{"title":"Nonconventional Luminescent Polymers: Emission Regulation and Applications","authors":"Xiang Chen, Yining Sun, Wang Zhang Yuan","doi":"10.1002/macp.202400401","DOIUrl":"https://doi.org/10.1002/macp.202400401","url":null,"abstract":"<p>Nonconventional luminescent polymers have gained significant interest due to their outstanding water solubility, biocompatibility, solution-processability, and scalability. Unlike traditional aromatic luminogens with extended π-conjugation, their distinctive photophysical properties arise from a mechanism known as clustering-triggered emission (CTE). CTE involves the clustering of electron-rich subunits, leading to enhanced electron delocalization and conformational rigidification, ultimately boosting photoluminescence (PL). Despite substantial advancements, challenges remain in optimizing the emission efficiency and PL tunability of these polymers. This review delves into the CTE mechanism, examining recent advances in regulating the photophysical properties of nonconventional luminescent polymers. The aim is to uncover universal principles and underlying mechanisms across diverse systems, providing a theoretical foundation for further development and potential applications of these materials in fields such as bioimaging, sensing, and optoelectronics.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 5","pages":""},"PeriodicalIF":2.5,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/macp.202400401","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555150","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}
Jana Klueppelberg, Ulrich A. Handge, Markus Thommes, Judith Winck
{"title":"Influence of Carbon Dioxide on the Phase Behavior of Pharmaceutical Drug-Polymer Dispersions","authors":"Jana Klueppelberg, Ulrich A. Handge, Markus Thommes, Judith Winck","doi":"10.1002/macp.202400359","DOIUrl":"https://doi.org/10.1002/macp.202400359","url":null,"abstract":"<p>The formulation as amorphous solid dispersion (ASD) addresses recent challenges in the oral administration of poorly-soluble drugs by embedding them in highly-soluble carrier polymers. In this context, utilizing CO<sub>2</sub> as a processing agent is an innovative strategy to facilitate the dissolution of the drug in the polymer at comparatively low temperatures without the use of any organic solvents. Within this study, the influence of CO<sub>2</sub> on the phase behavior of ASD formulations is investigated. Therefore, high-pressure differential scanning calorimetry is applied to evaluate the dissolution of the drugs in the polymers and the glass transition temperatures under CO<sub>2</sub> of four formulations containing the drugs acetaminophen and itraconazole as well as the polymers Soluplus and vinylpyrrolidone/vinyl acetate copolymer. The glass transition temperatures of the ASD formulations decrease with CO<sub>2</sub> fraction dissolved in the polymer. The extent of <i>T<sub>g</sub></i> reduction is related to the spatial structure and intermolecular interactions of the polymers. Furthermore, the sorption of CO<sub>2</sub> accelerates the diffusion of the drugs in the plasticized polymers. However, phase separation is observed in some formulations under CO<sub>2</sub> loading which has an impact on the stability of the ASD and has to be considered in process design.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 2","pages":""},"PeriodicalIF":2.5,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/macp.202400359","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143120671","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}
Anuja Kulkarni, Mahesh Loku Yaddehige, Daniel J. Cooke, Christine M. Hamadani, Alex S. Flynt, Eden E. L. Tanner, Emily L. Que, Davita L. Watkins
{"title":"Multifunctional Fluorinated Copolymer Nanoparticles via a Cationic Dendritic-Based Macromolecular RAFT-CTA","authors":"Anuja Kulkarni, Mahesh Loku Yaddehige, Daniel J. Cooke, Christine M. Hamadani, Alex S. Flynt, Eden E. L. Tanner, Emily L. Que, Davita L. Watkins","doi":"10.1002/macp.202400354","DOIUrl":"https://doi.org/10.1002/macp.202400354","url":null,"abstract":"<p>As the field of theranostics expands, an imminent need arises for multifaceted polymer-based nanotechnologies for clinical application. In this work, reversible addition-fragmentation chain transfer (RAFT) aqueous emulsion polymerization is used to form <sup>19</sup>F-containing amphiphilic hybrid block copolymers (HBCs). Employing a cationic dendritic macromolecular chain transfer agent (mCTA), polymer frameworks comprised of chemically distinctive blocks of differing architectures (i.e., dendritic and grafted/linear) are strategically designed and synthesized. In aqueous media, self-assembled polymer nanoparticles (PNPs) are formed. Their physicochemical properties and their potential as biomaterials for MRI applications are assessed. By showcasing a newly established mCTA and using these resulting PNPs as imaging probes, the work expands the design space of RAFT polymerization in biomedical research, paving the way for the development of more effective and versatile MRI imaging tools.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 2","pages":""},"PeriodicalIF":2.5,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143120673","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":"Boosting Phosphorescent Performance by a Three-Component Doping of Coumarin Derivatives, Metal Salts Into Polyvinyl Alcohol","authors":"Hua Feng, Zhongmin Su, Fushun Liang","doi":"10.1002/macp.202400406","DOIUrl":"https://doi.org/10.1002/macp.202400406","url":null,"abstract":"<p>Multi-component doping has become an effective way to achieve efficient room-temperature phosphorescence. In this paper, green phosphorescence emission from coumarin derivatives, i.e., coumarin-3-carboxylic acid (CCA) and coumarin-3-carboxylic ester (CEt) are activated by doping them into polyvinyl alcohol (PVA) matrix (two component doping). Then, a series of metal salts (Ca<sup>2+</sup>, Al<sup>3+</sup>, Mn<sup>2+</sup>, and Zn<sup>2+</sup>) are added as the third component to construct three-component doping system, with the aim to further improve the phosphorescence properties of the polymer films. Among them, CaCl<sub>2</sub> can significantly increase the emission intensity (9.2 times), prolong the phosphorescence lifetime (up to 361 ms), and increase the phosphorescence quantum yield (from 1.02% to 9.19%). The results indicated that RTP emission can be activated by inhibiting the non-radiative transition of coumarin derivatives embedded in the rigid PVA matrix. RTP performance can be further enhanced relying on the coordination effect between the coumarin guests and the metal salts. This study provides a simple and effective three-component doping method for boosting polymer film-based phosphorescence performance.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 4","pages":""},"PeriodicalIF":2.5,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143456078","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":"Search for Thiol-Protected Gold Clusters Doped with Different Elements Using Dendrimers","authors":"Hisanori Muramatsu, Tetsuya Kambe, Takamasa Tsukamoto, Takane Imaoka, Kimihisa Yamamoto","doi":"10.1002/macp.202400334","DOIUrl":"https://doi.org/10.1002/macp.202400334","url":null,"abstract":"<p>The synthesis of thiol-protected Au clusters MAu<sub>24</sub>(SR)<sub>18</sub> containing different elements (M: different element, SR: thiol ligand) generally requires various steps. Therefore, the finding of a new <i>M</i>Au<sub>24</sub>(SR)<sub>18</sub> cluster is not easy though it is necessary to take a great deal of effort to consider the synthesis. In this study, <i>M</i>Au<sub>24</sub>(SR)<sub>18</sub> is searched for and attempted cluster synthesis using a dendrimer-template method. It is also found that this method may be useful for exploring and discovering new clusters.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 4","pages":""},"PeriodicalIF":2.5,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143456077","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}
Mario Estrada, Takeo Suga, Ignacio Moreno-Villoslada
{"title":"Solvent Effects in the Synthesis of Highly Charged Foams of Poly(4-styrenesulfonate-co-glycidylmethacrylate) for Efficient Adsorption of Methylene Blue Enhanced by Aromatic–Aromatic Interactions","authors":"Mario Estrada, Takeo Suga, Ignacio Moreno-Villoslada","doi":"10.1002/macp.202400381","DOIUrl":"https://doi.org/10.1002/macp.202400381","url":null,"abstract":"<p>Water-resistant porous solid foams expressing a high amount of benzene sulfonate moieties have been fabricated to enhance the adsorption of cationic aromatic pollutants from wastewaters by aromatic–aromatic interactions. Copolymers of sodium 4-styrene sulfonate (NaSS) and glycidyl methacrylate (GMA) have been obtained and submitted to thermal treatment at 270 °C for 15 min. The influence of the solvent used in the copolymerization step on foamability and foam stability, when formed, has been studied. The use of water as cosolvent with <i>N</i>,<i>N</i>-dimethyl formamide (DMF) inhibited foam formation. The use of DMF or DMF/dimethyl sulfoxide (DMSO) = 1:1 as solvents allowed the expansion of copolymers, but the resulting foams are unstable in water, forming hydrogels. However, using DMF/DMSO = 5:1 as solvent, stable water-resistant foams showing NaSS molar fractions of 43, 57, and 68% are obtained, showing high maximum capacity of 244, 435 and 588 mg g<sup>−1</sup> and outstanding pseudo-second-order kinetic constants of 1.78, 4.49 and 5.64 g mg<sup>−1</sup> min<sup>−1</sup> toward adsorption of methylene blue (MB), between 2 and 5 orders-of-magnitude higher than referenced adsorbents. This is due to the highly exposed benzene sulfonate active sites / adsorbent mass ratio that induces strong aromatic–aromatic interactions with the cationic aromatic dye.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 4","pages":""},"PeriodicalIF":2.5,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143455928","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}
Yoshitomo Furushima, Akihiko Toda, Masaru Nakada, Subaru Konishi, Hirotaka Shioji, Yuki Yoshida, E. Billur Sevinis Ozbulut, Mehmet Dinc, Benedikt Keitel, Boris Mizaikoff, Masatoshi Ohkura
{"title":"Pre-Treatment Effects on Isothermal Crystallization Behavior of Isotactic Polypropylene","authors":"Yoshitomo Furushima, Akihiko Toda, Masaru Nakada, Subaru Konishi, Hirotaka Shioji, Yuki Yoshida, E. Billur Sevinis Ozbulut, Mehmet Dinc, Benedikt Keitel, Boris Mizaikoff, Masatoshi Ohkura","doi":"10.1002/macp.202400376","DOIUrl":"https://doi.org/10.1002/macp.202400376","url":null,"abstract":"<p>The effects of crystal nuclei or crystallization on the isothermal crystallization behavior of isotactic polypropylene homopolymer are examined using fast scanning calorimetry (FSC) and wide-angle X-ray scattering (WAXD). During crystalline nucleation below the glass transition temperature as described by Tammann's two-stage nucleation approach, an increased crystallization rate is observed, regardless of whether the mesophase structures formed in the low-temperature region or α-crystals formed in the high-temperature region. No increase in isothermal crystallization rate is detected following self-nucleation just above the melting point. Additionally, the influence of the pre-existing crystals on the subsequent crystallization behavior is investigated by combining crystallization time and temperature profiles, whereby crystallization at high temperatures is followed by slight crystallization at low temperatures, and in reverse order. Surprisingly, it is confirmed that the presence of pre-existing crystals do not affect the subsequent crystallization rate. The crystallization rate of iPP is influenced only by low-temperature pre-annealing that enhances the pre-nucleation.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 3","pages":""},"PeriodicalIF":2.5,"publicationDate":"2024-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143253130","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":"Red-shifted and Dramatically Enhanced Fluorescence Emissions from Sodium Alginate-Polyethyleneimine Polyelectrolyte Complexes","authors":"Yunqi Shi, Xiaomi Zhang, Yunhao Bai, Wendi Xie, Junwen Deng, Huiliang Wang","doi":"10.1002/macp.202400411","DOIUrl":"https://doi.org/10.1002/macp.202400411","url":null,"abstract":"<p>The development of nontraditional luminogens (NTLs) with enhanced and red-shifted emissions has attracted rapidly increasing attention. Here, a new strategy is provided for preparing NTLs with enhanced and red-shifted emissions based on polyelectrolyte complexes (PECs) formed by an anionic polyelectrolyte sodium alginate (SA) and a cationic polyelectrolyte polyethyleneimine (PEI). The direct blending of SA and PEI leads to enhanced emissions but no red-shift in emission wavelengths in the solution and dried films. After soaking in HCl solutions (pH≤2.0), SA-PEI PEC films are obtained. The SA-PEI PEC wet and dried films show maximum emissions at ≈ 370 and 470 nm as well as a significantly red-shifted emission at 550 nm. The SA-PEI PEC dried films maintain high quantum yields under a wide range of excitation wavelengths and the quantum yield is as high as 29.4% under 470 nm excitation. Furthermore, the films emit nearly white fluorescence under the irradiation of 290 or 370 nm UV light. The enhanced and red-shifted emission is attributed to the formation of the compact luminescent clusters with more extended through-space conjugation and rigidified conformations through ionic bonding between NH<sup>+</sup> groups and COO<sup>−</sup> groups and the enhanced hydrogen bonding.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"226 5","pages":""},"PeriodicalIF":2.5,"publicationDate":"2024-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555122","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}