<p>Precise control over microstructure in the ring-opening copolymerization of ε-caprolactone (CL) and lactide (LA) remains challenging because of intrinsic monomer reactivity differences and concomitant transesterification, which often obscure the origin of the final sequence distribution. Here we show that a single tetrameric multinuclear aluminum catalyst provides programmable access to block, near-statistical, and gradient CL/LA copolymers within one catalytic platform. The complex mediates well-controlled ring-opening polymerization of both monomers, enabling the synthesis of diblock, triblock, and multiblock architectures by sequential monomer addition under insertion-dominated conditions. Under simultaneous copolymerization conditions, variation of the reaction temperature modulates the balance between propagation and exchange processes and thereby governs the copolymer microstructure. At lower temperature, the copolymers display reactivity ratios close to unity, average sequence lengths near two, and thermal behavior consistent with near-statistical incorporation. At elevated temperature, enhanced transesterification leads to pronounced growth of homologous sequences and compositional drift along the chains, characteristic of gradient architectures. Taken together, these findings establish a unified kinetic–thermodynamic framework for sequence control in CL/LA copolymerization and reveal multinuclear aluminum catalysis as an effective strategy to traverse distinct copolymer microstructures using an earth-abundant metal system.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":"47 16","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/marc.70346","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148300465","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Photocontrolled Drug Release From Donor–Acceptor Stenhouse Adduct Amphiphile Doped Laden Polymeric Hydrogel","authors":"Wai-Ki Wong, Man-Huen Leung, Ka-Lung Hung, Leong-Hung Cheung, Kelvin Sze-Yim Cai, Nathanael Chun-Him Lai, Ka-Hing Wong, Franco King-Chi Leung","doi":"10.1002/marc.70360","DOIUrl":"10.1002/marc.70360","url":null,"abstract":"<div>\u0000 \u0000 <p>In chemotherapy, drug dosage should be carefully planned with precise pharmacokinetics. Compared to direct, soluble drug administration, a stimuli-responsive drug delivery material system provided an on-demand medication with minimum adverse effects. Among many stimuli, the use of external red light enables manual remote functionality compared to physiological stimuli such as pH. Herein, a 650 nm red-light-responsive, metal-free hydrogel scaffold for stimuli-responsive drug delivery is reported. The hydrogel network is built by poly(ethylene) glycol thiol and poly(ethylene) glycol acrylate via Michael addition. Donor–acceptor Stenhouse adduct amphiphile (DA), which acts as the moderator of hydrophobic drug doxorubicin, is encapsulated in a polyethylene glycol network to create a drug-loaded hydrogel scaffold. The preparation of DA is purely aqueous and shows a broad absorbance band over 430–800 nm, which enables potential operation in deep tissue. During the drug release experiments, the presence of amphiphile greatly slows the drug release rate in vitro. By using 650 nm laser irradiation, the drug release from amphiphile-encapsulated hydrogel can be triggered after the passive diffusion period. The proposed hydrogel serves as an example of the combination of a photo-switch conjugated amphiphile and a conventional, commercially available polymer hydrogel network, which could serve as a potential smart material for drug delivery.</p>\u0000 </div>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":"47 16","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148429502","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sasan Moradi, Osman Konuray, Javier G. Valverde-Bastidas, Xavier Fernández-Francos, Xavier Ramis
{"title":"Reprocessable Disulfide-Based Vitrimers with Adhesive Properties","authors":"Sasan Moradi, Osman Konuray, Javier G. Valverde-Bastidas, Xavier Fernández-Francos, Xavier Ramis","doi":"10.1002/marc.70353","DOIUrl":"10.1002/marc.70353","url":null,"abstract":"<p>A family of disulfide (S–S) containing thiol–vinyl–epoxy dynamic networks are presented. The networks are obtained through a dual-curing mechanism wherein a photoinduced thiol–ene reaction at room temperature is followed by a thermally activated, tertiary amine catalyzed thiol–epoxy curing stage, enabling controlled network development. Cured materials show reprocessability thanks to heat-triggered disulfide bond exchange. The influence of catalyst structure on curing behavior, thermomechanical properties, stress relaxation, and this reprocessability is systematically investigated. These solvent-free materials with a unique ternary composition exhibit efficient network rearrangement and successful thermal reprocessing, demonstrating their potential as sustainable materials.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":"47 16","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/marc.70353","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148381366","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Li Yang, Pengmin Shi, Bo Yang, Jing Yang, Jian Zhao, Chuanzhu Gao
{"title":"Research Progress of Platinum-Based Anticancer Drugs in Combination with Macrocyclic Drug Delivery System","authors":"Li Yang, Pengmin Shi, Bo Yang, Jing Yang, Jian Zhao, Chuanzhu Gao","doi":"10.1002/marc.70355","DOIUrl":"10.1002/marc.70355","url":null,"abstract":"<div>\u0000 \u0000 <p>Platinum-based anticancer drugs represent a cornerstone of clinical cancer chemotherapy, yet their clinical application is severely limited by inherent drug resistance and systemic toxic side effects. Macrocyclic compounds, such as cucurbiturils, cyclodextrins, crown ethers, calixarenes and pillararenes, possess unique cavity structures and excellent molecular recognition capabilities, offering promising strategies for optimizing the chemotherapeutic efficacy of platinum-based drugs. This review summarizes the latest research progress in supramolecular systems constructed from macrocyclic compounds and platinum-based drugs via host–guest interactions. It focuses on the roles of such supramolecular complexes in improving drug solubility, stability, tumor targeting, and controlled release performance, as well as their potential to overcome drug resistance and reduce toxicity. Furthermore, the applications of functionalized macrocyclic compounds in intelligent drug delivery and combination therapy are discussed, and future directions, including novel macrocyclic carriers, multifunctional nanoplatforms, and combination with immunotherapy and gene therapy, are prospected. This review aims to provide useful references for the development of precise and personalized applications of platinum-based drugs in cancer therapy.</p>\u0000 </div>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":"47 16","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148417119","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Fei Chen, Linlin Zhao, Yingyu Zhang, Chuandong Qin, Yingying Liu
{"title":"Proteoglycan-Mimetic Bottle-Brush Polymer Brushes for Osteoarthritis Therapy: Lubrication Enhancement and Multifunctional Disease Modulation","authors":"Fei Chen, Linlin Zhao, Yingyu Zhang, Chuandong Qin, Yingying Liu","doi":"10.1002/marc.70358","DOIUrl":"10.1002/marc.70358","url":null,"abstract":"<div>\u0000 \u0000 <p>Lubrication is essential for maintaining joint health and enabling smooth articulation. In healthy joints, natural lubricants such as proteoglycans endow articular cartilage with an exceptionally low coefficient of friction. Notably, proteoglycans possess a characteristic bottle-brush architecture that generates robust hydration layers at the cartilage surface, thereby facilitating effective lubrication. In osteoarthritis (OA), degradation of extracellular matrix components, depletion of proteoglycans, and increased friction and wear at inflamed joint interfaces collectively accelerate disease progression. Therefore, restoring joint lubrication has emerged as a promising strategy to reduce friction-induced damage and delay OA progression. In recent years, extensive efforts have been devoted to developing biomimetic lubricants, particularly proteoglycan-mimetic polymer brushes inspired by natural proteoglycan architectures. These systems are designed to replicate the bottle-brush architecture and hydration lubrication mechanism of native proteoglycans. In this review, we summarize the fundamental lubrication mechanisms of articular cartilage, with emphasis on boundary and hydration lubrication mediated by proteoglycans, and discuss the design principles and representative material systems of proteoglycan-mimetic polymer brushes. By linking native lubrication mechanisms with biomimetic brush design and translational considerations, this review highlights proteoglycan-inspired polymer brushes as promising disease-modifying candidates for OA treatment.</p>\u0000 </div>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":"47 16","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148417108","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"CO2-Responsive Dual-Charge-Switchable Membranes for Protein Foulant Cleaning","authors":"Niloofar Zamanian, Yue Zhao","doi":"10.1002/marc.70357","DOIUrl":"10.1002/marc.70357","url":null,"abstract":"<p>Known CO<sub>2</sub>-responsive membranes exhibit single-charge-switching (neutral–cationic), which limits their ability to regulate electrostatic interactions with oppositely charged foulants in membrane cleaning. Herein, CO<sub>2</sub>-responsive poly(ether sulfone) (PES) ultrafiltration membranes with a dual charge-switchable surface are prepared by adding an amphoteric diblock copolymer additive to PES via the nonsolvent-induced phase separation (NIPS) method. By tuning the isoelectric point (IEP) of the copolymer additive to around 5, the membrane surface charge reversibly switches between positive and negative states under alternating CO<sub>2</sub> bubbling, lowering pH to ∼4 (below IEP), and N<sub>2</sub> bubbling, raising pH to ∼7 (above IEP). ATR-FTIR and water contact angle analyses indicate that increasing the copolymer content in the casting solution increases the amount of amphoteric chains on the membrane surface. Using bovine serum albumin (BSA) as a model foulant with a similar IEP, protein-fouled membranes are effectively cleaned with water when CO<sub>2</sub> and N<sub>2</sub> are alternately bubbled due to the constantly existing electrostatic repulsion between the membrane and protein. The gas-triggered cleaning efficiency is comparable to conventional acid/alkaline cleaning and remains stable over repeated fouling-cleaning cycles, underscoring the potential of this approach for environmentally friendly and chemical-free membrane cleaning.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":"47 16","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/marc.70357","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148429494","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shijun Long, Han Ren, Qingbiao Cao, Yiwan Huang, Xuefeng Li
{"title":"Strain-Sensitive Double-Network Organogel With Strong Adhesion for Movement Monitoring","authors":"Shijun Long, Han Ren, Qingbiao Cao, Yiwan Huang, Xuefeng Li","doi":"10.1002/marc.70366","DOIUrl":"10.1002/marc.70366","url":null,"abstract":"<div>\u0000 \u0000 <p>Conductive organogels, as a class of soft materials, have demonstrated great application potential in the field of flexible electronics. However, they often suffer from several drawbacks, including low transparency, poor mechanical properties, low sensitivity, and weak adhesion. In this work, a highly adhesive and stretchable double-network organogel is constructed by the interpenetration of a nanofiber network self-assembled from 1,3:2,4-dibenzylidene sorbitol (DBS) and tough polyacrylamide (PAM) chains in glycerol. Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) is incorporated to modulate the ionic conductivity of the gel, forming multiple ionic and intermolecular interactions within the gel network. The DBS/PAM-Li conductive organogel exhibits high and durable adhesion strength to various substrates, as well as good optical transparency (92% transmittance at a thickness of 1.45 mm). Furthermore, when assembled into a strain sensor, the DBS/PAM-Li organogel exhibits a high gauge factor of 8.72, a fast response time of 133 ms, and the capability to detect both small (with a low detection limit of 0.25% strain) and large deformations. This material can be used to monitor human motion, expanding the applications of flexible gel materials in the field of wearable electronics.</p>\u0000 </div>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":"47 16","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148443568","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chenfei Xu, Zheqi Li, Jianping He, Shichao You, Yang He, Wangmeng Hou, Jiaoning Tang, Yi Shi, Yongming Chen
{"title":"High-Yield Synthesis of Molecular Bottlebrushes With Block Copolymer Side Chains by the Copper Superoxido Complex Enabled ATRP via a Grafting-From Approach","authors":"Chenfei Xu, Zheqi Li, Jianping He, Shichao You, Yang He, Wangmeng Hou, Jiaoning Tang, Yi Shi, Yongming Chen","doi":"10.1002/marc.70352","DOIUrl":"10.1002/marc.70352","url":null,"abstract":"<div>\u0000 \u0000 <p>The combination of controlled radical polymerization technique and grafting-from strategy has been widely employed for synthesizing molecular bottlebrushes (MBBs); however, this approach always meets challenges at the high monomer conversion stage due to the intra- and inter-molecular cross-linking caused by inevitable radical-radical coupling. Herein, we report the utilization of copper superoxido complex-enabled atom transfer radical polymerization (ATRP) for the grafting-from synthesis of MBBs with well-defined architectures in high yield. Owing to the use of a low concentration of copper catalyst, the intra- and inter-molecular cross-linking is greatly minimized, leading to the precise synthesis of MBBs with narrow distribution, near-quantitative monomer conversion, and worm-like architecture. Under this premise, we further evaluate the feasibility of this approach for the one-pot preparation of MBBs with block copolymer (BCP) side chains as well as dye-loaded functional MBBs. Overall, this work proposes an efficient grafting-from approach for MBBs with precise architectures and unprecedentedly high yield, which can be utilized for multicomponent MBBs with diverse functions.</p>\u0000 </div>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":"47 16","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148373947","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}