{"title":"Electrochromic Triarylamine-Based Polyamides and Their Application in Intelligent Color-Varying Windows.","authors":"Xiangwen Wu, Dongwen Zou, Dongwei Zhang, Imran Murtaza, Meimei Zhu, Yanan Zhu, Yaowu He, Hong Meng","doi":"10.1002/marc.202401071","DOIUrl":"https://doi.org/10.1002/marc.202401071","url":null,"abstract":"<p><p>Polyamide (PA) is a classical conductive polymer that has become a research hotspot in the field of electrochromism due to its easily modifiable structures, tunable absorption spectra, and superior film-forming properties. Herein, four PAs are successfully synthesized, including C4-PA, C7-PA, C9-PA, and TP-PA, to study their thermal, photophysical, electrochemical, and electrochromic properties. All four PAs exhibit good thermal stability and excellent solubility in the volatile solvent THF. The fluorescence intensity follows the trend of C9-PA > C7-PA > C4-PA = TP-PA. Notably, C4-PA, C7-PA, C9-PA, and TP-PA-based electrochromic devices (ECDs) exhibit reversible electrochromism from transparent to pure black, blue-black, blue-green, and turquoise colors, respectively. Especially, C4-PA demonstrate high contrast (70%), fast response time (coloring time of 3.1 s and fading time of 2.7 s), and pure black color (the lowest contrast < 1%) in the colored state ((a*, b*) = (-1.82, -0.39) in ECD. However, C7-PA, C9-PA, and TP-PA based ECDs exhibit longer response times and only demonstrate the lowest contrast of 6%, 22%, and 36% in the colored state, respectively. To achieve high contrast and fast response times, it is suggested to use shorter carbon chains in the design of PA-based EC materials.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e2401071"},"PeriodicalIF":4.2,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144075061","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":"Synthetic Glycopolymers in Tumor Immunotherapy.","authors":"Yuru Chen, Jiaxin Song, Xiangqian Chen, Gaojian Chen","doi":"10.1002/marc.202401089","DOIUrl":"https://doi.org/10.1002/marc.202401089","url":null,"abstract":"<p><p>Glycopolymers, as an emerging immunomodulatory material, exhibit considerable promise in the field of tumor immunotherapy. Compared to native saccharides, they offer significant advantages, including enhanced immune activity, controllable structure and sequence, elevated stability, and high purity. By mimicking the multivalency of native sugar chains, glycopolymers significantly enhance their interactions with receptors, a phenomenon known as the \"glycocluster effect.\" Glycopolymers are capable of modulating immune cell functions, inhibiting tumor immune evasion, and reconfiguring the tumor microenvironment. This review provides a comprehensive overview of recent advancements in the application of glycopolymers, protein-glycopolymer conjugates, glycopolymer-based micro/nanoparticles, and glycopolymer-engineered cells in tumor immunotherapy. These glycopolymer-based materials enhance antitumor immune responses by specifically interacting with immune cell surface receptors, significantly improving the precision and efficacy of immunotherapy, and providing valuable insights for the development of innovative therapeutic strategies in cancer treatment.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e2401089"},"PeriodicalIF":4.2,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144075069","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":"Recent Progress in Developing Conjugated Polymer-Microorganism Biohybrids for Semi-Artificial Photosynthetic Energy Conversion.","authors":"Jie Zhou, Jun Cheng, Hangxun Xu","doi":"10.1002/marc.202500234","DOIUrl":"https://doi.org/10.1002/marc.202500234","url":null,"abstract":"<p><p>Semi-artificial photosynthesis, which merges the precision of synthetic materials with the catalytic versatility of biological systems, offers a transformative route to solar-driven chemical fuel production and sustainable energy conversion. Conjugated polymers, with their high molar absorption coefficients, broad spectral responsiveness, and tunable semiconducting properties, have emerged as key components in advancing semi-artificial photosynthetic biohybrids. Their capacity for targeted surface modification not only facilitates enhanced interfacing with biological catalysts but also optimizes charge transfer across the bio-synthetic interface. This review traces the evolution of conjugated polymer-based biohybrids, highlighting recent advancements that extend microbial light harvesting, support cellular resilience against environmental stress, and optimize charge transfer via precise structure-activity relationships. Furthermore, this review explores the challenges and opportunities in this field, offering a roadmap for the design of durable and high-performance biohybrid systems. Through the integration of conjugated polymers and microorganisms, this review outlines a strategic approach for solar-driven chemical energy conversion, paving the way for eco-friendly energy solutions.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e2500234"},"PeriodicalIF":4.2,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144075067","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}
Anna Mauri, Pascal Kiefer, Wolfgang Wenzel, Mariana Kozlowska
{"title":"Photoreactivity of Norrish Type Photoinitiators for 3D Laser Printing via First Principles Calculations.","authors":"Anna Mauri, Pascal Kiefer, Wolfgang Wenzel, Mariana Kozlowska","doi":"10.1002/marc.202500231","DOIUrl":"https://doi.org/10.1002/marc.202500231","url":null,"abstract":"<p><p>In the rapidly evolving field of 3D laser nanoprinting, achieving high resolution and high printing speed relies heavily on the effective use and design of sensitive photoinitiators. However, their photoreactivity is hitherto not well described. This study investigates the photochemical and photophysical characteristics of a high-performing Norrish Type II photoinitiator (2E,6E)-2,6-bis(4-(dibutylamino)benzylidene)-4-methylcyclohexanone, known as BBK, as well as commonly employed Norrish Type I photoinitiators: Irgacure 651, Irgacure 369. Using quantum mechanical calculations, multiphoton absorption, the formation of the excited states, and the radical formation mechanisms most probably involved in the initiation of free radical polymerization are examined. Their relation to the observations during 3D printing experiments is discussed, aiming to uncover the molecular foundations behind varying performances of photoinitiators. Bond dissociation energies and energy barriers for bond cleavage of Irgacure photoinitiators are demonstrated to confirm radical formation in the lowest triplet state, whereas this pathway is shown to be less probable for BBK. The radical polymerization initiation upon absorption from the triplet manifold of BBK and reactions with pentaerythritol triacrylate (PETA) monomers are described. Deactivation pathway via reversible intersystem crossing, as well as the photoactivation characteristics, are compared with relation to the 7-diethylamino-3-thenoylcoumarin (DETC) photoinitiator.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e2500231"},"PeriodicalIF":4.2,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144075063","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}
Jinyan Wu, Yunhui Wen, Xin Li, Weixiao Feng, Yang Yang, Shaowei Shi
{"title":"Membrane Emulsification of Ellipsoidal Droplets and Particles.","authors":"Jinyan Wu, Yunhui Wen, Xin Li, Weixiao Feng, Yang Yang, Shaowei Shi","doi":"10.1002/marc.202500265","DOIUrl":"https://doi.org/10.1002/marc.202500265","url":null,"abstract":"<p><p>Polymer ellipsoids are typically accessible through a two-step fabrication procedure, involving the synthesis of spherical particles followed by thermal stretching, a time-consuming and complicated process. In this study, a straightforward method is presented for preparing polymer ellipsoids via emulsion polymerization, utilizing the jamming of nanoparticle surfactants at the oil-water interface and the membrane emulsification technique. The size and shape of polymer ellipsoids can be precisely controlled by adjusting the interfacial activity of nanoparticle surfactants and emulsification parameters. This approach provides a scalable and cost-effective pathway for the production of polymer ellipsoids, with potential applications across various fields.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e2500265"},"PeriodicalIF":4.2,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143961874","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}
Danila M de Carvalho, Maarit H Lahtinen, Patrícia Figueiredo, Sami P Hirvonen, Sami Hietala, Kirsi S Mikkonen
{"title":"Modulating the Spontaneous Adsorption of Lignin Nanoparticle at Oil-Water Interfaces.","authors":"Danila M de Carvalho, Maarit H Lahtinen, Patrícia Figueiredo, Sami P Hirvonen, Sami Hietala, Kirsi S Mikkonen","doi":"10.1002/marc.202500120","DOIUrl":"https://doi.org/10.1002/marc.202500120","url":null,"abstract":"<p><p>The performance of (nano)particles in the stabilization of Pickering emulsions depends on their physicochemical features. Therefore, synthetic particles are commonly applied in Pickering stabilization, despite the environmental issues their use raises. Recently, lignin nanoparticles (LNPs) derived from industrial side streams have been investigated as biobased alternatives to replace synthetic stabilizers. Having a well-defined surface chemistry, monodisperse morphology, and a unique core-shell composition, LNPs are hypothesized to show diverse functionality and adsorption capacity at the oil-water interface that affects the long-term Pickering emulsion stability. To gain an understanding on the effect of various colloidal parameters, i.e., type of LNP, type of oil-water system, pH, LNP concentration, and ionic strength, on the adsorption LNPs at hexadecane-water and rapeseed oil-water interfaces, a fundamental study using dynamic interfacial tension analysis is performed. Condition optimized for Pickering stabilization is defined and applied for preparing emulsions. Findings indicated that LNPs adsorbed spontaneously at oil-water interfaces, which is a unique trait compared to known particles' adsorption, usually requiring the application of high forces. LNP adsorption at interfaces is affected by conditions of colloidal parameters, with increasing of pH ensuring the greatest LNP adsorption. Emulsions stabilized with LNPs at the optimized pH 8.0 remained stable after subsequent adjustment to pH 5.0.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e2500120"},"PeriodicalIF":4.2,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143951612","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}
Longxing Niu, Shengjia Chen, Xiangshu Guo, Yanfei Feng, Rong Wang
{"title":"Physically Cross-Linked Silk Fibroin Hydrogel with Rapid Sol-Gel Transition and Enhanced Mechanical Performance.","authors":"Longxing Niu, Shengjia Chen, Xiangshu Guo, Yanfei Feng, Rong Wang","doi":"10.1002/marc.202401016","DOIUrl":"https://doi.org/10.1002/marc.202401016","url":null,"abstract":"<p><p>It remains a great challenge to fabricate physically cross-linked silk fibroin (SF) hydrogels with rapid gelation and robust mechanical properties. In this study, a novel SF hydrogel is obtained by synergistically modulating the SF molecular weight (MW) and the freeze-inducing process, avoiding the use of any exterior additives. First, the effects of MW on the self-assembly behaviors of SF are investigated under physiological temperature. The results demonstrate that high MW SF derived from papain degumming (PSF) facilitates the sol-gel transition with increasing β-sheet content, and contributed to the construction of the hierarchical micro-nanofiber structure. Subsequently, cryo-concentration treatment is applied to further accelerate the gelation process. The resultant PSF (F-PSF) exhibits rapid sol-gel transition (within 1 h), a high compressive modulus (54.2 ± 3.7 kPa), and a high storage modulus (up to 247.9 kPa), which are superior to traditional physically cross-linked SF hydrogels. The relatively low β-sheet content and dense structure endow the F-PSF hydrogels with excellent mechanical flexibility, physiological environmental stability, and long-term mechanical stability. In vitro cellular experiments show that F-PSF hydrogels are beneficial to cell proliferation and spreading. These attractive features enable the physically cross-linked SF hydrogels to be promising for tissue engineering and regenerative medicine.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e2401016"},"PeriodicalIF":4.2,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143952468","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}
Hayden Robertson, Joshua D Willott, Andrew R J Nelson, Stuart W Prescott, Erica J Wanless, Grant B Webber
{"title":"Solvent and Ion-Mediated Behavior of a Thermoresponsive Brush: Specific Ion Effects in Methanol-Water Electrolytes.","authors":"Hayden Robertson, Joshua D Willott, Andrew R J Nelson, Stuart W Prescott, Erica J Wanless, Grant B Webber","doi":"10.1002/marc.202500093","DOIUrl":"https://doi.org/10.1002/marc.202500093","url":null,"abstract":"<p><p>In this study, specific ion effects are explored in methanol-water mixtures, which play a critical role in a diverse range of applications, including protein solubilization and supercapacitors. Spectroscopic ellipsometry and neutron reflectometry are employed to investigate the solvent- and ion-mediated behavior of a poly(N-isopropylacrylamide) (PNIPAM) brush, a well-known thermoresponsive polymer. In the absence of ions and at low methanol mole fractions (x<sub>M</sub>), PNIPAM displays lower critical solution temperature (LCST) type behavior, with the thermotransition temperature decreasing as x<sub>M</sub> increased. Upon further increasing x<sub>M</sub>, a cononsolvency region is identified at approximately x<sub>M</sub> = 0.15, beyond which re-entrant swelling is observed in conjunction with a suppressed thermoresponse. In the presence of x<sub>M</sub> = 0.10 electrolytes, the observed specific ion effects adhere to a forward Hofmeister series. Strongly solvated ions, such as Cl<sup>-</sup> and Br<sup>-</sup>, decrease the LCST of the brush. In contrast, poorly solvated ions, such as SCN<sup>-</sup> and I<sup>-</sup>, lead to more swollen brush profiles and an increase in the LCST. We hypothesize that the stability of water-methanol clusters plays a crucial role in governing polymer solvation, providing insights into the fundamental interactions within mixed solvent systems. Moreover, a theoretical ion that does not impact the swelling or structure of a PNIPAM brush is proposed.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e2500093"},"PeriodicalIF":4.2,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143959730","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}
Allison Vercasson, Cristina Prieto, Sébastien Gaucel, Nathalie Gontard, Valérie Guillard, Hélène Angellier-Coussy, Jose M Lagaron
{"title":"Electrospun Polybutylene Succinate Coatings for Sustainable Cardboard Packaging: Structure-Property Relationships.","authors":"Allison Vercasson, Cristina Prieto, Sébastien Gaucel, Nathalie Gontard, Valérie Guillard, Hélène Angellier-Coussy, Jose M Lagaron","doi":"10.1002/marc.202500048","DOIUrl":"https://doi.org/10.1002/marc.202500048","url":null,"abstract":"<p><p>Producing thin biopolymer-coated paper and cardboard is essential for a large range of applications, such as food packaging, as it allows to maintain flexibility while reducing the environmental impact and enhancing barrier properties. This study investigates electrospinning to generate polybutylene succinate (PBS)-coated cardboards with contrasted structures (i.e., different thicknesses of the individual layers). Four contrasted structures of PBS-coated cardboards are produced, presenting low polymer thickness remaining on top of the substrate (10 to 25 µm) but differing in the thickness of their characteristic layers (including the impregnated layer). The effect of the electrospinning parameters (deposition time, method (direct vs indirect)) and annealing parameters on polymer-coated cardboards' structures are investigated. The annealing pressure only reduced the coated cardboard thickness, while the electrospinning method influenced the overall structure by affecting both the thickness of the impregnated layer and of the remaining layer of cardboard. The mechanical properties tested by tensile test are maintained or enhanced after coating while oxygen barrier properties are largely enhanced for some samples. Decreasing the impregnated layer thickness resulted in a Young's modulus increase (+3 to +23%) and a decrease in stress at break (-40 to -70%), highlighting the impact of polymer-coated cardboards's structures on their mechanical properties.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e2500048"},"PeriodicalIF":4.2,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143957884","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}
Badr Jismy, Pablo Durand, Jasmine P Jacob, Fanny Richard, Olivier Boyron, Benoit Heinrich, Bruno Schmaltz, Patrick Lévêque, Olivier Bardagot, Nicolas Leclerc
{"title":"Versatile Direct (Hetero)Arylation Polymerization of Electro-Deficient Unsubstituted Thiazolo[5,4-d]Thiazole: A Tool to Lower the LUMO Level.","authors":"Badr Jismy, Pablo Durand, Jasmine P Jacob, Fanny Richard, Olivier Boyron, Benoit Heinrich, Bruno Schmaltz, Patrick Lévêque, Olivier Bardagot, Nicolas Leclerc","doi":"10.1002/marc.202500243","DOIUrl":"https://doi.org/10.1002/marc.202500243","url":null,"abstract":"<p><p>A series of novel conjugated semiconducting polymers based on the unsubstituted thiazolo[5,4-d]thiazole (TzTz) unit is synthesized using atom-economic and environmentally friendly direct (hetero)arylation polymerization (DHAP). The versatility of the proposed polymerization conditions, employing a non-chlorinated and moderately toxic solvent and cooperative palladium/copper bimetallic catalytic system, is demonstrated through the use of seven comonomers with varying electron-withdrawing strength: 2,2'-bithiophene (BT), 6,7-difluoroquinoxaline (Qx), thieno[3,4-c]pyrrole-4,6(5H)-dione (TPD), 5,6-difluorobenzo[c][1,2,5]thiadiazole (BTD), isoindigo (IID), para-azaquinodimethane (AQM) and 2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (DPP). The resulting TzTz-based copolymers exhibit optical bandgaps between 1.5 and 2.0 eV with HOMO/LUMO energy levels spanning from -5.2/-3.3 eV to -5.4/-3.9 eV. They all show satisfactory thermal stability for electronic applications (Td = 300-360 °C). Notably, TzTz-based copolymers are observed they generally exhibit improved backbone planarity and deeper LUMO levels than their thiophene derivatives. A synthesis tool to finely lower the LUMO levels of next-generation A-A' copolymers in view of increasing the performance and air-stability of doped organic electronics is believed to be provided by this work.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e2500243"},"PeriodicalIF":4.2,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143955597","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}