Macromolecular Chemistry and Physics最新文献

{"title":"Bimodal Magneto‐Luminescent Response of Lanthanide Metallopolymers for Distinguishing of Phosphates in Aqueous Solutions","authors":"Alexey P. Dovzhenko, Vadim A. Vasilyev, Timur A. Kornev, Alexander A. Chinarev, Alexey V. Nizovtsev, Rustem R. Zairov, Oleg G. Sinyashin, Asiya R. Mustafina","doi":"10.1002/macp.202400253","DOIUrl":"https://doi.org/10.1002/macp.202400253","url":null,"abstract":"Linear <jats:italic>N</jats:italic>‐substituted polyacrylamides bearing tricarboxylic moieties pendant to the backbone are synthesized, and coordinative binding approach is developed to convert them into Gd<jats:sup>3+</jats:sup>/Eu<jats:sup>3+</jats:sup>‐metallopolymers. Inner‐sphere coordination of the lanthanide ions with the pendant chelating moieties, together with their outer‐sphere stabilization by the randomly coiled backbone, are the reasons for peculiar water proton relaxation and luminescence properties of the metallopolymers obtained. Indeed, for Gd<jats:sup>3+</jats:sup>‐metallopolymer, the values of longitudinal and transverse relaxivity (r<jats:sub>1</jats:sub> and r<jats:sub>2</jats:sub>) are 50 and 60 m<jats:sc>m</jats:sc><jats:sup>−1</jats:sup>·s<jats:sup>−1</jats:sup>, respectively, while for the Eu<jats:sup>3+</jats:sup>‐counterpart, Eu<jats:sup>3+</jats:sup>‐centered luminescence is significantly raised compared to Eu<jats:sup>3+</jats:sup> aquaions. Coil‐like conformation of the metallopolymer molecules undergoes a swelling at pH values above 5.0 as evidenced by transmission electron microscopy TEM and dynamic light scattering (DLS) data, which is followed by the changes in the Eu<jats:sup>3+</jats:sup>‐centered luminescence and r<jats:sub>1(2)</jats:sub>‐values of Gd<jats:sup>3+</jats:sup>/Eu<jats:sup>3+</jats:sup>‐metallopolymers. The phosphates additives (adenosine monophosphoric acid (AMP), adenosine diphosphoric acid (ADP), HPO<jats:sub>4</jats:sub><jats:sup>2−</jats:sup> and adenosine triphosphoric acid (ATP) induce well detectable changes in both water proton relaxation and luminescence of Gd<jats:sup>3+</jats:sup>/Eu<jats:sup>3+</jats:sup>‐metallopolymers. The luminescent changes distinguish AMP from the other phosphates, while the changes in water proton relaxation are greater for HPO<jats:sub>4</jats:sub><jats:sup>2−</jats:sup> and ATP compared to AMP and ADP. This study explains this by interplay of the effects associated with the formation of ternary phosphate‐lanthanide‐polymer complexes and stripping of lanthanide ions from the polymer molecules.","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"2 1","pages":""},"PeriodicalIF":2.5,"publicationDate":"2024-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142177863","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":"Orientation of Chitin Nanofibers Dispersed in a Thermoplastic Polymer Matrix Through Dry Thermal Stretching","authors":"Tetsuya Katsuragawa,&nbsp;Morihiko Yokoi,&nbsp;Ryosuke Kobe,&nbsp;Yoshikuni Teramoto","doi":"10.1002/macp.202400150","DOIUrl":"10.1002/macp.202400150","url":null,"abstract":"<p>Nanostructures derived from structural polysaccharides, such as cellulose and chitin, are notable for their sustainability, lightweight properties, and superior mechanical attributes. The macroscopic performance of these materials largely depends on the orientation of nanostructures. This study explores the preferential orientation of chitinous nanofibers (NFs) within a thermoplastic polymer matrix (PM) comprising poly(<i>N</i>-vinylpyrrolidone) and glycerol, achieved through dry thermal stretching techniques. Altering the PM composition enables the modulation of the system's glass transition temperature (<i>T</i>_g). Chitin NFs are effectively dispersed within the PM, with their orientation enhanced by stretching at temperatures ≈30 °C above the <i>T</i>_g of the composites, resulting in an elongation at rupture (<i>ε</i>) of 105%. Under similar temperature conditions, composites with chitosan NFs show strong interactions with the PM, hindering the stretching process (<i>ε</i> = 10%). In contrast, composites with acetylated chitin NFs demonstrate increased stretchability (<i>ε</i> = 170%) but have insufficient interactions to stabilize their orientation. These interactions, identified as hydrogen bonds through FTIR, vary significantly based on the functional groups present on the NF surfaces. This variation is supported by DSC and dynamic mechanical analysis. Oriented ChNFs hold potential for bioactive applications.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"225 20","pages":""},"PeriodicalIF":2.5,"publicationDate":"2024-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142223494","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":"Nanophase Segregation Drives Heterogeneous Dynamics in Amphiphilic PLMA-b-POEGMA Block-Copolymers with Densely Grafted Architecture","authors":"Achilleas Pipertzis,&nbsp;Athanasios Skandalis,&nbsp;Stergios Pispas,&nbsp;George Floudas","doi":"10.1002/macp.202400180","DOIUrl":"10.1002/macp.202400180","url":null,"abstract":"<p>The self-assembly and dynamics of amphiphilic diblock copolymers composed of densely grafted poly(oligo ethylene glycol methacrylate) (POEGMA) and poly(lauryl methacrylate) (PLMA) by means of calorimetry, small-angle X-ray scattering (SAXS), and dielectric spectroscopy are investigated. It is reported that the inherent immiscibility between the parent homopolymers, combined with the increased molar mass, results in strong segregation, maintained up to elevated temperatures (i.e.<i>, T</i> = 423 K). SAXS reveals that well-separated POEGMA and PLMA domains self-assemble into spheres with bicontinuous cubic packing and in lamellar nanostructure in copolymers with respective compositions of 16 and 52 wt.% PLMA. This strong segregation enables the weak crystallization/melting of the short ethylene glycol chains. Additionally, molecular dynamics are investigated through isothermal dielectric and calorimetry measurements. The segmental dynamics (i.e.<i>, T</i>_g-related) of POEGMA and PLMA closely resemble that found in respective homopolymers, implying heterogeneous dynamics. In the glassy state, the local motions of the POEGMA side chains predominantly govern the observed secondary processes in the copolymers. The results on the <i>heterogeneous dynamics</i> in the current <i>amphiphilic</i> diblock copolymers with the densely grafted architecture are compared and contrasted with copolymers having a bottle–brush architecture lacking the amphiphilic nature.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"225 19","pages":""},"PeriodicalIF":2.5,"publicationDate":"2024-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/macp.202400180","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142177864","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":"Narrowly Distributed Conjugated Polymers Synthesized Through Acid-Catalyzed Aldol Polycondensations in Nanoreactors","authors":"Huayu Shi,&nbsp;Xiaohua Huang,&nbsp;Donglai Tian,&nbsp;Huanghao Pan,&nbsp;Aiguo Hu","doi":"10.1002/macp.202400203","DOIUrl":"10.1002/macp.202400203","url":null,"abstract":"<p>Conjugated polymers are typically synthesized through transition metal-mediated coupling reactions, which are often costly and have significant environmental impacts. Aldol condensation represents a more cost-effective and sustainable synthetic technique for developing next-generation organic functional materials. However, controlling the molecular weight and distribution of the resulting polymers remains challenging due to the uncontrollable step-growth polymerization mechanism of aldol polycondensations. To this end, by selectively anchoring sulfonic acids inside the mesochannels of SBA-15, the aldol polycondensation is exclusively confined within the pores. Experimental results demonstrate that this nanoreactor, by providing a spatially confined reaction environment, aids in controlling the progression of the polymerization and the growth of polymer chains, thereby achieving good control over polymer molecular weight and distribution, giving linear conjugated polymers and soluble conjugated polymeric nanoparticles with polymer dispersity down to 1.31.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"225 21","pages":""},"PeriodicalIF":2.5,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142177865","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":"Temperature-Responsive Anisotropic Bilayer Hydrogel Actuators with Adaptive Shape Transformation for Enhanced Actuation and Smart Sensor Applications","authors":"Mulenga Kalulu,&nbsp;Christopher Mwanza,&nbsp;Onesmus Munyati,&nbsp;Jun Hu,&nbsp;Shephrah O. Ogungbesan,&nbsp;Guodong Fu","doi":"10.1002/macp.202400235","DOIUrl":"10.1002/macp.202400235","url":null,"abstract":"<p>Anisotropic bilayer hydrogel actuators are high-performance materials engineered to exhibit unique and programmable mechanical properties, including varying stiffness and directional bending capabilities, by integrating two hydrogel layers with distinct responses to stimuli. However, programming and constructing these bilayer hydrogels remains challenging due to their lack of mechanical robustness, rapid responsiveness, and dual-actuation capabilities, which hinder their practical applications and further development. Hence, developing a double-actuating bilayer hydrogel with a temperature-responsive and auxiliary layer could address these challenges. Herein, an anisotropic hydrogel actuator is developed using a simple and economical casting method, in which a unique multiasymmetric bilayer structure locked by an interfacial is fabricated. The as-prepared hydrogels demonstrate exceptional temperature-responsive bending abilities, achieving a 360 °C angle in just 8 s, and exhibit adaptive, complex shape transformation capabilities tailored to specific needs (e.g., two dimensional (2D) letters, leaves, flower, and butterfly hydrogel). Furthermore, the hydrogels possess excellent shape memory, mechanical strength, and conductivity. Additionally, gripper and humidity alarm prototypes made from the hydrogel are also successfully developed, illustrating that this approach opens new avenues for designing and producing smart hydrogels with practical applications in sensors, smart humidity alarms, and on-demand smart grippers and actuators.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"225 22","pages":""},"PeriodicalIF":2.5,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142177866","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":"Characterization and Properties of Polylactic Acid/Cottonseed Protein Bioplastics","authors":"Yanli Jiang,&nbsp;Peng Yan,&nbsp;Lingwei Mai,&nbsp;Hai Liu,&nbsp;Xiaobo Liu,&nbsp;Chufen Yang,&nbsp;Jinping Peng,&nbsp;Hangbo Yue","doi":"10.1002/macp.202400191","DOIUrl":"10.1002/macp.202400191","url":null,"abstract":"<p>In this study, polylactic acid (PLA) is compounded with cottonseed protein concentrate (CPC) by melt blending under the compatibilization of maleic anhydride (MA), and then hot-pressed to prepare PLA/CPC composite bioplastics. The attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy showed that high temperature and compatibilizer induced the protein secondary structure to transition. CPC can be used as a heterogeneous PLA nucleating agent, effectively accelerating PLA crystallization, which is characterized by polarization optical microscopy (POM), synchrotron radiation wide-angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC). The highest crystallinity of the PLA/CPC10 composite is 8.9% higher than that of neat PLA. The unfolding of the protein secondary structure is likely to promote an orderly arrangement of PLA crystals, showing strong binding forces between them. Moreover, the CPC/PLA interfacial compatibility is improved by the addition of a small amount of maleic anhydride. The increased crystallinity and interfacial compatibility contribute to the improved mechanical properties, water resistance, and thermal stability of the bioplastics. Environmentally friendly plastic handicrafts (e.g., commemorative emblems, flower pots, ornaments, etc.) can be fabricated using these biocomposites for future value-added applications.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"225 20","pages":""},"PeriodicalIF":2.5,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142177867","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":"Monodomain Liquid Crystal Elastomers Composed of Main-Chain Type Nematic Polyester Bonded to Rubbery Segments at Both Ends","authors":"Ryoji Suzuki,&nbsp;Yuki Ikeda,&nbsp;Suzune Ito,&nbsp;Mikihiro Hayashi,&nbsp;Naruki Kurokawa,&nbsp;Masatoshi Tokita","doi":"10.1002/macp.202400214","DOIUrl":"10.1002/macp.202400214","url":null,"abstract":"<p>Monodomain liquid crystal elastomers (LCEs) are prepared using liquid crystal block copolymers (LCBCPs) comprised of a nematic liquid crystal (NLC) main-chain polyester linked to cross-linkable polymethacrylate (PMA) at both ends. LCBCPs at a PMA weight fraction of ≈30% are doped with a tetra-thiol compound, stretched in one direction, and then illuminated by UV light, yielding LCBCPs that formed microlamellae consisting of alternate stacking crosslinked PMA blocks and NLC polyester blocks. The LC director lay along the stretching direction (SD). Raising the temperature to the NLC isotropization temperature, the crosslinked LCBCP strips fixed at one end contracted reversibly by a factor of 1.2–1.4 along the SD, deforming the microlamellae. The strips fixed at both ends increased the tensile stress to ≈200 kPa while maintaining the microlamellae undeformed. Regardless of strip fixation at one or both ends, the NLC decreased the orientational order. The contraction amounts and the tensile stress of strips are well associated with decreased NLC orientational order.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"225 21","pages":""},"PeriodicalIF":2.5,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141928909","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":"Barrier Properties of Biodegradable Aliphatic–Aromatic Copolyesters (PBXT Series)","authors":"Lizheng Wang,&nbsp;Zhu Tu,&nbsp;Jiaming Liang,&nbsp;Zhiyong Wei","doi":"10.1002/macp.202470030","DOIUrl":"10.1002/macp.202470030","url":null,"abstract":"<p><b>Front Cover</b>: The free volume within materials is crucial for gas adsorption and diffusion. Size and distribution of internal fractional free volume significantly impact barrier performance. This study innovatively combines experiments and theoretical calculations to corroborate that methylene group growth in aliphatic units leads to decreased crystallinity, elevated free volume fraction, enhanced segment mobility, ultimately diminishing barrier properties. More details can be found in article 2400051 by Zhiyong Wei and co-workers.\u0000\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"225 15","pages":""},"PeriodicalIF":2.5,"publicationDate":"2024-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/macp.202470030","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141934488","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":"Masthead: Macromol. Chem. Phys. 15/2024","authors":"","doi":"10.1002/macp.202470031","DOIUrl":"10.1002/macp.202470031","url":null,"abstract":"","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"225 15","pages":""},"PeriodicalIF":2.5,"publicationDate":"2024-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/macp.202470031","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141934485","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":"Compositional Influence of Cross-linked Polyion Hydrogels from Poly(L-Lysine) and Poly(L-Glutamic Acid) on Their Properties for Potential Skin Applications","authors":"Rafał Bielas,&nbsp;Sarinj Fattah,&nbsp;Łukasz Mielańczyk,&nbsp;German Pozdeev,&nbsp;Sally-Ann Cryan,&nbsp;Andreas Heise","doi":"10.1002/macp.202400201","DOIUrl":"10.1002/macp.202400201","url":null,"abstract":"<p>Chemically cross-linked hydrogels are synthesized from a set of protected L-lysine and L-glutamic acid containing homo and copolypetides. Cross-linking of the linear copolypeptides is achieved through the incorporation of L-tryptophan and its reaction with hexamethylene bis(triazolinodione). Upon deprotection, hydrogels with oppositely charged polypeptides of different L-lysine and L-glutamic acid composition form pH-dependent polyion complexes through electrostatic interaction. The obtained networks show distinct pH-dependent differences in their water swelling and rheological properties. Hydrogels at pH 4 display higher strengths compared to pH 8 and their rheological properties scale with L-lysine/L-glutamic acid ratio. At pH 8 results suggests that ionic interactions and presumably secondary structure effects have a significant impact on the hydrogel properties. This is further evident from the influence of the copolypetide structures, random versus block copolypeptides, used in the cross-linked hydrogel. None of the hydrogel shows any significant cytotoxicity against skin cell lines.</p>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"225 20","pages":""},"PeriodicalIF":2.5,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/macp.202400201","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141934484","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}