Pub Date : 2026-03-17DOI: 10.1021/acs.macromol.5c02687
Yuxing Wang, Honor Westlake, Sebastien Rochat
Their unique combination of high surface area and solvent processability has made polymers of intrinsic microporosity (PIMs) useful in numerous separation processes in the gas or liquid phase. Recently, their optical properties have gained attention. Here, we characterize the optoelectronic properties of two representative PIMs composed of planar polyaromatic systems linked by spiro-centers, alongside their monomer and dimer analogs, using density functional theory and experimental methods. Computations reveal that the orthogonal geometry of the spiro-linked segments produces nearly degenerate frontier orbitals and split excitation transitions in the dimer models, suggesting enhanced electron delocalization by spiroconjugation. Experimental optical spectra and fluorescence quenching experiments support these findings, with polymers displaying extended electron delocalization compared to monomers and dimers, akin to phenomena observed in conjugated polymers. Overall, our results provide a new understanding of PIMs and highlight their potential for applications in chemical sensing, photocatalysis, or light harvesting, where they remain underexplored.
{"title":"Theoretical and Experimental Studies of the Optoelectronic Properties of Polymers of Intrinsic Microporosity","authors":"Yuxing Wang, Honor Westlake, Sebastien Rochat","doi":"10.1021/acs.macromol.5c02687","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c02687","url":null,"abstract":"Their unique combination of high surface area and solvent processability has made polymers of intrinsic microporosity (PIMs) useful in numerous separation processes in the gas or liquid phase. Recently, their optical properties have gained attention. Here, we characterize the optoelectronic properties of two representative PIMs composed of planar polyaromatic systems linked by spiro-centers, alongside their monomer and dimer analogs, using density functional theory and experimental methods. Computations reveal that the orthogonal geometry of the spiro-linked segments produces nearly degenerate frontier orbitals and split excitation transitions in the dimer models, suggesting enhanced electron delocalization by spiroconjugation. Experimental optical spectra and fluorescence quenching experiments support these findings, with polymers displaying extended electron delocalization compared to monomers and dimers, akin to phenomena observed in conjugated polymers. Overall, our results provide a new understanding of PIMs and highlight their potential for applications in chemical sensing, photocatalysis, or light harvesting, where they remain underexplored.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"24 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478804","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-17DOI: 10.1021/acs.macromol.6c00262
Shijing Yan, Yingying Han, Meng Wu, Zhiwei Yang, Hui You, Weihua Xu, Jun Du, Cailiu Yin
The development of sustainable electronics demands materials that combine high performance with designed degradability, yet achieving this balance remains a challenge. Here, we demonstrate that systematically engineering the soft-segment molecular weight in fully degradable, biobased polyurethanes (PUs) unlocks a suite of tunable properties for high-performance pressure sensing. By varying poly(butylene adipate) (PBA) diol molecular weight in networks containing isosorbide and acid-cleavable hexahydrotriazine, we establish that longer PBA chains enhance soft-segment crystallinity and elongation (up to 978%), while an optimal intermediate molecular weight (2000 g/mol) yields the highest tensile strength (25.7 MPa) and excellent biocompatibility. This optimized PU exhibits robust shape-memory behavior (Rf > 98%) and undergoes controlled dual degradation: enzymatic (up to 50% mass loss in 6 weeks) and complete acid-triggered dissolution, enabling quantitative recovery of conductive carbon black filler. A microstructured composite sensor fabricated from this material achieves high sensitivity (15.32 kPa–1) with fast response/recovery and successfully monitors human motion. This work establishes molecular design rules for degradable PUs and provides a viable pathway toward sustainable, high-performance flexible electronics.
{"title":"From Soft-Segment Engineering to Multifunctional Performance: A Study on Fully Degradable Poly(butylene adipate)-Based Polyurethanes","authors":"Shijing Yan, Yingying Han, Meng Wu, Zhiwei Yang, Hui You, Weihua Xu, Jun Du, Cailiu Yin","doi":"10.1021/acs.macromol.6c00262","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c00262","url":null,"abstract":"The development of sustainable electronics demands materials that combine high performance with designed degradability, yet achieving this balance remains a challenge. Here, we demonstrate that systematically engineering the soft-segment molecular weight in fully degradable, biobased polyurethanes (PUs) unlocks a suite of tunable properties for high-performance pressure sensing. By varying poly(butylene adipate) (PBA) diol molecular weight in networks containing isosorbide and acid-cleavable hexahydrotriazine, we establish that longer PBA chains enhance soft-segment crystallinity and elongation (up to 978%), while an optimal intermediate molecular weight (2000 g/mol) yields the highest tensile strength (25.7 MPa) and excellent biocompatibility. This optimized PU exhibits robust shape-memory behavior (<i>R</i><sub>f</sub> > 98%) and undergoes controlled dual degradation: enzymatic (up to 50% mass loss in 6 weeks) and complete acid-triggered dissolution, enabling quantitative recovery of conductive carbon black filler. A microstructured composite sensor fabricated from this material achieves high sensitivity (15.32 kPa<sup>–1</sup>) with fast response/recovery and successfully monitors human motion. This work establishes molecular design rules for degradable PUs and provides a viable pathway toward sustainable, high-performance flexible electronics.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"11 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466121","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-17DOI: 10.1021/acs.macromol.6c00178
Jiaojiao Qin, Jun Wen, Xiaoyan Tang
Poly[(thio)ester amide]s (PEAs and PTEAs) represent an important class of functional polymers, uniquely integrating the exceptional degradability of poly(thio)esters with the superior mechanical properties of polyamides. Ring-opening copolymerization (ROCOP) of aziridine and cyclic (thio)anhydride stands out as a highly efficient method for constructing alternating PEAs and PTEAs; however, existing ROCOP systems largely rely on N-alkyl or N-sulfonyl aziridines, which precludes interchain hydrogen bonding. Here, we report a protected–deprotected strategy based on N-tert-butyloxycarbonyl aziridine (AzBoc) as a N–H aziridine precursor, enabling the postpolymerization deprotection to restore the amide N–H groups and introduce hydrogen-bonding interactions. Efficient ROCOP of AzBoc with various cyclic (thio)anhydrides, such as phthalic thioanhydride (PTA), phthalic anhydride (PA), diphenic anhydride (DPA), and camphoric anhydride (CA), was achieved using either organic bases (e.g., phosphazene) or nucleophilic salts (e.g., tetrabutyl ammonium chloride), affording cyclic PEAs and PTEAs with well-defined alternating structures and high molar masses. Structure–property relationship studies demonstrate that Boc deprotection, sulfur atom incorporation, and anhydride ring size collectively govern the thermal properties of the resulting polymers, underscoring the critical role of amide hydrogen bonding in modulating material performance.
{"title":"Controlled Synthesis of Hydrogen-Bonded Poly[(thio)ester amide]s via Deprotection of Alternating Copolymers from N-tert-Butyloxycarbonyl Aziridine and Cyclic Anhydrides","authors":"Jiaojiao Qin, Jun Wen, Xiaoyan Tang","doi":"10.1021/acs.macromol.6c00178","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c00178","url":null,"abstract":"Poly[(thio)ester amide]s (PEAs and PTEAs) represent an important class of functional polymers, uniquely integrating the exceptional degradability of poly(thio)esters with the superior mechanical properties of polyamides. Ring-opening copolymerization (ROCOP) of aziridine and cyclic (thio)anhydride stands out as a highly efficient method for constructing alternating PEAs and PTEAs; however, existing ROCOP systems largely rely on <i>N</i>-alkyl or <i>N</i>-sulfonyl aziridines, which precludes interchain hydrogen bonding. Here, we report a protected–deprotected strategy based on <i>N</i>-<i>tert</i>-butyloxycarbonyl aziridine (Az<sup>Boc</sup>) as a <i>N</i>–H aziridine precursor, enabling the postpolymerization deprotection to restore the amide <i>N</i>–H groups and introduce hydrogen-bonding interactions. Efficient ROCOP of Az<sup>Boc</sup> with various cyclic (thio)anhydrides, such as phthalic thioanhydride (PTA), phthalic anhydride (PA), diphenic anhydride (DPA), and camphoric anhydride (CA), was achieved using either organic bases (e.g., phosphazene) or nucleophilic salts (e.g., tetrabutyl ammonium chloride), affording cyclic PEAs and PTEAs with well-defined alternating structures and high molar masses. Structure–property relationship studies demonstrate that Boc deprotection, sulfur atom incorporation, and anhydride ring size collectively govern the thermal properties of the resulting polymers, underscoring the critical role of amide hydrogen bonding in modulating material performance.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"57 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466119","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-17DOI: 10.1021/acs.macromol.5c03607
Zhaoqiang Song, Linyi Liu, Linghui He, Yong Ni
Contrary to traditional theories, recent experiments reveal that immediate skin formation acts as a transport barrier, rendering drying kinetics during the entire drying process insensitive to relative humidity. Herein, we present a framework integrating elasto-visco-plastic constitutive modeling and Flory–Rehner theory within nonequilibrium thermodynamics to elucidate the unresolved evaporation phenomena. Our model reveals that the viscoelastic skin transforms the mass transport from humidity-controlled interfacial evaporation to internal viscoelastic-diffusive transport. The relaxation time of the skin orchestrates the coupling among stress evolution, volumetric deformation, and water diffusion, establishing a universal scaling relationship, where maximum evaporation occurs at Deborah number De ∼ O(1). While previous theories accounted for thickness-induced resistance, we identify plasticization-enhanced transport as the critical, previously overlooked mechanism. It is the competition between these two mechanisms that drive the observed decoupling from ambient conditions. Notably, the peak compressive stress at De ∼ O(1) can also induce transient skin layer buckling. These findings reconcile experimental observations of humidity-insensitive evaporation with theoretical predictions, providing essential insights into drying processes under variable environmental conditions.
与传统理论相反，最近的实验表明，立即形成的皮肤起着运输屏障的作用，使整个干燥过程中的干燥动力学对相对湿度不敏感。在此，我们提出了一个将弹粘塑性本构模型和非平衡热力学中的Flory-Rehner理论相结合的框架来解释未解决的蒸发现象。我们的模型表明粘弹性表皮将质量传递从湿度控制的界面蒸发转变为内部粘弹性扩散传递。皮肤的松弛时间协调了应力演化、体积变形和水扩散之间的耦合，建立了普遍的尺度关系，其中最大蒸发发生在Deborah number De ~ O(1)。虽然以前的理论解释了厚度诱导的阻力，但我们认为塑化增强的运输是关键的，以前被忽视的机制。正是这两种机制之间的竞争推动了观察到的与环境条件的脱钩。值得注意的是，De ~ O(1)处的峰值压应力也会引起瞬态蒙皮层屈曲。这些发现调和了对湿度不敏感蒸发的实验观察与理论预测，为在可变环境条件下的干燥过程提供了重要的见解。
{"title":"The Mechanics of Drying Polymer Solutions Explain Observations of Humidity Insensitivity and Transient Buckling","authors":"Zhaoqiang Song, Linyi Liu, Linghui He, Yong Ni","doi":"10.1021/acs.macromol.5c03607","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c03607","url":null,"abstract":"Contrary to traditional theories, recent experiments reveal that immediate skin formation acts as a transport barrier, rendering drying kinetics during the entire drying process insensitive to relative humidity. Herein, we present a framework integrating elasto-visco-plastic constitutive modeling and Flory–Rehner theory within nonequilibrium thermodynamics to elucidate the unresolved evaporation phenomena. Our model reveals that the viscoelastic skin transforms the mass transport from humidity-controlled interfacial evaporation to internal viscoelastic-diffusive transport. The relaxation time of the skin orchestrates the coupling among stress evolution, volumetric deformation, and water diffusion, establishing a universal scaling relationship, where maximum evaporation occurs at Deborah number <i>De</i> ∼ O(1). While previous theories accounted for thickness-induced resistance, we identify plasticization-enhanced transport as the critical, previously overlooked mechanism. It is the competition between these two mechanisms that drive the observed decoupling from ambient conditions. Notably, the peak compressive stress at <i>De</i> ∼ O(1) can also induce transient skin layer buckling. These findings reconcile experimental observations of humidity-insensitive evaporation with theoretical predictions, providing essential insights into drying processes under variable environmental conditions.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"10 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147477988","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-17DOI: 10.1021/acs.macromol.6c00172
Joost Kimpel, Iona Anderson, Di Zhu, Jyotsana Kala, Przemyslaw Sowinski, Alexander Giovannitti, Lars Öhrström, Jenny Nelson, Christian Müller
Knowledge of the molecular arrangement in the solid state is essential for designing high-performance conjugated polymers. The crystal structures and thermal behavior of their monomers provide important insight into their chain conformation and solid-state structure. Here, single crystals of aromatic thieno[3,2-b]thiophene units bearing mono- to tetraethylene glycol chains, building blocks of some high-performance organic mixed ionic-electronic conductors, are isolated using a robust crystallization protocol and analyzed using single-crystal X-ray diffraction and thermal analysis. Increasing oligoethylene glycol chain length shifts packing from π–π stacking to chain entanglement, accompanied by a melting temperature decrease from 149 to 41 °C. Molecular dynamics simulations using force fields parametrized with density functional theory show greater crystal stability for shorter chains, consistent with stronger π–π interactions relative to chain entanglement. Single crystals of a more extended conjugated system, thiophene-flanked thieno[3,2-b]thiophene with triethylene glycol, show mixed packing motifs and significant disruption of expected S···O interactions, revealing the importance of both side chain and π–π interactions. This work can be anticipated to aid the workup of monomers for synthesis, clarify packing motifs that govern structure–property relationships in conjugated polymers, and enable force-field implementation to guide organic semiconductor design and deepen understanding of their microstructure.
{"title":"From π–π Stacking to Chain Entanglements: Single Crystals of Oligoether-Substituted Thieno[3,2-b]thiophenes","authors":"Joost Kimpel, Iona Anderson, Di Zhu, Jyotsana Kala, Przemyslaw Sowinski, Alexander Giovannitti, Lars Öhrström, Jenny Nelson, Christian Müller","doi":"10.1021/acs.macromol.6c00172","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c00172","url":null,"abstract":"Knowledge of the molecular arrangement in the solid state is essential for designing high-performance conjugated polymers. The crystal structures and thermal behavior of their monomers provide important insight into their chain conformation and solid-state structure. Here, single crystals of aromatic thieno[3,2-<i>b</i>]thiophene units bearing mono- to tetraethylene glycol chains, building blocks of some high-performance organic mixed ionic-electronic conductors, are isolated using a robust crystallization protocol and analyzed using single-crystal X-ray diffraction and thermal analysis. Increasing oligoethylene glycol chain length shifts packing from π–π stacking to chain entanglement, accompanied by a melting temperature decrease from 149 to 41 °C. Molecular dynamics simulations using force fields parametrized with density functional theory show greater crystal stability for shorter chains, consistent with stronger π–π interactions relative to chain entanglement. Single crystals of a more extended conjugated system, thiophene-flanked thieno[3,2-<i>b</i>]thiophene with triethylene glycol, show mixed packing motifs and significant disruption of expected S···O interactions, revealing the importance of both side chain and π–π interactions. This work can be anticipated to aid the workup of monomers for synthesis, clarify packing motifs that govern structure–property relationships in conjugated polymers, and enable force-field implementation to guide organic semiconductor design and deepen understanding of their microstructure.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"11 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466118","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The development of solvent-free processing routes is essential for advancing sustainable manufacturing in soft electronics. Here, we introduce a melt-processable strategy for fabricating stretchable OFETs based on the physical blending of a low-melting point diketopyrrolopyrrole-based polymer and SEBS. Blends prepared across a wide compositional range were characterized to compare solvent-processed and melt-processed films. Materials characterization in the solid state revealed predominantly amorphous morphologies with composition-dependent differences in nanoscale organization. Free-standing tensile testing demonstrated a systematic decrease in Young’s modulus with increasing SEBS content, confirming enhanced flexibility. Rheological measurements further showed pronounced shear-thinning behavior at high SEBS loadings, advantageous for extrusion-based fabrication and compatible with both melt processing and traditional solution-based methods. Notably, organic field-effect transistors fabricated from melt-processed films exhibited charge carrier mobilities comparable to, and in some cases exceeding, those from solvent-processed blends, with stable performance maintained across diverse compositions. Overall, this work presents a sustainable, solvent-free approach to producing stretchable semiconducting films with tunable mechanical properties and robust electronic performance, offering a versatile platform for soft and stretchable electronic devices.
{"title":"Advancing Green Stretchable Electronics with Solvent-Free Melt-Processed Semiconducting Blends","authors":"Piumi Kulatunga, Alyssa Shaw, Ming-Hao Chang, Deanna Fisher, Yu-Cheng Chiu, Xiaodan Gu, Simon Rondeau-Gagné","doi":"10.1021/acs.macromol.6c00003","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c00003","url":null,"abstract":"The development of solvent-free processing routes is essential for advancing sustainable manufacturing in soft electronics. Here, we introduce a melt-processable strategy for fabricating stretchable OFETs based on the physical blending of a low-melting point diketopyrrolopyrrole-based polymer and SEBS. Blends prepared across a wide compositional range were characterized to compare solvent-processed and melt-processed films. Materials characterization in the solid state revealed predominantly amorphous morphologies with composition-dependent differences in nanoscale organization. Free-standing tensile testing demonstrated a systematic decrease in Young’s modulus with increasing SEBS content, confirming enhanced flexibility. Rheological measurements further showed pronounced shear-thinning behavior at high SEBS loadings, advantageous for extrusion-based fabrication and compatible with both melt processing and traditional solution-based methods. Notably, organic field-effect transistors fabricated from melt-processed films exhibited charge carrier mobilities comparable to, and in some cases exceeding, those from solvent-processed blends, with stable performance maintained across diverse compositions. Overall, this work presents a sustainable, solvent-free approach to producing stretchable semiconducting films with tunable mechanical properties and robust electronic performance, offering a versatile platform for soft and stretchable electronic devices.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"87 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466116","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-17DOI: 10.1021/acs.macromol.5c03412
Vijay Yadav, Prabhat K. Jaiswal, Rudolf Podgornik, Sunita Kumari
The ability to precisely control surface charge using charged polymers is fundamental to many nanotechnology applications, enabling the design and fabrication of materials with tailored properties and functionalities. Here, we study the effect of charge regulation (CR) on the interaction between two nanoparticles (NPs) mediated by an oppositely charged polyelectrolyte (PE) in an electrolyte solution. To this end, we employ a hybrid CR Monte Carlo/molecular dynamics simulation framework to systematically explore the effects of pH, salt concentration, and polymer chain length on NP surface charge behavior. For comparison, we also conduct molecular simulations under constant charge (CC) conditions. Our results reveal that CR enhances PE adsorption onto NP surfaces compared to the CC case, where polymer bridging dominates across a wide range of NP intersurface separations. This enhanced adsorption under CR leads to a weak net repulsion driven by osmotic forces. In contrast, the CC model yields a stronger net attraction due to the bridging force. Furthermore, we find that the CR effects are more pronounced under deionized conditions, whereas at a higher salt concentration, counterion screening dominates in both CR and CC cases, diminishing the CR effect. These findings highlight the importance of incorporating charge regulation in characterizing nanoparticle interactions within a complex biochemical environment, particularly in low salt concentrations.
{"title":"Charge Regulation Effect on Nanoparticle Interaction Mediated by a Polyelectrolyte","authors":"Vijay Yadav, Prabhat K. Jaiswal, Rudolf Podgornik, Sunita Kumari","doi":"10.1021/acs.macromol.5c03412","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c03412","url":null,"abstract":"The ability to precisely control surface charge using charged polymers is fundamental to many nanotechnology applications, enabling the design and fabrication of materials with tailored properties and functionalities. Here, we study the effect of charge regulation (CR) on the interaction between two nanoparticles (NPs) mediated by an oppositely charged polyelectrolyte (PE) in an electrolyte solution. To this end, we employ a hybrid CR Monte Carlo/molecular dynamics simulation framework to systematically explore the effects of pH, salt concentration, and polymer chain length on NP surface charge behavior. For comparison, we also conduct molecular simulations under constant charge (CC) conditions. Our results reveal that CR enhances PE adsorption onto NP surfaces compared to the CC case, where polymer bridging dominates across a wide range of NP intersurface separations. This enhanced adsorption under CR leads to a weak net repulsion driven by osmotic forces. In contrast, the CC model yields a stronger net attraction due to the bridging force. Furthermore, we find that the CR effects are more pronounced under deionized conditions, whereas at a higher salt concentration, counterion screening dominates in both CR and CC cases, diminishing the CR effect. These findings highlight the importance of incorporating charge regulation in characterizing nanoparticle interactions within a complex biochemical environment, particularly in low salt concentrations.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"52 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466115","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-17DOI: 10.1021/acs.macromol.5c03417
Tianyi Ma, Qin Yan, Zhibo Li, Dujin Wang, Guoming Liu
The crystal structure of poly(α-methylene-δ-valerolactone), P(MVL)ROP, synthesized by chemoselective ring-opening polymerization of α-methylene-δ-valerolactone, was determined through a combination of X-ray diffraction analysis and density functional theory (DFT) calculation. The results reveal a triclinic crystal system (space group P1̅) with unit cell parameters: a = 7.26 Å, b = 6.86 Å, c = 7.39 Å, α = 122.09°, β = 89.14°, and γ = 104.88°. The P(MVL)ROP chain adopts an all-trans conformation, as validated by DFT optimization and infrared spectroscopy analysis. Unlike conventional polyesters, P(MVL)ROP, featured with unsaturated bonds on the side chain, exhibits a distinctive triclinic unit cell, with two antiparallel chains included. Independent Gradient Model based on Hirshfeld partition (IGMH) analysis revealed that a series of distinct C–H···O═C interactions between adjacent parallel or antiparallel chains are the key stabilizing forces for the interchain packing.
{"title":"Crystal Structure of Poly(α-methylene-δ-valerolactone)","authors":"Tianyi Ma, Qin Yan, Zhibo Li, Dujin Wang, Guoming Liu","doi":"10.1021/acs.macromol.5c03417","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c03417","url":null,"abstract":"The crystal structure of poly(α-methylene-δ-valerolactone), P(MVL)<sub>ROP</sub>, synthesized by chemoselective ring-opening polymerization of α-methylene-δ-valerolactone, was determined through a combination of X-ray diffraction analysis and density functional theory (DFT) calculation. The results reveal a triclinic crystal system (space group <i>P</i>1̅) with unit cell parameters: <i>a</i> = 7.26 Å, <i>b</i> = 6.86 Å, <i>c</i> = 7.39 Å, α = 122.09°, β = 89.14°, and γ = 104.88°. The P(MVL)<sub>ROP</sub> chain adopts an all-<i>trans</i> conformation, as validated by DFT optimization and infrared spectroscopy analysis. Unlike conventional polyesters, P(MVL)<sub>ROP</sub>, featured with unsaturated bonds on the side chain, exhibits a distinctive triclinic unit cell, with two antiparallel chains included. Independent Gradient Model based on Hirshfeld partition (IGMH) analysis revealed that a series of distinct C–H···O═C interactions between adjacent parallel or antiparallel chains are the key stabilizing forces for the interchain packing.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"10 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147477987","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-16DOI: 10.1021/acs.macromol.5c03406
Hong Yan, Gang Li, Jiaoyang Zhang, Haitao Leng, Siwei Chen, Feiyang Yu, Li Han, Wanshuang Liu, Hongwei Ma
The precise control of monomer sequence and microstructure is a core challenge in synthetic polymers, particularly for achieving dynamic structural switching during chain growth. This work presents a novel strategy based on a sterically confined carbanionic active center to not only regulate the addition pathway of dienes but also drive programmable structural transitions, enabling the precise synthesis of AB’-type alternating sequence and AB’B-type periodic sequence. Specifically, the half-enclosed structure of 5-methylene-10,11-dihydro-5H-dibenzo [a, d]7 annulene-Li (MDDAE-Li) not only confers monomer selectivity but also dictates the addition mechanism of (1-cyclopropyl-1,3-butadien-1-yl) benzene (CPBB), exclusively favoring the 4,3-addition pathway accompanied by anion-migrated ring-opening polymerization (AMROP) to form a C7 skeleton. This behavior stands in sharp contrast to that observed with other DPE derivatives. Through strategic modulation of the reaction temperature, the copolymer sequence could be deliberately transitioned from strictly alternating to an AB′B-type ternary periodic sequence, wherein two consecutively incorporated CPBB units exhibit distinct microstructures (C7 skeleton and C4 skeleton). Furthermore, leveraging the reversible “lock–unlock” mechanism of MDDAE, a well-defined ABC-type periodic polymer with high molecular weight was successfully synthesized in the MDDAE/CPBB/St system. Thermal analysis revealed a clear correlation among sequence structure, carbon skeleton length, and glass transition temperature (Tg). This work establishes a new approach to regulate diene addition pathways and trigger structural transitions through active center and kinetic regulation, offering new insights into the “structure–property” relationship of periodic polymers.
{"title":"Structural Switching between Binary Alternating and Ternary Periodic with Reversible Lock–Unlock Carbanionic Polymerization Method","authors":"Hong Yan, Gang Li, Jiaoyang Zhang, Haitao Leng, Siwei Chen, Feiyang Yu, Li Han, Wanshuang Liu, Hongwei Ma","doi":"10.1021/acs.macromol.5c03406","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c03406","url":null,"abstract":"The precise control of monomer sequence and microstructure is a core challenge in synthetic polymers, particularly for achieving dynamic structural switching during chain growth. This work presents a novel strategy based on a sterically confined carbanionic active center to not only regulate the addition pathway of dienes but also drive programmable structural transitions, enabling the precise synthesis of AB’-type alternating sequence and AB’B-type periodic sequence. Specifically, the half-enclosed structure of 5-methylene-10,11-dihydro-5H-dibenzo [a, d]<sup>7</sup> annulene-Li (MDDAE-Li) not only confers monomer selectivity but also dictates the addition mechanism of (1-cyclopropyl-1,3-butadien-1-yl) benzene (CPBB), exclusively favoring the 4,3-addition pathway accompanied by anion-migrated ring-opening polymerization (AMROP) to form a C7 skeleton. This behavior stands in sharp contrast to that observed with other DPE derivatives. Through strategic modulation of the reaction temperature, the copolymer sequence could be deliberately transitioned from strictly alternating to an AB′B-type ternary periodic sequence, wherein two consecutively incorporated CPBB units exhibit distinct microstructures (C7 skeleton and C4 skeleton). Furthermore, leveraging the reversible “lock–unlock” mechanism of MDDAE, a well-defined ABC-type periodic polymer with high molecular weight was successfully synthesized in the MDDAE/CPBB/St system. Thermal analysis revealed a clear correlation among sequence structure, carbon skeleton length, and glass transition temperature (<i>T</i><sub>g</sub>). This work establishes a new approach to regulate diene addition pathways and trigger structural transitions through active center and kinetic regulation, offering new insights into the “structure–property” relationship of periodic polymers.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"36 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461890","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-16DOI: 10.1021/acs.macromol.5c03429
Jingchao Qin, Whitney S. Loo
Blends of oppositely charged polymers are capable of self-assembling into well-ordered nanostructures via supramolecular self-assembly. A series of monosulfonated-terminated polystyrene (PS) and monopiperidine–terminated poly(dimethylsiloxane) (PDMS) polymers with different molecular weights were synthesized and blended to investigate their phase behavior. A new synthetic route for piperidine-terminated PDMS with low dispersity and high end-group fidelity was developed based on a functionalized initiator accessible from commercially available reagents and compatible with anionic ring-opening polymerization. The resulting nanostructure of the blends was measured via small-angle X-ray scattering (SAXS) performed across a range of temperatures and revealed disordered structures in blends prepared with low molecular weight polymers. A model derived by Tanaka using the random phase approximation (RPA) was applied to extract the heteroassociation fraction (z) and effective interaction parameter (χeff), and a quantitatively similar value of z was observed across all blends with disordered morphologies. High molecular weight blends exhibited a variety of hybrid ordered nanostructures, and by precisely tuning the mixing ratio, we were able to induce phase transitions and achieve a variety of ordered nanostructures with long-range order. A molecular-scale mechanism to balance the electrostatic strength of end group association and segregation strength between the constituent polymers is proposed to rationalize the observed phase behavior.
{"title":"Supramolecular Assembly of End-Functionalized Polystyrene and Polydimethylsiloxane with Hybrid Nanostructures","authors":"Jingchao Qin, Whitney S. Loo","doi":"10.1021/acs.macromol.5c03429","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c03429","url":null,"abstract":"Blends of oppositely charged polymers are capable of self-assembling into well-ordered nanostructures via supramolecular self-assembly. A series of monosulfonated-terminated polystyrene (PS) and monopiperidine–terminated poly(dimethylsiloxane) (PDMS) polymers with different molecular weights were synthesized and blended to investigate their phase behavior. A new synthetic route for piperidine-terminated PDMS with low dispersity and high end-group fidelity was developed based on a functionalized initiator accessible from commercially available reagents and compatible with anionic ring-opening polymerization. The resulting nanostructure of the blends was measured via small-angle X-ray scattering (SAXS) performed across a range of temperatures and revealed disordered structures in blends prepared with low molecular weight polymers. A model derived by Tanaka using the random phase approximation (RPA) was applied to extract the heteroassociation fraction (<i>z</i>) and effective interaction parameter (χ<sub>eff</sub>), and a quantitatively similar value of <i>z</i> was observed across all blends with disordered morphologies. High molecular weight blends exhibited a variety of hybrid ordered nanostructures, and by precisely tuning the mixing ratio, we were able to induce phase transitions and achieve a variety of ordered nanostructures with long-range order. A molecular-scale mechanism to balance the electrostatic strength of end group association and segregation strength between the constituent polymers is proposed to rationalize the observed phase behavior.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"51 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466122","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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