Macromolecules最新文献

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Solvent-Responsive Glass Transition Behavior of Polyelectrolyte Complexes
IF 5.5 1区 化学
Macromolecules Pub Date : 2024-12-23 DOI: 10.1021/acs.macromol.4c02417
Hongwei Li, Dmitry Tolmachev, Piotr Batys, Maria Sammalkorpi, Jodie L. Lutkenhaus
{"title":"Solvent-Responsive Glass Transition Behavior of Polyelectrolyte Complexes","authors":"Hongwei Li, Dmitry Tolmachev, Piotr Batys, Maria Sammalkorpi, Jodie L. Lutkenhaus","doi":"10.1021/acs.macromol.4c02417","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02417","url":null,"abstract":"Polyelectrolyte complexes (PECs) have attracted considerable attention owing to their unique physicochemical properties and potential applications as smart materials. Herein, the glass transitions of PECs solvated with varying alcohols are investigated in poly(diallyldimethylammonium)/poly(acrylic acid) (PDADMA/PAA) complexes by using modulated differential scanning calorimetry (MDSC). Solvents with one or two hydroxyl groups are selected to examine the effect of PAA-solvent interactions on the glass transition temperature (<i>T</i><sub>g</sub>). Except for glycerol, all alcohol solvents yield PECs with detectable <i>T</i><sub>g</sub>’s and plasticization behavior. Furthermore, a linear relationship for 1/<i>T</i><sub>g</sub> and the natural logarithm of the number of hydroxyl groups to intrinsic ion pair ratio [ln(<i>n</i><sub>hydroxyl</sub>/<i>n</i><sub>intrinsic-ion-pair</sub>)] is found. This result is significant because prior work demonstrated the relationship only for water and no other solvents. All-atom molecular dynamics (MD) simulations analyze the ability of the solvent to form hydrogen bonds via the solvent’s OH groups to the PAA, revealing that the solvent molecule size and available hydroxyl groups govern the change in the glass transition. Overall, the clear dependence of a PEC’s glass transition on the solvent’s chemical structure provides a simple guideline for predicting their relationship.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"41 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874288","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}
引用次数: 0
Sustainable Terephthalic Polyesters with Medium/Long Methylene Sequence: Structure–Property Relationships and Closed-Loop Chemical Recycling
IF 5.5 1区 化学
Macromolecules Pub Date : 2024-12-23 DOI: 10.1021/acs.macromol.4c01793
Junfeng Liu, Jianfei Xia, Chang Zeng, Chengtao Yu, Ying Zheng, Bao Wang, Shanshan Xu, Pengju Pan
{"title":"Sustainable Terephthalic Polyesters with Medium/Long Methylene Sequence: Structure–Property Relationships and Closed-Loop Chemical Recycling","authors":"Junfeng Liu, Jianfei Xia, Chang Zeng, Chengtao Yu, Ying Zheng, Bao Wang, Shanshan Xu, Pengju Pan","doi":"10.1021/acs.macromol.4c01793","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c01793","url":null,"abstract":"Traditional short-chain terephthalic polyesters such as poly(ethylene terephthalate) (PET) are among the most produced plastics in today’s polymer industry, while their large-scale chemical recycling has been a long-standing challenge. The long-chain polyesters have shown good recyclability under mild conditions, whereas the structure–property relationships and chemical recycling performance of long-chain terephthalic polyesters are still unclear. Herein, we synthesized a series of medium/long-chain terephthalic polyesters with different methylene sequence lengths (CH<sub>2</sub> number in diol monomer <i>n</i><sub>CH<sub>2</sub></sub> = 6, 8, 10, 12) and investigated their thermal properties, crystallization behavior, mechanical properties, and chemical recycling performance. All terephthalic polyesters show good crystallizability; their melting temperature decreases, and melting enthalpy increases gradually as <i>n</i><sub>CH<sub>2</sub></sub> increases from 2 to 12. All polyesters adopt a triclinic crystal lattice while slightly different crystalline lamellar structures. The medium/long-chain terephthalic polyesters exhibit improved ductility and good melt processability, enabling them to be used as three-dimensional (3D) printing materials. In addition, the medium- and long-chain terephthalic polyesters are chemically recyclable and can depolymerize under mild conditions (e.g., 140 °C in methanol). The monomers obtained by depolymerization can be reused to synthesize again the according polyesters. This study provides new inspiration for developing sustainable high-performance polyesters with great industrial potential.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"149 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874287","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}
引用次数: 0
Molecular Mechanism of Mechanical Breathing in Organic Mixed Ionic-Electronic Conductors
IF 5.5 1区 化学
Macromolecules Pub Date : 2024-12-23 DOI: 10.1021/acs.macromol.4c01893
Xixian Yang, Hong Sun, Xiaomei He, Kejie Zhao
{"title":"Molecular Mechanism of Mechanical Breathing in Organic Mixed Ionic-Electronic Conductors","authors":"Xixian Yang, Hong Sun, Xiaomei He, Kejie Zhao","doi":"10.1021/acs.macromol.4c01893","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c01893","url":null,"abstract":"Mechanical breathing of organic mixed ionic-electronic conductors (OMIECs) is a structural response upon redox reactions. The breathing strain is often in the range of a few percentages to a few hundred percentages in different OMIECs operated in different chemical environments. Such mechanical activation needs to be tailored such as to be maximized in actuators and to be minimized in increasing the device reliability. We perform atomistic modeling to understand the molecular mechanism of mechanical swelling of OMIECs immersed in various electrolytes and at different oxidation states. We study poly(3,4-propylenedioxythiophene) (PProDOT) which is widely used in organic electrochromic devices as a model system and compare its swelling behavior in electrolytes of different salt concentrations, solvents, and anions. PProDOT deforms more in the electrolyte of lower salt concentration and larger anions. Mass transport of the electrolyte, especially the organic solvent, is dominant in regulating mechanical swelling of PProDOT compared to the electrostatic interactions. We examine the evolution of microstructural features and local bonding environments associated with the mixed conduction upon oxidation. We calculate the diffusion coefficients of the cation, anions, and solvents in the mixture of PProDOT and the electrolyte, which inform the swelling kinetics of PProDOT and the solvation structure in the electrolyte. The results are further validated by different self-aggregated PProDOT configurations and modeling protocols. The finding is in good agreement with the experiments and provides fundamental understanding of the molecular motifs underpinning the breathing strain in OMIECs.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"24 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874289","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}
引用次数: 0
Thermally Activated Delayed Fluorescence (TADF) Carbonized Polymer Dots for Efficient Red-Light-Induced Reversible Deactivation Radical Polymerization
IF 5.5 1区 化学
Macromolecules Pub Date : 2024-12-22 DOI: 10.1021/acs.macromol.4c02570
Yang Xiao, Wanchao Hu, Bei Liu, Shiyi Li, Changli Lü
{"title":"Thermally Activated Delayed Fluorescence (TADF) Carbonized Polymer Dots for Efficient Red-Light-Induced Reversible Deactivation Radical Polymerization","authors":"Yang Xiao, Wanchao Hu, Bei Liu, Shiyi Li, Changli Lü","doi":"10.1021/acs.macromol.4c02570","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02570","url":null,"abstract":"Thermally activated delayed fluorescence (TADF) carbon dots (CDs) have generated interest due to their ability to capture singlet and triplet excitons for efficient emission. However, there are still challenges in achieving high photocatalytic efficiency for traditional TADF CDs prepared by matrix-confinement strategies. Herein, we propose a facile one-pot solvothermal synthesis strategy of matrix-free TADF carbonized polymer dots (CPDs) with an absorption wavelength up to the red-light region and a long delayed fluorescence lifetime of 7.66 μs in DMSO. The unprecedented high-efficiency photocatalytic ability of TADF CPDs as a photocatalyst in both organic and aqueous solvents has been demonstrated for the first time in red-light-triggered photoinduced electron/energy transfer–reversible addition–fragmentation chain transfer (PET-RAFT) polymerization and photoinduced atom transfer radical polymerization (photo-ATRP), with high monomer conversion (&gt;90%) and narrow polymer dispersity (<i>M</i><sub>w</sub>/<i>M</i><sub>n</sub> &lt; 1.20). In addition, the designed CPDs are also successfully utilized in the inverse miniemulsion PET-RAFT polymerization system, expanding the application scope of CDs in photoinduced reversible deactivation radical polymerization (photo-RDRP). This work offers a unique avenue for designing and regulating the intersystem crossing (ISC) and reverse intersystem crossing (RISC) processes to achieve matrix-free TADF CD photocatalysts with long-lived excited states for effectively photocatalyzed RDRP.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"12 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874293","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}
引用次数: 0
Enhanced Ionic Conductivity via Suppressed Crystallization and Strengthened Dynamics in Solid Polymer-Blend Electrolytes: A Comprehensive Broadband Dielectric Spectroscopy Study
IF 5.5 1区 化学
Macromolecules Pub Date : 2024-12-22 DOI: 10.1021/acs.macromol.4c01879
Seunghan Yun, Insu Hwang, Jang Wook Choi, So Youn Kim
{"title":"Enhanced Ionic Conductivity via Suppressed Crystallization and Strengthened Dynamics in Solid Polymer-Blend Electrolytes: A Comprehensive Broadband Dielectric Spectroscopy Study","authors":"Seunghan Yun, Insu Hwang, Jang Wook Choi, So Youn Kim","doi":"10.1021/acs.macromol.4c01879","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c01879","url":null,"abstract":"In this study, we introduce solid polymer-blend electrolytes (SPBEs) in which the crystallization of poly(ethylene glycol) (PEG) is completely suppressed. This achievement was realized by utilizing low molecular weight PEG and incorporating high molecular weight poly(vinylidene fluoride) (PVDF) as the blend matrix, resulting in flexible and self-standing SPBEs. Complete inhibition of PEG crystallization is observed when employing the lower molecular weight of PEG or the higher concentration of lithium salt, leading to an impressive ionic conductivity of 2.9 × 10<sup>–4</sup> S/cm at room temperature. Temperature-dependent ionic conductivity shows a strong correlation between ionic transport and segmental motion of the blend matrix, following the Vogel–Tammann–Fulcher (VTF) relation. Further analysis of AC conductivity, electric modulus, and dielectric loss isotherms, obtained through broadband dielectric spectroscopy, reveals a coupling behavior between the relaxation times and the ionic conductivity. This experimental system can serve as a model system for designing high-performance polymer-blend-based solid electrolytes to achieve good mechanical properties and superior ionic conductivities.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"24 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874290","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}
引用次数: 0
A General Chain Lubrication Strategy for Ultra-Stretchable Polyacrylate Elastomers
IF 5.5 1区 化学
Macromolecules Pub Date : 2024-12-22 DOI: 10.1021/acs.macromol.4c02437
Guojun Zheng, Wenjie Xiong, Yiting Xu, Birong Zeng, Conghui Yuan, Lizong Dai
{"title":"A General Chain Lubrication Strategy for Ultra-Stretchable Polyacrylate Elastomers","authors":"Guojun Zheng, Wenjie Xiong, Yiting Xu, Birong Zeng, Conghui Yuan, Lizong Dai","doi":"10.1021/acs.macromol.4c02437","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02437","url":null,"abstract":"Polyacrylate elastomers have enormous application potential in various fields. However, facile and universal synthetic strategies remain rare for ultrastretchable polyacrylates (especially those with extension ratios ≥50) that are adaptable to various building blocks. Here, we develop a novel chain lubrication strategy to reduce the interchain friction and improve the slip of polymer chains during deformation. By constructing polyacrylates with soft, hard, and quaternary ammonium segments, we fabricate ultrastretchable elastomers (extension ratios up to 323) through emulsion polymerization and film casting, using quaternary ammonium surfactants (QASs) as emulsifiers. The lubricating mechanism of QASs is explored by varying the chemical structures of QASs, and it is demonstrated that QASs enhance the fluidity of polymer chains while forming eutectics with quaternary ammonium segments to construct physical cross-linking sites in the polymer networks. We also demonstrate the successful synthesis of a variety of ultrastretchable elastomers by replacing soft and hard segment monomers or surfactants, confirming the effectiveness and generalizability of the chain lubrication strategy. The chain lubrication strategy promises to pioneer new methods for fabricating highly ductile elastomers and advancing industrial rubbers.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"26 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874291","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}
引用次数: 0
Microphase Separation Transformation in Bio-Based Benzoxazine/Phenolic/PEO-b-PCL Diblock Copolymer Mixtures Induced by Transesterification Reaction
IF 5.5 1区 化学
Macromolecules Pub Date : 2024-12-20 DOI: 10.1021/acs.macromol.4c02072
Yang-Chin Kao, Yi-Hsuan Ku, Mohamed Gamal Mohamed, Wei-Hung Su, Shiao-Wei Kuo
{"title":"Microphase Separation Transformation in Bio-Based Benzoxazine/Phenolic/PEO-b-PCL Diblock Copolymer Mixtures Induced by Transesterification Reaction","authors":"Yang-Chin Kao, Yi-Hsuan Ku, Mohamed Gamal Mohamed, Wei-Hung Su, Shiao-Wei Kuo","doi":"10.1021/acs.macromol.4c02072","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02072","url":null,"abstract":"Herein, we synthesized a difunctionalized bio-based vanillin azine monomer (4,4′-((1<i>E</i>,1′<i>E</i>)-hydrazine-1,2-diylidenebis(methaneylylidene))bis(2-methoxyphenol), VBAZ-2OH) via a Schiff base reaction between vanillin and hydrazine monohydride. Subsequently, we successfully prepared 2,2′-(((1<i>E</i>,1′<i>E</i>)-hydrazine-1,2-diylidenebis(methaneylylidene))bis(8-methoxy-2<i>H</i>-benzo[<i>e</i>][1,3]oxazine-6,3(4<i>H</i>)-diyl))bis(ethan-1-ol), VBAZ-BZ-2OH), which contains oxazine units, through a Mannich condensation reaction of VBAZ-2OH with ethanolamine and paraformaldehyde in 1,4-dioxane as the solvent. The chemical structures of these two monomers (VBAZ-2OH and VBAZ-BZ-2OH) were characterized by using NMR and FTIR analyses. Our study aimed to investigate the transesterification reactions by blending different VBAZ-BZ-2OH/phenolic resin (BP) compositions with a PEO<sub>112</sub>-<i>b</i>-PCL<sub>99</sub> (EC) diblock copolymer to form various BP/EC blends. These blends exhibit competitive hydrogen-bonding interaction phenomena, which were analyzed using one-dimensional and two-dimensional FTIR analyses. Interestingly, after thermal treatment of BP/EC blends at 150 °C, the ordered self-assembled lamellae or hexagonal packed cylinder structures transform into the disordered micelle or disorder structure in BP/EC blends as a result of the transesterification reaction due to EC becoming miscible with a VBAZ-BZ-2OH monomer, disrupting the ordered self-assembled structure, which was confirmed through TEM and SAXS analyses. The transesterification reaction could easily understand the order–disorder morphological transformation using BP/EC blends to replace thermogravimetric analysis (TGA) coupled with microcomputed gas chromatography (TGA-GC) analyses.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"71 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857974","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}
引用次数: 0
Highly Efficient Synthesis of Alkyl-Linked Poly(arylene alkylene) Anion Exchange Membranes via Postfunctionalization Integrated with Olefin Hydroboration and Suzuki Coupling Reaction
IF 5.5 1区 化学
Macromolecules Pub Date : 2024-12-20 DOI: 10.1021/acs.macromol.4c02263
Jian-Rong Wu, Zheng-Yang Huang, Rong-Bin Zang, Jia-Feng Qian, Zhen-Dong Wen, Pan-Pan Huang, Jin Yao, Qingyi He, Deng-Yuan Li, Boxin Xue, Pei-Nian Liu
{"title":"Highly Efficient Synthesis of Alkyl-Linked Poly(arylene alkylene) Anion Exchange Membranes via Postfunctionalization Integrated with Olefin Hydroboration and Suzuki Coupling Reaction","authors":"Jian-Rong Wu, Zheng-Yang Huang, Rong-Bin Zang, Jia-Feng Qian, Zhen-Dong Wen, Pan-Pan Huang, Jin Yao, Qingyi He, Deng-Yuan Li, Boxin Xue, Pei-Nian Liu","doi":"10.1021/acs.macromol.4c02263","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02263","url":null,"abstract":"Postfunctionalization of poly(arylene alkylene) offers a simple and effective strategy to prepare robust anion exchange membranes (AEMs). The introduction of extended alkyl spacers not only enhances the chemical stability but also promotes the formation of microphase separation. Herein, we report a novel postfunctionalization approach that integrates alkyl linkers onto the poly(arylene alkylene) backbone through a one-pot reaction combining olefin hydroboration with Suzuki coupling. This methodology demonstrates exceptional reactivity and ensures complete functionalization with 100% efficiency while eliminating the need for complex monomer synthesis or purification. Two AEMs with dications were subsequently prepared via the Menshutkin reaction. These AEMs exhibit distinct phase separation structures, ultrahigh OH<sup>–</sup> conductivity, excellent alkaline stability, and superior performance in anion exchange membrane water electrolysis. This study presents a viable postfunctionalization strategy for developing high-performance AEMs and is expected to provide new insights into polymer chemistry and functional materials design.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"41 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142867342","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}
引用次数: 0
Binding-Induced Bond Polarization in Polymer Solutions to Drive Micelle and Vesicle Formation
IF 5.5 1区 化学
Macromolecules Pub Date : 2024-12-20 DOI: 10.1021/acs.macromol.4c02430
Shubhra Goel, Zitan Huang, Robert A. Riggleman, Ralph H. Colby, Robert J. Hickey
{"title":"Binding-Induced Bond Polarization in Polymer Solutions to Drive Micelle and Vesicle Formation","authors":"Shubhra Goel, Zitan Huang, Robert A. Riggleman, Ralph H. Colby, Robert J. Hickey","doi":"10.1021/acs.macromol.4c02430","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02430","url":null,"abstract":"Driving self-assembly through donor–acceptor interactions to create nanostructured materials is a key feature of supramolecular chemistry; however, the connection between molecular-level changes and larger-scale organization is still unknown. Here, we propose the concept of Lewis adduct binding-induced bond polarization, where the formation of the Lewis adduct leads to a large dipole (here estimated to be 12.5 D), significantly altering the intermolecular interactions between different species and inducing self-assembly. Specifically, a diblock copolymer, poly(2-(dimethylamino)ethyl methacrylate)-polystyrene (PDMAEMA-PS), self-assembles into nanostructured colloidal aggregates on the addition of the Lewis acid tris(pentafluorophenyl) borane (BCF) in toluene. The morphology of the nanostructured colloidal structures is controlled by tuning the block mole fraction of the poly(Lewis base) (polyLB, i.e., PDMAEMA) within the diblock copolymer, resulting in spherical micelles, vesicles, and large compound vesicles with an increasing PDMAEMA block mole fraction. The self-assembly is driven by binding-induced bond polarization during Lewis adduct formation, where the degree of bond polarization of the Lewis adducts is quantified by measuring the dielectric constant of adduct mixtures. We propose that the large dipole formed because of the Lewis adduct leads to substantial changes in the polymer–solvent interactions, driving the self-assembly. The reported findings regarding the Lewis adduct-induced self-assembly in polymer systems have far-ranging potential implications in supermolecular chemistry.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"1 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857825","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}
引用次数: 0
Interfacial Mechanical Behavior of Cellulose Nanocrystals and Chitosan
IF 5.5 1区 化学
Macromolecules Pub Date : 2024-12-19 DOI: 10.1021/acs.macromol.4c02323
Xiangrui Zheng, Yinsong Li, Shuhan Xu, Haoming Yang, Yao Zhang
{"title":"Interfacial Mechanical Behavior of Cellulose Nanocrystals and Chitosan","authors":"Xiangrui Zheng, Yinsong Li, Shuhan Xu, Haoming Yang, Yao Zhang","doi":"10.1021/acs.macromol.4c02323","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02323","url":null,"abstract":"Natural nanocomposites based on cellulose and chitosan have attracted much attention as alternatives to petroleum-based plastics. However, much less is understood about the interfacial properties between cellulose nanocrystals (CNCs) and chitosan that are essential for tuning the thermomechanical properties of CNC–chitosan nanocomposites. Here, we systematically investigate the interfacial behavior of CNC–CNC and CNC–chitosan systems by using atomistic molecular dynamics. The introduction of an interface has a significant influence on the structure and molecular mobility of chitosan near the interface, while it has a negligible effect on the CNC–CNC system due to its layered structure in the traverse directions perpendicular to the chain direction. The tension separation simulations demonstrate that in comparison with the CNC–CNC interface, the interfacial adhesive strength and stiffness of the CNC–chitosan interface decease but still maintain relatively high values. The hydrophilic (110) and (010) surfaces of CNC exhibit a better dispersion factor (∼0.7) in the chitosan matrix than the hydrophobic (100) surface. Moreover, the shear responses indicate that the underlayer CNC exhibits a stick–slip behavior at the CNC–CNC interface, while a smooth sliding is observed at the CNC–chitosan interface, leading to a smaller interfacial shear strength. With the insertion of chitosan as an intermediate layer at the CNC–CNC interface, the interfacial shear modulus progressively decreases with the increasing chitosan content for a chitosan thickness smaller than 9 nm, and it has a linear relationship with the reciprocal of molecular mobility of the chitosan layer. Our study provides fundamental insights into the influence of chitosan on the interfacial mechanical properties of CNCs and sheds light on the design of high-performance CNC–chitosan nanocomposites.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"79 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857971","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}
引用次数: 0
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