Pub Date : 2024-08-20Epub Date: 2024-07-18DOI: 10.1021/acsmacrolett.4c00278
Meng Huo, Ruixue Zhu
Statistical copolymers have been extensively used in chemical industries and our daily lives, owing to their ease of synthesis and functionalization. However, self-assembly based on statistical copolymers has been haunted by high interfacial energy, poor stability, and low concentration. We proposed the statistical copolymerization-induced self-assembly (stat-PISA) as a general strategy for one-step preparing stable statistical copolymer assemblies with high solids content. The concept was demonstrated through a model dispersion polymerization system comprising a charged hydrophilic monomer and a core-forming monomer, producing spherical micelles via a spinodal decomposition mechanism with an interconnected network intermediate. The stat-PISA was tunable by varying the fraction of charged monomer, the polymer chain length, and the solids content. The statistical copolymer micelles were demonstrated to be a potential Pickering emulsifier with superior stabilizing performances compared to their block copolymer counterparts. The general applicability of stat-PISA was demonstrated by preparing statistical copolymer assemblies with varying surface charges and chemical compositions. Particularly, this strategy is feasible for conventional free radical polymerization, promising for industrial scale-up.
{"title":"Statistical Copolymerization-Induced Self-Assembly.","authors":"Meng Huo, Ruixue Zhu","doi":"10.1021/acsmacrolett.4c00278","DOIUrl":"10.1021/acsmacrolett.4c00278","url":null,"abstract":"<p><p>Statistical copolymers have been extensively used in chemical industries and our daily lives, owing to their ease of synthesis and functionalization. However, self-assembly based on statistical copolymers has been haunted by high interfacial energy, poor stability, and low concentration. We proposed the statistical copolymerization-induced self-assembly (<i>stat</i>-PISA) as a general strategy for one-step preparing stable statistical copolymer assemblies with high solids content. The concept was demonstrated through a model dispersion polymerization system comprising a charged hydrophilic monomer and a core-forming monomer, producing spherical micelles via a spinodal decomposition mechanism with an interconnected network intermediate. The <i>stat</i>-PISA was tunable by varying the fraction of charged monomer, the polymer chain length, and the solids content. The statistical copolymer micelles were demonstrated to be a potential Pickering emulsifier with superior stabilizing performances compared to their block copolymer counterparts. The general applicability of <i>stat</i>-PISA was demonstrated by preparing statistical copolymer assemblies with varying surface charges and chemical compositions. Particularly, this strategy is feasible for conventional free radical polymerization, promising for industrial scale-up.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.1,"publicationDate":"2024-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141631869","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-20Epub Date: 2024-07-22DOI: 10.1021/acsmacrolett.4c00330
Zhiliang Gao, Hongning Sun, Shuang Yang, Mengqi Li, Na Qi, Jiwei Cui
Cell-like particles represent a category of synthetic particles designed to emulate the structures or functions of natural cells. Herein, we present the assembly of cell-like poly(ethylene glycol) (PEG) particles with different stiffnesses and shapes via replication of animal cells and investigate the impact of particle stiffness on their biological behaviors. As a proof of concept, we fabricate red blood cell-like and spherical PEG particles with varying cross-linking densities. A systematic exploration of their properties, encompassing morphology, stiffness, deformability, and biodistribution, reveal the vital influence of particle stiffness on in vivo fate, elucidating its role in governing the traversal of capillaries and the dynamic interactions with phagocytic cells.
{"title":"Red Blood Cell-Like Poly(ethylene glycol) Particles: Influence of Particle Stiffness on Biological Behaviors.","authors":"Zhiliang Gao, Hongning Sun, Shuang Yang, Mengqi Li, Na Qi, Jiwei Cui","doi":"10.1021/acsmacrolett.4c00330","DOIUrl":"10.1021/acsmacrolett.4c00330","url":null,"abstract":"<p><p>Cell-like particles represent a category of synthetic particles designed to emulate the structures or functions of natural cells. Herein, we present the assembly of cell-like poly(ethylene glycol) (PEG) particles with different stiffnesses and shapes <i>via</i> replication of animal cells and investigate the impact of particle stiffness on their biological behaviors. As a proof of concept, we fabricate red blood cell-like and spherical PEG particles with varying cross-linking densities. A systematic exploration of their properties, encompassing morphology, stiffness, deformability, and biodistribution, reveal the vital influence of particle stiffness on <i>in vivo</i> fate, elucidating its role in governing the traversal of capillaries and the dynamic interactions with phagocytic cells.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.1,"publicationDate":"2024-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141746717","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-19DOI: 10.1021/acsmacrolett.4c0037810.1021/acsmacrolett.4c00378
Harrison Landfield, and , Muzhou Wang*,
We utilize single particle tracking studies to investigate the diffusion of polylysine through concentrated matrices of cationic polylysine and anionic polyglutamic acid with no added salts. These studies show that diffusivity has a strong apparently exponential dependence on concentration in crowded systems that does not appear to be a function of the charge sign. These trends are consistent in both single-phase systems prepared at concentrated conditions and polymer-rich coacervate phases formed from dilute phase-separating systems. The likely origin of this behavior is the onset of glassy dynamics spurred by a decrease in plasticization by water and the large excluded volume associated with charge-bearing species. This effect can be contextualized through free volume-based theories such as the Vrentas–Duda model. Overall, we obtain dynamic behavior that is distinctly different from behavior observed in more dilute systems and warrants further investigation.
{"title":"Diffusive Trends in Concentrated Oppositely-Charged Polyelectrolyte Solutions and Onset of Glassy Dynamics","authors":"Harrison Landfield, and , Muzhou Wang*, ","doi":"10.1021/acsmacrolett.4c0037810.1021/acsmacrolett.4c00378","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00378https://doi.org/10.1021/acsmacrolett.4c00378","url":null,"abstract":"<p >We utilize single particle tracking studies to investigate the diffusion of polylysine through concentrated matrices of cationic polylysine and anionic polyglutamic acid with no added salts. These studies show that diffusivity has a strong apparently exponential dependence on concentration in crowded systems that does not appear to be a function of the charge sign. These trends are consistent in both single-phase systems prepared at concentrated conditions and polymer-rich coacervate phases formed from dilute phase-separating systems. The likely origin of this behavior is the onset of glassy dynamics spurred by a decrease in plasticization by water and the large excluded volume associated with charge-bearing species. This effect can be contextualized through free volume-based theories such as the Vrentas–Duda model. Overall, we obtain dynamic behavior that is distinctly different from behavior observed in more dilute systems and warrants further investigation.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.1,"publicationDate":"2024-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142237771","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-19DOI: 10.1021/acsmacrolett.4c0018710.1021/acsmacrolett.4c00187
Yusheng Qian, Danjing Yang, Jiaming Zhu, Shuting Huang, Sijin Chen, Jing Zeng, Jin Xu, Jing He* and Chuncai Zhou*,
Bacteria in tumor microenvironments promote carcinogenesis and trigger complications, suggesting the significance of intervening in bacterial growth in cancer treatment. Here, dendrimer-derived mimics (DMs) of host defense peptides (HDPs) were designed for antibacterial and anticancer therapy, which feature a dendronized polylysine core and polycaprolactone arms. DMs displayed not only remarkable activities against Staphylococcus aureus and human lung cancer cells, but also exceptional selectivity. The membranolytic mechanism revealed by morphology analysis explained their low susceptibility to induce resistance. Further, the optimized DM inhibited tumor growth in the subcutaneous tumor model when administered via intraperitoneal injection and exhibited negligible toxicity to tissues. Overall, we combined the superiority of dendrimers and the mechanism from HDPs to design agents with dual antibacterial and anticancer activities that possess great potential for clinical oncology therapy.
{"title":"Mimics of Host Defense Peptides Derived from Dendronized Polylysines for Antibacterial and Anticancer Therapy","authors":"Yusheng Qian, Danjing Yang, Jiaming Zhu, Shuting Huang, Sijin Chen, Jing Zeng, Jin Xu, Jing He* and Chuncai Zhou*, ","doi":"10.1021/acsmacrolett.4c0018710.1021/acsmacrolett.4c00187","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00187https://doi.org/10.1021/acsmacrolett.4c00187","url":null,"abstract":"<p >Bacteria in tumor microenvironments promote carcinogenesis and trigger complications, suggesting the significance of intervening in bacterial growth in cancer treatment. Here, dendrimer-derived mimics (DMs) of host defense peptides (HDPs) were designed for antibacterial and anticancer therapy, which feature a dendronized polylysine core and polycaprolactone arms. DMs displayed not only remarkable activities against <i>Staphylococcus aureus</i> and human lung cancer cells, but also exceptional selectivity. The membranolytic mechanism revealed by morphology analysis explained their low susceptibility to induce resistance. Further, the optimized DM inhibited tumor growth in the subcutaneous tumor model when administered <i>via</i> intraperitoneal injection and exhibited negligible toxicity to tissues. Overall, we combined the superiority of dendrimers and the mechanism from HDPs to design agents with dual antibacterial and anticancer activities that possess great potential for clinical oncology therapy.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.1,"publicationDate":"2024-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142237772","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-19DOI: 10.1021/acsmacrolett.4c00378
Harrison Landfield, Muzhou Wang
We utilize single particle tracking studies to investigate the diffusion of polylysine through concentrated matrices of cationic polylysine and anionic polyglutamic acid with no added salts. These studies show that diffusivity has a strong apparently exponential dependence on concentration in crowded systems that does not appear to be a function of the charge sign. These trends are consistent in both single-phase systems prepared at concentrated conditions and polymer-rich coacervate phases formed from dilute phase-separating systems. The likely origin of this behavior is the onset of glassy dynamics spurred by a decrease in plasticization by water and the large excluded volume associated with charge-bearing species. This effect can be contextualized through free volume-based theories such as the Vrentas–Duda model. Overall, we obtain dynamic behavior that is distinctly different from behavior observed in more dilute systems and warrants further investigation.
{"title":"Diffusive Trends in Concentrated Oppositely-Charged Polyelectrolyte Solutions and Onset of Glassy Dynamics","authors":"Harrison Landfield, Muzhou Wang","doi":"10.1021/acsmacrolett.4c00378","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00378","url":null,"abstract":"We utilize single particle tracking studies to investigate the diffusion of polylysine through concentrated matrices of cationic polylysine and anionic polyglutamic acid with no added salts. These studies show that diffusivity has a strong apparently exponential dependence on concentration in crowded systems that does not appear to be a function of the charge sign. These trends are consistent in both single-phase systems prepared at concentrated conditions and polymer-rich coacervate phases formed from dilute phase-separating systems. The likely origin of this behavior is the onset of glassy dynamics spurred by a decrease in plasticization by water and the large excluded volume associated with charge-bearing species. This effect can be contextualized through free volume-based theories such as the Vrentas–Duda model. Overall, we obtain dynamic behavior that is distinctly different from behavior observed in more dilute systems and warrants further investigation.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142002851","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-16DOI: 10.1021/acsmacrolett.4c0039110.1021/acsmacrolett.4c00391
Tong Wang, Yixuan Chen, Boran Chen, Mathew J. Suazo, Nathan S. Purwanto and John M. Torkelson*,
We synthesized covalent adaptable networks (CANs) made from chain-growth comonomers using nonisocyanate thiourethane chemistry. We derivatized glycidyl methacrylate with cyclic dithiocarbonate (GMA-DTC), did a free-radical polymerization of n-hexyl methacrylate with GMA-DTC to obtain a statistical copolymer with 8 mol % GMA-DTC, and cross-linked it with difunctional amine. The dynamic covalent thionourethane and disulfide bonds lead to CAN reprocessability with full recovery of the cross-link density; the temperature dependence of the rubbery plateau modulus indicates that associative character dominates the dynamic response. The CAN exhibits complete self-healing at 110 °C with tensile property recovery and excellent creep resistance at 90–100 °C. Stress relaxation at 140–170 °C reveals an activation energy of 105 ± 6 kJ/mol, equal to the activation energy (Ea) of the CAN poly(n-hexyl methacrylate) backbone α-relaxation. We hypothesize that CANs with exclusively or predominantly associative dynamics have their stress-relaxation Ea defined by the α-relaxation Ea. This hypothesis is supported by stress relaxation studies on a similar poly(n-lauryl methacrylate)-based CAN.
我们利用非异氰酸酯硫代氨基甲酸酯化学合成了由链增长共聚物制成的共价适应性网络 (CAN)。我们用环状二硫代碳酸酯(GMA-DTC)对甲基丙烯酸缩水甘油酯进行了衍生,用 GMA-DTC 对甲基丙烯酸正己酯进行了自由基聚合,得到了含有 8 mol % GMA-DTC 的统计共聚物,并用双官能胺对其进行了交联。动态共价的硫代氨基甲酸乙酯键和二硫键使 CAN 具有可再加工性,并能完全恢复交联密度;橡胶高原模量的温度依赖性表明,缔合特性在动态响应中占主导地位。CAN 在 110 °C 时表现出完全的自愈性,在 90-100 °C 时可恢复拉伸性能和优异的抗蠕变性。140-170 °C 时的应力松弛显示出 105 ± 6 kJ/mol 的活化能,与 CAN 聚(甲基丙烯酸正己酯)骨架 α 松弛的活化能 (Ea) 相等。我们假设,完全或主要具有关联动力学的 CAN 的应力松弛 Ea 是由α-松弛 Ea 确定的。对类似的聚甲基丙烯酸正十二烷基酯 CAN 进行的应力松弛研究支持了这一假设。
{"title":"Reprocessable, Self-Healing, and Creep-Resistant Covalent Adaptable Network Made from Chain-Growth Monomers with Dynamic Covalent Thionourethane and Disulfide Cross-Links","authors":"Tong Wang, Yixuan Chen, Boran Chen, Mathew J. Suazo, Nathan S. Purwanto and John M. Torkelson*, ","doi":"10.1021/acsmacrolett.4c0039110.1021/acsmacrolett.4c00391","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00391https://doi.org/10.1021/acsmacrolett.4c00391","url":null,"abstract":"<p >We synthesized covalent adaptable networks (CANs) made from chain-growth comonomers using nonisocyanate thiourethane chemistry. We derivatized glycidyl methacrylate with cyclic dithiocarbonate (GMA-DTC), did a free-radical polymerization of <i>n</i>-hexyl methacrylate with GMA-DTC to obtain a statistical copolymer with 8 mol % GMA-DTC, and cross-linked it with difunctional amine. The dynamic covalent thionourethane and disulfide bonds lead to CAN reprocessability with full recovery of the cross-link density; the temperature dependence of the rubbery plateau modulus indicates that associative character dominates the dynamic response. The CAN exhibits complete self-healing at 110 °C with tensile property recovery and excellent creep resistance at 90–100 °C. Stress relaxation at 140–170 °C reveals an activation energy of 105 ± 6 kJ/mol, equal to the activation energy (<i>E</i><sub>a</sub>) of the CAN poly(<i>n</i>-hexyl methacrylate) backbone α-relaxation. We hypothesize that CANs with exclusively or predominantly associative dynamics have their stress-relaxation <i>E</i><sub>a</sub> defined by the α-relaxation <i>E</i><sub>a</sub>. This hypothesis is supported by stress relaxation studies on a similar poly(<i>n</i>-lauryl methacrylate)-based CAN.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.1,"publicationDate":"2024-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142237850","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-15DOI: 10.1021/acsmacrolett.4c0047210.1021/acsmacrolett.4c00472
Jiamei Liu, Tao Wang and Hui Sun*,
The investigation of the amorphous to crystalline transformation and the corresponding influence on the self-assembly behavior of amphiphilic polymers are of significant interest in this field. Herein, we propose the concept of intramolecular cyclization-induced self-assembly (ICISA) to prepare crystalline nanoflowers at a high solid content of 15% on the basis of the amorphous to crystalline transformation of poly(amic acid) (PAA). Taking advantage of the reactive property of the PAA, rigid and crystalline polyimide (PI) segments are introduced to the backbone of the PAA to give P(AA-stat-I) induced by the intramolecular cyclization reaction upon thermal treatment, leading to the in situ formation of crystalline nanoflowers. Revealing the formation mechanism of the nanoflowers, we found that the nanosheets are formed at the early stage and then stacked to form the nanoflowers at high concentrations. The relationship between the degree of imidization and incubation temperature is quantitatively analyzed, and the effects of temperature on the morphology, degree of imidization, and crystallinity of the assemblies are also investigated. Furthermore, computer simulations demonstrate the optimized temperature of ICISA of 160 °C, which ensures the match between the intramolecular cyclization reaction rate, the self-assembly process, and the lowest energy state of the self-assembly system, resulting in the formation of nanoflowers with high crystallinity. Overall, a facile one-step strategy is proposed to prepare crystalline nanoflowers based on the in situ thermally triggered intramolecular cyclization reaction of a PAA, which may bring fresh insights into the dynamic amorphous to the crystalline transformation of polymers.
{"title":"Crystalline Nanoflowers Derived from the Intramolecular Cyclization-Induced Self-Assembly of an Amorphous Poly(amic acid) at High Solid Content","authors":"Jiamei Liu, Tao Wang and Hui Sun*, ","doi":"10.1021/acsmacrolett.4c0047210.1021/acsmacrolett.4c00472","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00472https://doi.org/10.1021/acsmacrolett.4c00472","url":null,"abstract":"<p >The investigation of the amorphous to crystalline transformation and the corresponding influence on the self-assembly behavior of amphiphilic polymers are of significant interest in this field. Herein, we propose the concept of intramolecular cyclization-induced self-assembly (ICISA) to prepare crystalline nanoflowers at a high solid content of 15% on the basis of the amorphous to crystalline transformation of poly(amic acid) (PAA). Taking advantage of the reactive property of the PAA, rigid and crystalline polyimide (PI) segments are introduced to the backbone of the PAA to give P(AA-<i>stat</i>-I) induced by the intramolecular cyclization reaction upon thermal treatment, leading to the in situ formation of crystalline nanoflowers. Revealing the formation mechanism of the nanoflowers, we found that the nanosheets are formed at the early stage and then stacked to form the nanoflowers at high concentrations. The relationship between the degree of imidization and incubation temperature is quantitatively analyzed, and the effects of temperature on the morphology, degree of imidization, and crystallinity of the assemblies are also investigated. Furthermore, computer simulations demonstrate the optimized temperature of ICISA of 160 °C, which ensures the match between the intramolecular cyclization reaction rate, the self-assembly process, and the lowest energy state of the self-assembly system, resulting in the formation of nanoflowers with high crystallinity. Overall, a facile one-step strategy is proposed to prepare crystalline nanoflowers based on the in situ thermally triggered intramolecular cyclization reaction of a PAA, which may bring fresh insights into the dynamic amorphous to the crystalline transformation of polymers.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.1,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142246329","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-15DOI: 10.1021/acsmacrolett.4c0039710.1021/acsmacrolett.4c00397
Catherine Beaumont, Thomas Lemieux, Stefania Aivali, Mona Hamidzad Sangachin, Akpeko Gasonoo, Tristan Marcoux St-Pierre, Marissa Bélanger, Serge Beaupré, Gregory C. Welch and Mario Leclerc*,
The development of modern optoelectronic devices increases the need for lightweight and flexible transparent conductors. It is thus essential to develop new eco-friendly materials that can be easily processed for the fabrication of such devices. For this purpose, the synthesis of self-doped, highly conducting, transmissive, and water-processable polythiophene derivatives was performed via the direct heteroarylation polymerization method and a protection/deprotection strategy. Stable conductivities up to 1000 S cm–1 have been obtained. Champion materials (P1 and P7) were scaled and processed via the roll-to-roll compatible slot-die coating method to demonstrate their large area applicability. The best coated films exhibited optical transmittance greater than 79% at 550 nm with sheet resistances of 116 Ω □–1. These values are comparable to indium–tin oxide on plastic and thus present a viable alternative to metal oxide-based electrodes.
{"title":"Highly Transmissive, Processable, Highly Conducting and Stable Polythiophene Derivatives via Direct (Hetero)arylation Polymerization","authors":"Catherine Beaumont, Thomas Lemieux, Stefania Aivali, Mona Hamidzad Sangachin, Akpeko Gasonoo, Tristan Marcoux St-Pierre, Marissa Bélanger, Serge Beaupré, Gregory C. Welch and Mario Leclerc*, ","doi":"10.1021/acsmacrolett.4c0039710.1021/acsmacrolett.4c00397","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00397https://doi.org/10.1021/acsmacrolett.4c00397","url":null,"abstract":"<p >The development of modern optoelectronic devices increases the need for lightweight and flexible transparent conductors. It is thus essential to develop new eco-friendly materials that can be easily processed for the fabrication of such devices. For this purpose, the synthesis of self-doped, highly conducting, transmissive, and water-processable polythiophene derivatives was performed via the direct heteroarylation polymerization method and a protection/deprotection strategy. Stable conductivities up to 1000 S cm<sup>–1</sup> have been obtained. Champion materials (<b>P1</b> and <b>P7</b>) were scaled and processed via the roll-to-roll compatible slot-die coating method to demonstrate their large area applicability. The best coated films exhibited optical transmittance greater than 79% at 550 nm with sheet resistances of 116 Ω □<sup>–1</sup>. These values are comparable to indium–tin oxide on plastic and thus present a viable alternative to metal oxide-based electrodes.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.1,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142237858","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-14DOI: 10.1021/acsmacrolett.4c0042610.1021/acsmacrolett.4c00426
Chao Duan, and , Rui Wang*,
Polyelectrolyte (PE) brushes are widely used in biomaterials and nanotechnology to regulate the surface properties and interactions. Here, we apply the electrostatic correlation augmented self-consistent field theory to investigate the interactions between opposing PE brushes in a mixture of 1:1 and 3:1 salt solutions. Our theory predicts a hysteretic feature of the normal stress induced by strong ion correlations. In the presence of trivalent ions, the force profile is discontinuous: repulsive in the compression branch and adhesive in the separation branch. The molecular origin of the hysteretic force is the coexistence of two collapsed modes: two separated condensed layers on each surface in the compression and a single bundled condensed layer in the separation. With the systematic inclusion of ion correlations, our theory captures well the hysteretic force, adhesive separation, “jump-in” and “jump-out” features, and the “specific ion effect”, all in good agreement with the reported experimental results.
{"title":"Ion Correlation-Driven Hysteretic Adhesion and Repulsion between Opposing Polyelectrolyte Brushes","authors":"Chao Duan, and , Rui Wang*, ","doi":"10.1021/acsmacrolett.4c0042610.1021/acsmacrolett.4c00426","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00426https://doi.org/10.1021/acsmacrolett.4c00426","url":null,"abstract":"<p >Polyelectrolyte (PE) brushes are widely used in biomaterials and nanotechnology to regulate the surface properties and interactions. Here, we apply the electrostatic correlation augmented self-consistent field theory to investigate the interactions between opposing PE brushes in a mixture of 1:1 and 3:1 salt solutions. Our theory predicts a hysteretic feature of the normal stress induced by strong ion correlations. In the presence of trivalent ions, the force profile is discontinuous: repulsive in the compression branch and adhesive in the separation branch. The molecular origin of the hysteretic force is the coexistence of two collapsed modes: two separated condensed layers on each surface in the compression and a single bundled condensed layer in the separation. With the systematic inclusion of ion correlations, our theory captures well the hysteretic force, adhesive separation, “jump-in” and “jump-out” features, and the “specific ion effect”, all in good agreement with the reported experimental results.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.1,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142237846","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-14DOI: 10.1021/acsmacrolett.4c0040410.1021/acsmacrolett.4c00404
Maria Regato-Herbella, Daniele Mantione, Agustín Blachman, Antonela Gallastegui, Graciela C. Calabrese, Sergio E. Moya*, David Mecerreyes* and Miryam Criado-Gonzalez*,
Multiresponsive hydrogels are valuable as biomaterials due to their ability to respond to multiple biologically relevant stimuli, i.e., temperature, pH, or reactive oxygen species (ROS), which can be present simultaneously in the body. In this work, we synthesize triple-responsive hydrogels through UV light photopolymerization of selected monomer compositions that encompass thermoresponsive N-isopropylacrylamide (NIPAM), pH-responsive methacrylic acid (MAA), and a tailor-made ROS-responsive diacrylate thioether monomer (EG3SA). As a result, smart P[NIPAMx-co-MAAy-co-(EG3SA)z] hydrogels capable of being manufactured by digital light processing (DLP) 4D printing are obtained. The thermo-, pH-, and ROS-response of the hydrogels are studied by swelling tests and rheological measurements at different temperatures (25 and 37 °C), pHs (3, 5, 7.4, and 11), and in the absence or presence of ROS (H2O2). The hydrogels are employed as matrixes for the encapsulation of ketoprofen (KET), an anti-inflammatory drug that shows a tunable release, depending on the hydrogel composition and stimuli applied. The cytotoxicity properties of the hydrogels are tested in vitro with mouse embryonic fibroblasts (NIH 3T3) and RAW 264.7 murine macrophage (RAW) cells. Finally, the anti-inflammatory properties are assessed, and the results exhibit a ≈70% nitric oxide reduction up to base values of pro-inflammatory RAW cells, which highlights the anti-inflammatory capacity of P[NIPAM80-co-MAA15-co-(EG3SA)5] hydrogels, per se, without being necessary to encapsulate an anti-inflammatory drug within their network. It opens the route for the fabrication of customizable 4D printable scaffolds for the effective treatment of inflammatory pathologies.
{"title":"Multiresponsive 4D Printable Hydrogels with Anti-Inflammatory Properties","authors":"Maria Regato-Herbella, Daniele Mantione, Agustín Blachman, Antonela Gallastegui, Graciela C. Calabrese, Sergio E. Moya*, David Mecerreyes* and Miryam Criado-Gonzalez*, ","doi":"10.1021/acsmacrolett.4c0040410.1021/acsmacrolett.4c00404","DOIUrl":"https://doi.org/10.1021/acsmacrolett.4c00404https://doi.org/10.1021/acsmacrolett.4c00404","url":null,"abstract":"<p >Multiresponsive hydrogels are valuable as biomaterials due to their ability to respond to multiple biologically relevant stimuli, i.e., temperature, pH, or reactive oxygen species (ROS), which can be present simultaneously in the body. In this work, we synthesize triple-responsive hydrogels through UV light photopolymerization of selected monomer compositions that encompass thermoresponsive <i>N</i>-isopropylacrylamide (NIPAM), pH-responsive methacrylic acid (MAA), and a tailor-made ROS-responsive diacrylate thioether monomer (EG<sub>3</sub>SA). As a result, smart P[NIPAM<sub><i>x</i></sub>-<i>co</i>-MAA<sub><i>y</i></sub>-<i>co</i>-(EG<sub>3</sub>SA)<sub><i>z</i></sub>] hydrogels capable of being manufactured by digital light processing (DLP) 4D printing are obtained. The thermo-, pH-, and ROS-response of the hydrogels are studied by swelling tests and rheological measurements at different temperatures (25 and 37 °C), pHs (3, 5, 7.4, and 11), and in the absence or presence of ROS (H<sub>2</sub>O<sub>2</sub>). The hydrogels are employed as matrixes for the encapsulation of ketoprofen (KET), an anti-inflammatory drug that shows a tunable release, depending on the hydrogel composition and stimuli applied. The cytotoxicity properties of the hydrogels are tested <i>in vitro</i> with mouse embryonic fibroblasts (NIH 3T3) and RAW 264.7 murine macrophage (RAW) cells. Finally, the anti-inflammatory properties are assessed, and the results exhibit a ≈70% nitric oxide reduction up to base values of pro-inflammatory RAW cells, which highlights the anti-inflammatory capacity of P[NIPAM<sub>80</sub>-<i>co</i>-MAA<sub>15</sub>-<i>co</i>-(EG<sub>3</sub>SA)<sub>5</sub>] hydrogels, <i>per se</i>, without being necessary to encapsulate an anti-inflammatory drug within their network. It opens the route for the fabrication of customizable 4D printable scaffolds for the effective treatment of inflammatory pathologies.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.1,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmacrolett.4c00404","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142237848","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}