{"title":"Thiourea-Based Polymers as Functional Materials: Synthetic Challenges, Supramolecular Design, and Emerging Applications.","authors":"Ros Azlinawati Ramli, Bohari Mohd Yamin","doi":"10.1002/marc.70298","DOIUrl":"https://doi.org/10.1002/marc.70298","url":null,"abstract":"<p><p>Thiourea-based polymers are an emerging class of functional materials characterized by strong directional hydrogen bonding, tunable polarity, and versatile supramolecular interactions. These features enable materials with adaptive mechanical behavior, molecular recognition capability, and environmental responsiveness. Despite their promise, the development of thiourea-functionalized polymers remains limited by persistent synthetic challenges, including poor solubility, competing side reactions, restricted architectural control, and difficulties in scalable processing. In addition, existing literature has largely focused on small-molecule thiourea systems, leaving polymer-level structure-property relationships insufficiently explored. This review critically examines recent advances in the design, synthesis, and functional applications of thiourea-based polymers, emphasizing structure-defining synthetic constraints, supramolecular organization, and materials performance. Strategies for incorporating thiourea motifs into polymer backbones, side chains, and cross-linked networks are discussed in relation to their influence on hydrogen-bonding networks, mechanical integrity, and environmental stability. Emerging applications in optoelectronic, separation, self-healing, and biomedical materials are highlighted, and key challenges and opportunities for sustainable design and scalable fabrication are identified.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e70298"},"PeriodicalIF":4.3,"publicationDate":"2026-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147831587","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}
Lin Du, Chao Rong, Xinan Ma, Bowei Zhang, Fu-Zhen Xuan
{"title":"Ultrastrong and Conductive MXene Films Enabled by Hydrogen and Lonic Bonds.","authors":"Lin Du, Chao Rong, Xinan Ma, Bowei Zhang, Fu-Zhen Xuan","doi":"10.1002/marc.70301","DOIUrl":"https://doi.org/10.1002/marc.70301","url":null,"abstract":"<p><p>Two-dimensional MXene materials are promising for flexible electronics due to their high conductivity and mechanical strength, yet their films often suffer from poor mechanical robustness and a trade-off between conductivity and mechanical performance. This study introduces a bioinspired \"sequential bridging\" strategy to fabricate PDA/MXene/SA/Ca<sup>2+</sup> films (PMSC) via synergistic polydopamine (PDA) surface modification, sodium alginate (SA) hydrogen-bond crosslinking, and Ca<sup>2+</sup> ionic bridging. The film exhibits exceptional comprehensive properties, achieving a tensile strength of 256.64 MPa, a Young's modulus of 8.06 GPa, and a toughness of 8.39 MJ/m<sup>3</sup>, which are 7.8, 3.2, and 10.9 times higher than those of pure MXene film, respectively, while retaining a high electrical conductivity of 1700.91 S/cm. Systematic characterization analysis identified multiple enhancement mechanisms, including PDA surface modification, SA induced hydrogen-bond crosslinking, and Ca<sup>2+</sup> mediated ionic-bond energy dissipation. This multi-crosslinking approach overcomes the limitations of single network strategies, offering a scalable route to high-performance flexible electronics.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e70301"},"PeriodicalIF":4.3,"publicationDate":"2026-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147831623","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":"Vulcanization on Polymer Film Surfaces With Elemental Sulfur.","authors":"Shang-Yu Tsai, Yue-Sheng Lai, Ying-Ling Liu","doi":"10.1002/marc.70300","DOIUrl":"https://doi.org/10.1002/marc.70300","url":null,"abstract":"<p><p>Elemental sulfur has been widely utilized as a sustainable feedstock for the synthesis of sulfur-modified and sulfur-rich polymers. This study aims to extend the sulfur chemistry to surfaces vulcanization of polymer films. The process involves the infiltration of molten sulfur into the polymer film from surface, followed by in situ vulcanization. The surface vulcanization yields a vulcanized polymer layer on the top portion of the polymer film, resulting in an asymmetric structure. To demonstrate this synthetic route, a mainchain polybenzoxazine (PBz) film is employed. The resulting surface vulcanized and crosslinked PBz films are characterized using a scanning electron microscopy equipped with an energy-dispersive X-ray, an X-ray photoelectron spectroscopy, and a Fourier transform infrared spectroscopy. The surface vulcanization strategy establishes a platform for the development of preparation of a new class of sulfur-containing materials.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e70300"},"PeriodicalIF":4.3,"publicationDate":"2026-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147831608","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":"Electrospinning Achieving Supramolecular Cyclodextrin-Polyaniline Layered Fabric for Expanding Conductive Performance of Flexible Electrode.","authors":"Xu Zhang, Xiao-Yong Yu, Chen Zhang, Zhuo Lei, Xu Pan, Xue-Jian Zhang, Ying-Ming Zhang, Yong Chen, Yu Liu","doi":"10.1002/marc.70299","DOIUrl":"https://doi.org/10.1002/marc.70299","url":null,"abstract":"<p><p>Supercapacitor electrode materials are increasingly indispensable for energy storage in wearable and flexible electronics. Herein, the electrospun assembled supramolecular nanofibrous P-PC@CD was fabricated from polyacrylonitrile (PAN), camphorsulfonic acid-doped polyaniline (PANI-CSA), and various cyclodextrins (CDs) and their derivatives. Subsequently, an in situ polymerized polyaniline (PANI) layer was introduced, forming a low-resistance layered electrode P-PC@CD@PANI. Among these, β-CD significantly enhances electrochemical performance, delivering an areal capacitance 353 times higher than that of PAN + PANI mixed fibers prior to polymerization. The P-PC@β-CD@PANI electrode also exhibits excellent flexibility, maintaining 97.0% capacitance after 100 cycles of repeated 180° bending and 94.0% after 1000 cycles. Moreover, after 24 h storage at 75% relative humidity and room temperature, as well as at 37°C, capacitance retention remains at 97.3% and 98.7%, respectively. The device can stably power a light-emitting diode (LED). This work provides a high-performance supramolecular flexible electrode and offers new insights into electrospinning-based supramolecular assembly for electrochemical applications.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e70299"},"PeriodicalIF":4.3,"publicationDate":"2026-05-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147808934","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":"A Programmable Hydrogel Platform with Tunable Phase Transition Temperature and Mechanical Properties for Information Encryption and Soft Actuation.","authors":"Hongyan Liu, Yingxin Guan, Aochen Yang, Weiwei Li, Debin Wang, Huijuan Zhang","doi":"10.1002/marc.70294","DOIUrl":"https://doi.org/10.1002/marc.70294","url":null,"abstract":"<p><p>It is still challenging to enable a precise and editable hydrogel design by quantitatively relating the molecular composition and hierarchy with the properties and functions. Herein, a programmable hydrogel system was successfully produced by copolymerizing N-isopropylacrylamide (NIPAM) with N, N'-dimethylacrylamide (DMAA) and acrylamide (AM), combined with the physical entanglement effect of hydroxypropyl cellulose (HPC). The incorporation of DMAA increased the hydrophilicity of the network, enabling precise adjustment of the lower critical solution temperature (LCST) within the range of 34°C∼49°C. The compressive modulus decreased from 18.3 to 12.3 kPa with increasing DMAA content, while the incorporation of AM significantly improved the compressive modulus from 16.2 to 24.0 kPa and reduced the mechanical loss rate to only 3.6% after 100 compressive cycles. The application of the hydrogel in information encryption was demonstrated by utilizing its quick and reversible transparent-opaque transition to achieve temperature-dependent quick response (QR) code encryption and dynamic password display. A soft actuator capable of rapid thermally induced bending was developed by constructing a bilayered poly(N-isopropylacrylamide)-co-poly(N,N-dimethylacrylamide)/poly(N-isopropylacrylamide)-co-poly(N,N-dimethylacrylamide-co-acrylamide) (P(NIPAM-co-DMAA)/P(NIPAM-co-DMAA-co-AM))structure with a modulus gradient. Finite element simulation confirmed the exponential relationship between the bending curvature and the interlayer modulus difference. This study provides a simple and rational strategy for designing a smart hydrogel platform.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e70294"},"PeriodicalIF":4.3,"publicationDate":"2026-05-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147808951","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}
Xinhaoran Hu, Chenyu Sun, Yang Hu, Li Yang, Cencong Wang, Quanling Yang, Chuanxi Xiong, Zhuqun Shi
{"title":"Transparent Ionic Skin: Minimal [EMIM]Cl Enhances Nanocellulose Hydrogel Conductivity for Superior Wearable Sensing.","authors":"Xinhaoran Hu, Chenyu Sun, Yang Hu, Li Yang, Cencong Wang, Quanling Yang, Chuanxi Xiong, Zhuqun Shi","doi":"10.1002/marc.70238","DOIUrl":"10.1002/marc.70238","url":null,"abstract":"<p><p>Growing focus on health and quality of life is driving increasing demand for skin-like wearable sensors in human motion monitoring and healthcare. Unlike traditional e-skin, ionic skin utilizes a polymer network scaffold with mobile ions, effectively overcoming the issue of poor dispersion of conductive fillers in polymer matrices. As an ionic liquid with facile synthesis and low cost, 1-ethyl-3-methylimidazolium chloride ([EMIM]Cl) forms strong interactions with both polymers and water molecules. Cellulose is a natural polymeric material with advantages such as low cost, environmental friendliness, and renewability. 2,2,6,6-Tetramethylpiperidinyl-1-oxyl (TEMPO)-oxidized cellulose nanofibrils (TOCNs) exhibit excellent biocompatibility. In this work, the TOCN-[EMIM]Cl ionic hydrogel was formed by mixing a TOCN dispersion with [EMIM]Cl ionic liquid, followed by Ca<sup>2</sup> <sup>+</sup> cross-linking. By adjusting the [EMIM]Cl content from 0 to 3 wt.%, the conductivity of the TOCN-[EMIM]Cl hydrogel increased from 9.43 × 10<sup>-5</sup> to 4.13 × 10<sup>-4</sup> S cm<sup>-1</sup>. The obtained ionic skin exhibits high transparency, with a sensitivity of 2.11 kPa<sup>-1</sup>, rapid response/recovery times (< 50 ms), and excellent cyclic stability (> 5000 cycles). Stable and distinguishable signal outputs have been achieved for human joint movements (wrist, elbow, and knee), demonstrating significant potential in flexible wearable sensors and health monitoring applications.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e70238"},"PeriodicalIF":4.3,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146199727","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":"Molecular Engineering in Benzobisazole-Linked Polymers: Unveiling the Linkage Effect on Proton Conductivity and Transport Pathways.","authors":"Khalid Mehmood, Jianing Wang, Runhao Huang, Qiang Ma, Junyi Han, Iram Arif, Tao Zhang","doi":"10.1002/marc.70245","DOIUrl":"10.1002/marc.70245","url":null,"abstract":"<p><p>Benzobisazole-linked polymers hold potential as proton-exchange electrolytes; however, their structural rigidity and restricted chain dynamics limit their practical applications. This study investigates the linkage motif effect in three acid-doped, vinylene-bridged zwitterionic benzobisazole-based polymers: benzobisoxazole (PA@v-ZLP-NO), benzobisthiazole (PA@v-ZLP-NS), and benzobisimidazole (PA@v-ZLP-NN), synthesized via aldol polycondensation, which exhibit distinct thermal and morphological properties to overcome this limitation. Interestingly, although PA@v-ZLP-NN is less electron-deficient than PA@v-ZLP-NO and PA@v-ZLP-NS, it shows superior proton conductivity of 2.0 × 10<sup>-2</sup> S/cm at 80°C and 98% relative humidity, which is about 1.3 times higher than PA@v-ZLP-NS and 5.1 times higher than PA@v-ZLP-NO under identical conditions. The improved performance of PA@v-ZLP-NN stems from the presence of NH groups, which enable additional sites for hydrogen bonding in synergy with SO<sub>3</sub> <sup>-</sup> ions, self-protonation, and dynamic proton transfer via acid-base interactions, thereby forming efficient proton-transfer pathways. Their low activation energy (0.11-0.25 eV) supports Grotthuss-type proton transport, highlighting their potential as superior proton-exchange electrolytes.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e70245"},"PeriodicalIF":4.3,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147288847","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}
Gopalakrishnan T, P Rajeswari, S Purushothaman, P R Kalyana Chakravarthy, Deepa Simon
{"title":"Progress and Perspectives in Poly(meth) Acrylate/Acrylamide Derived Biosensing Technologies.","authors":"Gopalakrishnan T, P Rajeswari, S Purushothaman, P R Kalyana Chakravarthy, Deepa Simon","doi":"10.1002/marc.202500862","DOIUrl":"10.1002/marc.202500862","url":null,"abstract":"<p><p>Poly(meth)acrylate and vinyl-based polymers have emerged as highly versatile functional materials for next-generation sensing technologies. Their tunable architectures, chemical stability, and ability to incorporate stimuli-responsive, fluorescent, or bioactive moieties enable precise detection in biomedical, environmental, and chemical systems. Recent advancements in controlled radical polymerization, including ATRP, RAFT, NMP methods, have significantly improved structural control, allowing the fabrication of well-defined polymeric sensors with high sensitivity and selectivity. Methacrylate derived hydrogels, copolymers, and block architectures support applications ranging from molecular recognition and targeted drug delivery to imaging, electrochemical sensing, and pollutant detection. Incorporation of functional groups such as peptides, metal-binding ligands, and imaging agents has enabled advanced biosensors capable of detecting biomarkers, cancer cells, ions, explosives, and reactive species. Progress in multimodal imaging, fluorescent tagging, and molecular imprinting further expands their applicability. This review summarizes major developments in polymer synthesis and sensor design, highlights structure property function relationships, and outlines emerging opportunities for miniaturized, high-performance polymer-based sensing platforms. The insights provided aim to guide future innovation in smart, adaptive, and multifunctional polymeric sensors.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00862"},"PeriodicalIF":4.3,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146256828","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":"Multicomponent Open-Shell Donor-Acceptor Diradical Polymers: Design, Synthesis, and Characterization.","authors":"Xinyue Zeng, Yuan Li","doi":"10.1002/marc.70242","DOIUrl":"10.1002/marc.70242","url":null,"abstract":"<p><p>Organic semiconductive polymers can be classified into unary, binary, and ternary ones in previous work. The binary polymers based on the donor-acceptor architecture have witnessed significant progress of this field. Conjugated polymers with four or more components have been rarely reported. Exemplified by a ten-component system, we report multi-component polymers P10-FTTPA, P10-FTBT, and P10-FTBBTA. The chemical structure and photothermal conversion performance of them were studied using <sup>1</sup>H NMR, UV-vis-NIR absorption, cyclic voltammetry, electron spin resonance, and photothermal performance testing. The open-shell diradical character increased as the molecular bandgap decreased. P10-FTBBT exhibited reduced fluorescence quantum yield, enhanced open-shell diradical character and photothermal conversion efficiency. Especially, the open-shell diradical of P10-FTTPA, P10-FTBT was attributed to our aggregation-induced radical concept and quinoid-diradical mechanism with the loss of aromaticity and double bonds since 2017 (J. Phys. Chem. C., 2017, 121, 8579-8588), which is different from the recovery of aromaticity mechanism of BBT-diradical (J. Phys. Org. Chem. 2011, 24, 821-832), which is from the outdated Chichibabin diradical since 1907.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e70242"},"PeriodicalIF":4.3,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147589027","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":"A Multi-Responsive Film from Polymerizable Cholesteric Liquid Crystal Microcapsules for Advanced Anti-Counterfeiting.","authors":"Longxiang He, Jiaxin Huo, Baohua Yuan, Yue Feng, Yingjie Shi, Cheng Zou, Meina Yu, Yuanwei Chen, Yanzi Gao, Huai Yang","doi":"10.1002/marc.202500954","DOIUrl":"10.1002/marc.202500954","url":null,"abstract":"<p><p>Cholesteric liquid crystals (CLCs) can be encapsulated within liquid crystal microcapsules (CLCMs) via ultrasonic emulsification, and this microcapsule structure offers advantages in liquid crystal (LC) orientation control and stability. However, CLCMs still face challenges in multiple stimulus responsiveness. In this study, polymerizable LC monomers are introduced as the core filler of CLCMs and polymerized under UV irradiation to form polymer networks. As a result, the structural color of the film changes, and the patterned coloration of the final prepared film gradually disappears upon exposure to sunlight. Furthermore, with the temperature increasing, the pattern of the film first appears and then disappears, ultimately rendering the film completely transparent. Overall, the results show that the CLCM films incorporating polymerizable LC core exhibit multi-stimuli responsiveness to light, heat, and humidity, demonstrating the potential of polymerizable CLCMs for advanced applications such as anti-counterfeiting technologies and sensors.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00954"},"PeriodicalIF":4.3,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462435","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}