Macromolecules最新文献

{"title":"Increasing Viscosity of a Rodlike Polyelectrolyte Solution with a Monovalent Salt","authors":"John M. Migliore,&nbsp;Maruti Hegde,&nbsp;Amar S. Kumbhar,&nbsp;Qishun Tang and Theo J. Dingemans*,&nbsp;","doi":"10.1021/acs.macromol.4c0305310.1021/acs.macromol.4c03053","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c03053https://doi.org/10.1021/acs.macromol.4c03053","url":null,"abstract":"<p >The behavior of a synthetic self-assembled rodlike polyelectrolyte is investigated both in salt-free solutions and in the presence of monovalent salt. The inherent rigidity and rodlike nature of poly(2,2′-disulfonyl-4,4′-benzidine terephthalamide) (PBDT) in salt-free aqueous solutions results in a nematic liquid-crystalline transition at a 1.0 wt % concentration. Specific viscosity η_sp of PBDT scales with concentration (<i>c</i>) as η_sp ∼ <i>c</i>^1.2 in semidilute salt-free solutions, which deviates from the behavior of most semidilute polyelectrolyte solutions that follow Fuoss law (η_sp ∼ <i>c</i>^0.5). Additionally, PBDT solutions containing 30 mM NaCl reveal a crossover concentration (<i>c</i> &gt; <i>c</i>_<i>x</i>) and show up to a greater than 20-fold increase in η_<i>sp</i> compared with salt-free PBDT solutions at the same concentration. Oscillatory rheology experiments display a rise in modulus at all frequencies for PBDT solutions containing 10 mM NaCl and above, suggesting an increase in rod–rod association strength. X-ray scattering studies in salt-free semidilute PBDT solutions reveal polyelectrolyte correlation length (ξ) scaling as ε ∼ <i>c</i>^{–0.43±0.03}, which is a weaker dependence than typical scaling (ξ ∼ <i>c</i>^–1/2) due to the balance of electrostatic and associative intermolecular interactions. We propose that PBDT can serve as a synthetic model system for studying the solution behavior of associative rodlike polyelectrolytes.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 3","pages":"1367–1379 1367–1379"},"PeriodicalIF":5.1,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143376059","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}

{"title":"Increasing Viscosity of a Rodlike Polyelectrolyte Solution with a Monovalent Salt","authors":"John M. Migliore, Maruti Hegde, Amar S. Kumbhar, Qishun Tang, Theo J. Dingemans","doi":"10.1021/acs.macromol.4c03053","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c03053","url":null,"abstract":"The behavior of a synthetic self-assembled rodlike polyelectrolyte is investigated both in salt-free solutions and in the presence of monovalent salt. The inherent rigidity and rodlike nature of poly(2,2′-disulfonyl-4,4′-benzidine terephthalamide) (PBDT) in salt-free aqueous solutions results in a nematic liquid-crystalline transition at a 1.0 wt % concentration. Specific viscosity η_sp of PBDT scales with concentration (<i>c</i>) as η_sp ∼ <i>c</i>^1.2 in semidilute salt-free solutions, which deviates from the behavior of most semidilute polyelectrolyte solutions that follow Fuoss law (η_sp ∼ <i>c</i>^0.5). Additionally, PBDT solutions containing 30 mM NaCl reveal a crossover concentration (<i>c</i> &gt; <i>c</i>_<i>x</i>) and show up to a greater than 20-fold increase in η_<i>sp</i> compared with salt-free PBDT solutions at the same concentration. Oscillatory rheology experiments display a rise in modulus at all frequencies for PBDT solutions containing 10 mM NaCl and above, suggesting an increase in rod–rod association strength. X-ray scattering studies in salt-free semidilute PBDT solutions reveal polyelectrolyte correlation length (ξ) scaling as ε ∼ <i>c</i>^{–0.43±0.03}, which is a weaker dependence than typical scaling (ξ ∼ <i>c</i>^–1/2) due to the balance of electrostatic and associative intermolecular interactions. We propose that PBDT can serve as a synthetic model system for studying the solution behavior of associative rodlike polyelectrolytes.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"17 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143056860","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}

{"title":"Linear and Network-Forming Acetal Polymerization of Multifunctional Alcohols with Dichloromethane for Degradable and Recyclable Materials","authors":"Joshua T. Kamps,&nbsp;Bruce E. Kirkpatrick,&nbsp;Sean P. Keyser,&nbsp;Connor E. Miksch,&nbsp;Benjamin R. Nelson,&nbsp;John F. Rynk,&nbsp;Benjamin D. Fairbanks,&nbsp;Kristi S. Anseth and Christopher N. Bowman*,&nbsp;","doi":"10.1021/acs.macromol.4c0307810.1021/acs.macromol.4c03078","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c03078https://doi.org/10.1021/acs.macromol.4c03078","url":null,"abstract":"<p >Although thermoplastic and thermoset materials have revolutionized modern living, their widespread use has also led to significant environmental challenges due to limited recyclability and persistence in the environment. To address these issues, the development of new materials that are both functional and sustainable is crucial. In this work, an acetal-based polymerization is demonstrated, wherein dichloromethane (DCM) serves as a methylene synthon for forming acetals between alcohol end groups in the presence of a strong base, facilitating the production of fully degradable polymers and networks, as well as facile recovery of repolymerizable monomers. The incorporation of functional groups via primary alcohols, such as norbornene methanol, enables simultaneous functionalization of the polymer structure. Glycol-based linear polymers and macromers are utilized as primary building blocks, offering a versatile platform for generating tunable polymer architectures. Additionally, acetal-based oligomerization of decanediol is achieved at increased temperature and pressure, broadening the scope of potential materials accessible through this method. This historically understudied reaction holds great promise for the design of functional, degradable, and recyclable polymers.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 3","pages":"1578–1584 1578–1584"},"PeriodicalIF":5.1,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375938","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}

{"title":"Thermoset Light-Responsive Biopolyester Composite with Intrinsic Permanent Shape Reconfigurability and Degradability","authors":"Nur Syahirra Nordin,&nbsp;Xiangping Chen,&nbsp;Mun-Oon Fong,&nbsp;Tow-Jie Lok,&nbsp;Yaoting Xue,&nbsp;Siyang Li,&nbsp;Tao Feng,&nbsp;Yifeng Shen,&nbsp;Qiannan Hu,&nbsp;Kaihang Zhang,&nbsp;Qian Zhao,&nbsp;Tuck-Whye Wong*,&nbsp;Jie-Wei Wong* and Tiefeng Li*,&nbsp;","doi":"10.1021/acs.macromol.4c0308810.1021/acs.macromol.4c03088","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c03088https://doi.org/10.1021/acs.macromol.4c03088","url":null,"abstract":"<p >Adding functional nanoparticles to polymers is a popular approach to indirectly trigger the shape-memory effect (SME). Existing shape-memory polymer composites usually involve the use of solvents, catalysts, and initiators during synthesis. By polyesterification, in this article, we present a sustainable polyester matrix for a shape-memory polymer (SMP) composite consisting of carbon nanotubes (CNTs), which possess combined features. Owing to the photothermal conversion capability of the CNTs, selective triggering of the shape-memory behavior in different regions of the composite and photoweldability are made possible. Leveraging its intrinsic dynamic bond nature, the material can be reshaped at least five times, which is comparable with existing bond exchange networks. Additionally, ester bonds within the material enable hydrolytic degradation after its applications. We envision that this material design principle can be potentially applied on the fabrication of stimuli-responsive actuators for soft robots with complex geometries that also require degradability.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 3","pages":"1357–1366 1357–1366"},"PeriodicalIF":5.1,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143376139","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}

{"title":"Control of Fluoropolymer Crystallinity for Flexible, Transparent Optical Thin Films with Low Refractive Indexes","authors":"Yineng Zhao, Fei Hu, Wyatt E. Tenhaeff","doi":"10.1021/acs.macromol.4c02242","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02242","url":null,"abstract":"Fluoropolymers possess among the lowest indexes of refraction for dense, continuous materials, but their crystallinity typically leads to light scattering and haze. In this work, we studied poly(1<i>H</i>,1<i>H</i>,2<i>H</i>,2<i>H</i>-perfluorodecyl acrylate) (pPFDA) as a low-index fluoropolymer and successfully suppressed its crystallization while preserving its desirable low index of refraction (1.36 at 633 nm wavelength) and hydrophobicity (water contact angle of 122°). This was achieved through copolymerization between the hydrophobic 1<i>H</i>,1<i>H</i>,2<i>H</i>,2<i>H</i>-perfluorodecyl acrylate (PFDA) and <i>N</i>-vinylpyrrolidone (NVP) using initiated chemical vapor deposition (iCVD). The resulting copolymer p(PFDA-<i>co</i>-VP) film was smooth (roughness &lt;2 nm), highly transparent, thermally robust, and mechanically flexible. This contrasted with pPFDA homopolymer films, which were rough (roughness &gt;30 nm), hazy, and disintegrated at 70 °C due to melting. Moreover, the copolymerization resulted in a 16-fold improvement in the deposition kinetics. To demonstrate its excellent performance in practical applications, the low-index copolymer was paired with a high-index poly(divinylbenzene) (pDVB) (<i>n</i>₆₃₃ = 1.59) to build a six-layer interference coating. A six-layer fully polymeric interference coating with precise, independent control of each individual layer’s thickness was prepared for the first time by iCVD. Optimized for broadband antireflection, it reduced the surface reflectance to 1% over the entire visible spectrum, while withstanding large mechanical strain.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"36 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055458","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}

{"title":"Control of Fluoropolymer Crystallinity for Flexible, Transparent Optical Thin Films with Low Refractive Indexes","authors":"Yineng Zhao,&nbsp;Fei Hu and Wyatt E. Tenhaeff*,&nbsp;","doi":"10.1021/acs.macromol.4c0224210.1021/acs.macromol.4c02242","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02242https://doi.org/10.1021/acs.macromol.4c02242","url":null,"abstract":"<p >Fluoropolymers possess among the lowest indexes of refraction for dense, continuous materials, but their crystallinity typically leads to light scattering and haze. In this work, we studied poly(1<i>H</i>,1<i>H</i>,2<i>H</i>,2<i>H</i>-perfluorodecyl acrylate) (pPFDA) as a low-index fluoropolymer and successfully suppressed its crystallization while preserving its desirable low index of refraction (1.36 at 633 nm wavelength) and hydrophobicity (water contact angle of 122°). This was achieved through copolymerization between the hydrophobic 1<i>H</i>,1<i>H</i>,2<i>H</i>,2<i>H</i>-perfluorodecyl acrylate (PFDA) and <i>N</i>-vinylpyrrolidone (NVP) using initiated chemical vapor deposition (iCVD). The resulting copolymer p(PFDA-<i>co</i>-VP) film was smooth (roughness &lt;2 nm), highly transparent, thermally robust, and mechanically flexible. This contrasted with pPFDA homopolymer films, which were rough (roughness &gt;30 nm), hazy, and disintegrated at 70 °C due to melting. Moreover, the copolymerization resulted in a 16-fold improvement in the deposition kinetics. To demonstrate its excellent performance in practical applications, the low-index copolymer was paired with a high-index poly(divinylbenzene) (pDVB) (<i>n</i>₆₃₃ = 1.59) to build a six-layer interference coating. A six-layer fully polymeric interference coating with precise, independent control of each individual layer’s thickness was prepared for the first time by iCVD. Optimized for broadband antireflection, it reduced the surface reflectance to 1% over the entire visible spectrum, while withstanding large mechanical strain.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 3","pages":"1265–1278 1265–1278"},"PeriodicalIF":5.1,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.macromol.4c02242","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143376446","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Achieving Color-Tunable and Stable Luminescent Hydrophilic Phosphorescent Films in the Presence of Cucurbit[8]uril for Advanced Anti-counterfeiting","authors":"Rui-Han Gao, Qingmei Ge, Zhu Tao, Hang Cong","doi":"10.1021/acs.macromol.4c02722","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02722","url":null,"abstract":"Environmentally friendly hydrophilic polymer materials are easily affected by air humidity at room temperature, which weakens their quantum yield and lifetime. Based on the advantages of polymer hydrogen bonds and host–guest limits in the preparation of phosphorescent materials, we prepared a series of flexible dual-network films with high tensile strength and moisture resistance by using the properties of cucurbit[8]uril that can encapsulate bimolecularly at the same time, achieving color-tunable RTP from green to warm white after turning off the UV. These flexible and processable films had broad application prospects for multicolor afterglow displays, UV detection, and multilevel information encryption activities. In the meantime, due to their excellent moisture resistance and tensile properties, the service lifetimes of the phosphorescent films were greatly extended.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"9 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055460","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}

{"title":"Achieving Color-Tunable and Stable Luminescent Hydrophilic Phosphorescent Films in the Presence of Cucurbit[8]uril for Advanced Anti-counterfeiting","authors":"Rui-Han Gao,&nbsp;Qingmei Ge,&nbsp;Zhu Tao and Hang Cong*,&nbsp;","doi":"10.1021/acs.macromol.4c0272210.1021/acs.macromol.4c02722","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02722https://doi.org/10.1021/acs.macromol.4c02722","url":null,"abstract":"<p >Environmentally friendly hydrophilic polymer materials are easily affected by air humidity at room temperature, which weakens their quantum yield and lifetime. Based on the advantages of polymer hydrogen bonds and host–guest limits in the preparation of phosphorescent materials, we prepared a series of flexible dual-network films with high tensile strength and moisture resistance by using the properties of cucurbit[8]uril that can encapsulate bimolecularly at the same time, achieving color-tunable RTP from green to warm white after turning off the UV. These flexible and processable films had broad application prospects for multicolor afterglow displays, UV detection, and multilevel information encryption activities. In the meantime, due to their excellent moisture resistance and tensile properties, the service lifetimes of the phosphorescent films were greatly extended.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 3","pages":"1401–1408 1401–1408"},"PeriodicalIF":5.1,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143376049","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}

{"title":"Linear and Network-Forming Acetal Polymerization of Multifunctional Alcohols with Dichloromethane for Degradable and Recyclable Materials","authors":"Joshua T. Kamps, Bruce E. Kirkpatrick, Sean P. Keyser, Connor E. Miksch, Benjamin R. Nelson, John F. Rynk, Benjamin D. Fairbanks, Kristi S. Anseth, Christopher N. Bowman","doi":"10.1021/acs.macromol.4c03078","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c03078","url":null,"abstract":"Although thermoplastic and thermoset materials have revolutionized modern living, their widespread use has also led to significant environmental challenges due to limited recyclability and persistence in the environment. To address these issues, the development of new materials that are both functional and sustainable is crucial. In this work, an acetal-based polymerization is demonstrated, wherein dichloromethane (DCM) serves as a methylene synthon for forming acetals between alcohol end groups in the presence of a strong base, facilitating the production of fully degradable polymers and networks, as well as facile recovery of repolymerizable monomers. The incorporation of functional groups via primary alcohols, such as norbornene methanol, enables simultaneous functionalization of the polymer structure. Glycol-based linear polymers and macromers are utilized as primary building blocks, offering a versatile platform for generating tunable polymer architectures. Additionally, acetal-based oligomerization of decanediol is achieved at increased temperature and pressure, broadening the scope of potential materials accessible through this method. This historically understudied reaction holds great promise for the design of functional, degradable, and recyclable polymers.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"59 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055461","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}

{"title":"Pearl-Necklace to Unimolecular Micelle Formation by Heterograft Bottlebrush Polymers in Solution","authors":"Yiyan Kuang, Elena E. Dormidontova","doi":"10.1021/acs.macromol.4c02451","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02451","url":null,"abstract":"Bottlebrush polymers (BBPs) have attracted considerable attention due to their unique properties and a variety of applications. Using coarse-grained molecular dynamics simulations, we investigate and compare the structural properties of cyclic and linear poly(vinyl alcohol)-<i>graft</i>-poly(ethylene oxide)/poly(ethylene) (PVA-<i>g</i>-PEO/PE) in aqueous solution as a function of hydrophobic side-chain fraction. The side chains of different chemical nature allow the bottlebrush polymer to self-organize into different unimolecular structures. We found that with an increasing polyethylene fraction or PE side-chain length, an amphiphilic BBP self-organizes first into a pearl-necklace structure, which contains several hydrophobic aggregates engulfed and separated by hydrophilic side chains followed by a dumbbell-like structure. When the separation between two neighboring PE side chains becomes less than half of a PE side-chain length (<i>d</i>_sep &lt; <i>l</i>_PE/2), a spherical unimolecular micelle with a single hydrophobic core surrounded by hydrophilic corona forms. Linear heterograft BBPs exhibit a higher propensity for the pearl-necklace regime at lower PE fractions, while for the cyclic heterograft BBPs, the backbone curvature enhances formation of dumbbell-like structures and facilitates packing into a more compact core of unimolecular micelles at higher PE content. The shape anisotropy of linear heterograft BBPs systematically decreases with an increase of PE fraction as the shape changes from 1D worm-like to a 3D spherically symmetric unimolecular micelle, while for cyclic heterograft BBPs, the shape anisotropy increases, reaches a maximum, and decreases reflecting conformational changes from a planar 2D structure to 1D dumbbell to 3D spherical conformations, accordingly. Among the different conformations of heterograft BBPs in solution, a spherical unimolecular micelle with the smallest hydrophobic core exhibits minimal contacts with water and maximum protection by the hydrophilic corona. These results demonstrate that heterograft BBPs offer a variety of conformations controlled by the side-chain length and composition that can be exploited in different applications including encapsulation of hydrophobic moieties for therapeutic or imaging applications.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"40 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055500","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}