ACS polymers AuPub Date : 2022-09-15DOI: 10.1021/acspolymersau.2c00036
Abigail Mae Clapperton, Jon Babi and Helen Tran*,
{"title":"A Field Guide to Optimizing Peptoid Synthesis","authors":"Abigail Mae Clapperton, Jon Babi and Helen Tran*, ","doi":"10.1021/acspolymersau.2c00036","DOIUrl":"10.1021/acspolymersau.2c00036","url":null,"abstract":"<p >N-Substituted glycines (peptoids) are a class of peptidomimetic molecules used as materials for health, environmental, and drug delivery applications. Automated solid-phase synthesis is the most widely used approach for preparing polypeptoids, with a range of published protocols and modifications for selected synthetic targets. Simultaneously, emerging solution-phase syntheses are being leveraged to overcome limitations in solid-phase synthesis and access high-molecular weight polypeptoids. This Perspective aims to outline strategies for the optimization of both solid- and solution-phase synthesis, provide technical considerations for robotic synthesizers, and offer an outlook on advances in synthetic methodologies. The solid-phase synthesis sections explore steps for protocol optimization, accessing complex side chains, and adaptation to robotic synthesizers; the sections on solution-phase synthesis cover the selection of initiators, side chain compatibility, and strategies for controlling polymerization efficiency and scale. This text acts as a “field guide” for researchers aiming to leverage the flexibility and adaptability of peptoids in their research.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"2 6","pages":"417–429"},"PeriodicalIF":0.0,"publicationDate":"2022-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/7a/41/lg2c00036.PMC9756346.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"10841160","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}
ACS polymers AuPub Date : 2022-09-08DOI: 10.1021/acspolymersau.2c00031
Zijian Huo, Stephen J Skala, Lavinia R Falck, Jennifer E Laaser and Antonia Statt*,
{"title":"Computational Study of Mechanochemical Activation in Nanostructured Triblock Copolymers","authors":"Zijian Huo, Stephen J Skala, Lavinia R Falck, Jennifer E Laaser and Antonia Statt*, ","doi":"10.1021/acspolymersau.2c00031","DOIUrl":"10.1021/acspolymersau.2c00031","url":null,"abstract":"<p >Force-driven chemical reactions have emerged as an attractive platform for diverse applications in polymeric materials. However, the microscopic chain conformations and topologies necessary for efficiently transducing macroscopic forces to the molecular scale are not well-understood. In this work, we use a coarse-grained model to investigate the impact of network-like topologies on mechanochemical activation in self-assembled triblock copolymers. We find that mechanochemical activation during tensile deformation depends strongly on both the polymer composition and chain conformation in these materials. Activation primarily occurs in the tie chains connecting different glassy domains and in loop chains that are hooked onto each other by physical entanglements. Activation also requires a higher stress in materials having a higher glassy block content. Overall, the lamellar samples show the highest percent activation at high stress. In contrast, at low stress, the spherical morphology, which has the lowest glassy fraction, shows the highest activation. Additionally, we observe a spatial pattern of activation, which appears to be tied to distortion of the self-assembled morphology. Higher activation is observed in the tips of the chevrons formed during deformation of lamellar samples as well as in the centers between the cylinders in the cylindrical morphology. Our work shows that changes in the network-like topology in different morphologies significantly impact mechanochemical activation efficiencies in these materials, suggesting that this area will be a fruitful avenue for further experimental research.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"2 6","pages":"467–477"},"PeriodicalIF":0.0,"publicationDate":"2022-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/88/ec/lg2c00031.PMC9756960.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"10400594","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}
ACS polymers AuPub Date : 2022-08-26DOI: 10.1021/acspolymersau.2c00027
Paul Joshua Hurst, Annissa A. Graham and Joseph P. Patterson*,
{"title":"Gaining Structural Control by Modification of Polymerization Rate in Ring-Opening Polymerization-Induced Crystallization-Driven Self-Assembly","authors":"Paul Joshua Hurst, Annissa A. Graham and Joseph P. Patterson*, ","doi":"10.1021/acspolymersau.2c00027","DOIUrl":"10.1021/acspolymersau.2c00027","url":null,"abstract":"<p >Polymerization-induced self-assembly (PISA) has become an important one pot method for the preparation of well-defined block copolymer nanoparticles. In PISA, morphology is typically controlled by changing molecular architecture and polymer concentration. However, several computational and experimental studies have suggested that changes in polymerization rate can lead to morphological differences. Here, we demonstrate that catalyst selection can be used to control morphology independent of polymer structure and concentration in ring-opening polymerization-induced crystallization-driven self-assembly (ROPI-CDSA). Slower rates of polymerization give rise to slower rates of self-assembly, resulting in denser lamellae and more 3D structures when compared to faster rates of polymerization. Our explanation for this is that the fast samples transiently exist in a nonequilibrium state as self-assembly starts at a higher solvophobic block length when compared to the slow polymerization. We expect that subsequent examples of rate variation in PISA will allow for greater control over morphological outcome.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"2 6","pages":"501–509"},"PeriodicalIF":0.0,"publicationDate":"2022-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/b4/da/lg2c00027.PMC9756957.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"10400599","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}
ACS polymers AuPub Date : 2022-08-24DOI: 10.1021/acspolymersau.2c00032
Long Li, Libin Wu, Moritz Urschbach, David Straßburger, Xiaomei Liu, Pol Besenius* and Guosong Chen*,
{"title":"Modular Platform of Carbohydrates-modified Supramolecular Polymers Based on Dendritic Peptide Scaffolds","authors":"Long Li, Libin Wu, Moritz Urschbach, David Straßburger, Xiaomei Liu, Pol Besenius* and Guosong Chen*, ","doi":"10.1021/acspolymersau.2c00032","DOIUrl":"10.1021/acspolymersau.2c00032","url":null,"abstract":"<p >Glycopeptide supramolecular polymers displaying multivalent carbohydrates are particularly suitable for immune-relevant biomaterials, due to the important functions of carbohydrates in mediating cell-cell communication and modulating immune responses. However, the diversity and complexity of carbohydrates limited the generation of glycopeptide supramolecular monomers. Thereby, a modular platform of presenting various carbohydrates, especially more complex oligosaccharides, is highly desirable but remains underexplored. Here, we first prepared the linear amphiphilic glycopeptides that self-assembled into spherical nanoparticles and worm-like nanoparticles. Furthermore, the dendritic glycopeptides that self-assembled into uniform nanorods were designed to generate modular supramolecular polymers with variable functionality, via redesigning the molecular backbone. With various functional oligosaccharide-modified supramolecular polymers, the in vitro studies further indicated that these polymers were not cytotoxic to macrophages, and significantly modulated the production of proinflammatory cytokines. These findings provide a promising platform to develop supramolecular glycopeptide biomaterials with potential applications in immunomodulation and immunotherapy.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"2 6","pages":"478–485"},"PeriodicalIF":0.0,"publicationDate":"2022-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/20/c6/lg2c00032.PMC9756342.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"10400597","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}
ACS polymers AuPub Date : 2022-08-23DOI: 10.1021/acspolymersau.2c00033
Timothy P. Lodge*, Claire L. Seitzinger, Sarah C. Seeger, Sanghee Yang, Supriya Gupta and Kevin D. Dorfman,
{"title":"Dynamics and Equilibration Mechanisms in Block Copolymer Particles","authors":"Timothy P. Lodge*, Claire L. Seitzinger, Sarah C. Seeger, Sanghee Yang, Supriya Gupta and Kevin D. Dorfman, ","doi":"10.1021/acspolymersau.2c00033","DOIUrl":"10.1021/acspolymersau.2c00033","url":null,"abstract":"<p >Self-assembly of block copolymers into interesting and useful nanostructures, in both solution and bulk, is a vibrant research arena. While much attention has been paid to characterization and prediction of equilibrium phases, the associated dynamic processes are far from fully understood. Here, we explore what is known and not known about the equilibration of particle phases in the bulk, and spherical micelles in solution. The presumed primary equilibration mechanisms are chain exchange, fusion, and fragmentation. These processes have been extensively studied in surfactants and lipids, where they occur on subsecond time scales. In contrast, increased chain lengths in block copolymers create much larger barriers, and time scales can become prohibitively slow. In practice, equilibration of block copolymers is achievable only in proximity to the critical micelle temperature (in solution) or the order–disorder transition (in the bulk). Detailed theories for these processes in block copolymers are few. In the bulk, the rate of chain exchange can be quantified by tracer diffusion measurements. Often the rate of equilibration, in terms of number density and aggregation number of particles, is much slower than chain exchange, and consequently observed particle phases are often metastable. This is particularly true in regions of the phase diagram where Frank–Kasper phases occur. Chain exchange in solution has been explored quantitatively by time-resolved SANS, but the results are not well captured by theory. Computer simulations, particularly via dissipative particle dynamics, are beginning to shed light on the chain escape mechanism at the molecular level. The rate of fragmentation has been quantified in a few experimental systems, and TEM images support a mechanism akin to the anaphase stage of mitosis in cells, via a thin neck that pinches off to produce two smaller micelles. Direct measurements of micelle fusion are quite rare. Suggestions for future theoretical, computational, and experimental efforts are offered.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"2 6","pages":"397–416"},"PeriodicalIF":0.0,"publicationDate":"2022-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/6a/16/lg2c00033.PMC9756915.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"10400596","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}
ACS polymers AuPub Date : 2022-08-18DOI: 10.1021/acspolymersau.2c00030
Seigo Watanabe, Teru Takayama and Kenichi Oyaizu*,
{"title":"Transcending the Trade-off in Refractive Index and Abbe Number for Highly Refractive Polymers: Synergistic Effect of Polarizable Skeletons and Robust Hydrogen Bonds","authors":"Seigo Watanabe, Teru Takayama and Kenichi Oyaizu*, ","doi":"10.1021/acspolymersau.2c00030","DOIUrl":"10.1021/acspolymersau.2c00030","url":null,"abstract":"<p >High-refractive-index polymers (HRIPs) are attractive materials for the development of optical devices with high performances. However, because practical components and structures for HRIPs are limited from the viewpoint of synthetic techniques, it has proved difficult using traditional strategies to enhance the refractive index (RI) of HRIPs to more than a certain degree (over 1.8) while maintaining their visible transparency. Here, we found that poly(phenylene sulfide) (<b>PPS</b>) derivatives featuring both methylthio and hydroxy groups can simultaneously exhibit balanced properties of an ultrahigh RI of <i>n</i><sub>D</sub> = 1.85 and Abbe number of ν<sub>D</sub> = 20 owing to the synergistic effect of high molar refraction and dense intermolecular hydrogen bonds (H-bonds). This brand new strategy is anticipated to contribute to the development of HRIPs displaying ultrahigh RI with adequate Abbe numbers beyond the empirical <i>n</i><sub>D</sub>–ν<sub>D</sub> threshold, which has not been achieved to date.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"2 6","pages":"458–466"},"PeriodicalIF":0.0,"publicationDate":"2022-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/86/12/lg2c00030.PMC9955235.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9363067","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}
ACS polymers AuPub Date : 2022-08-05DOI: 10.1021/acspolymersau.2c00028
Toru Ishibe, Natalia Gonzalez-Martinez, Panagiotis G. Georgiou, Kathryn A. Murray and Matthew I. Gibson*,
{"title":"Synthesis of Poly(2-(methylsulfinyl)ethyl methacrylate) via Oxidation of Poly(2-(methylthio)ethyl methacrylate): Evaluation of the Sulfoxide Side Chain on Cryopreservation","authors":"Toru Ishibe, Natalia Gonzalez-Martinez, Panagiotis G. Georgiou, Kathryn A. Murray and Matthew I. Gibson*, ","doi":"10.1021/acspolymersau.2c00028","DOIUrl":"10.1021/acspolymersau.2c00028","url":null,"abstract":"<p >Conventional cryopreservation solutions rely on the addition of organic solvents such as DMSO or glycerol, but these do not give full recovery for all cell types, and innovative cryoprotectants may address damage pathways which these solvents do not protect against. Macromolecular cryoprotectants are emerging, but there is a need to understand their structure–property relationships and mechanisms of action. Here we synthesized and investigated the cryoprotective behavior of sulfoxide (i.e., “DMSO-like”) side-chain polymers, which have been reported to be cryoprotective using poly(ethylene glycol)-based polymers. We also wanted to determine if the polarized sulfoxide bond (S<sup>+</sup>O<sup>–</sup> character) introduces cryoprotective effects, as this has been seen for mixed-charge cryoprotective polyampholytes, whose mechanism of action is not yet understood. Poly(2-(methylsulfinyl)ethyl methacrylate) was synthesized by RAFT polymerization of 2-(methylthio)ethyl methacrylate and subsequent oxidation to sulfoxide. A corresponding <i>N</i>-oxide polymer was also prepared and characterized: (poly(2-(dimethylamineoxide)ethyl methacrylate). Ice recrystallization inhibition assays and differential scanning calorimetry analysis show that the sulfoxide side chains do not modulate the frozen components during cryopreservation. In cytotoxicity assays, it was found that long-term (24 h) exposure of the polymers was not tolerated by cells, but shorter (30 min) incubation times, which are relevant for cryopreservation, were tolerated. It was also observed that overoxidation to the sulfone significantly increased the cytotoxicity, and hence, these materials require a precision oxidation step to be deployed. In suspension cell cryopreservation investigations, the polysulfoxides did not increase cell recovery 24 h post-thaw. These results show that unlike hydrophilic backboned polysulfides, which can aid cryopreservation, the installation of the sulfoxide group onto a polymer does not necessarily bring cryoprotective properties, highlighting the challenges of developing and discovering macromolecular cryoprotectants.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"2 6","pages":"449–457"},"PeriodicalIF":0.0,"publicationDate":"2022-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9756334/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"10400595","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}
ACS polymers AuPub Date : 2022-07-27DOI: 10.1021/acspolymersau.2c00023
Gadi Slor, Shahar Tevet and Roey J. Amir*,
{"title":"Stimuli-Induced Architectural Transition as a Tool for Controlling the Enzymatic Degradability of Polymeric Micelles","authors":"Gadi Slor, Shahar Tevet and Roey J. Amir*, ","doi":"10.1021/acspolymersau.2c00023","DOIUrl":"10.1021/acspolymersau.2c00023","url":null,"abstract":"<p >Enzyme-responsive polymeric micelles hold great potential as drug delivery systems due to the overexpression of disease-associated enzymes. To achieve selective and efficient delivery of their therapeutic cargo, micelles need to be highly stable and yet disassemble when encountering their activating enzyme at the target site. However, increased micellar stability is accompanied by a drastic decrease in enzymatic degradability. The need to balance between stability and enzymatic degradation has severely limited the therapeutic applicability of enzyme-responsive nanocarriers. Here, we report a general modular approach for designing stable enzyme-responsive micelles whose enzymatic degradation can be enhanced on demand. The control over their response to the activating enzyme is achieved by stimuli-induced splitting of triblock amphiphiles into two identical diblock amphiphiles, which have the same hydrophilic–lipophilic balance as the parent amphiphile. This architectural transition drastically affects the micelle–unimer equilibrium and therefore increases the sensitivity of the micelles toward enzymatic degradation. As a proof of concept, we designed UV- and reduction-activated splitting mechanisms, demonstrating the ability to use architectural transition as a tool for tuning amphiphile–protein interactions, providing a general solution toward overcoming the stability–degradability barrier for enzyme-responsive nanocarriers.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"2 5","pages":"380–386"},"PeriodicalIF":0.0,"publicationDate":"2022-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9955281/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"10817843","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}
ACS polymers AuPub Date : 2022-07-25DOI: 10.1021/acspolymersau.2c00017
Christian Czysch, Thi Dinh, Yannick Fröder, Leon Bixenmann, Patric Komforth, Alexander Balint, Hans-Joachim Räder, Stefan Naumann and Lutz Nuhn*,
{"title":"Nontoxic N-Heterocyclic Olefin Catalyst Systems for Well-Defined Polymerization of Biocompatible Aliphatic Polycarbonates","authors":"Christian Czysch, Thi Dinh, Yannick Fröder, Leon Bixenmann, Patric Komforth, Alexander Balint, Hans-Joachim Räder, Stefan Naumann and Lutz Nuhn*, ","doi":"10.1021/acspolymersau.2c00017","DOIUrl":"https://doi.org/10.1021/acspolymersau.2c00017","url":null,"abstract":"<p >Herein, <i>N</i>-heterocyclic olefins (NHOs) are utilized as catalysts for the ring-opening polymerization (ROP) of functional aliphatic carbonates. This emerging class of catalysts provides high reactivity and rapid conversion. Aiming for the polymerization of monomers with high side chain functionality, six-membered carbonates derived from 2,2-bis(hydroxymethyl)propionic acid (bis-MPA) served as model compounds. Tuning the reactivity of NHO from predominant side chain transesterification at room temperature toward ring-opening at lowered temperatures (−40 °C) enables controlled ROP. These refined conditions give narrowly distributed polymers of the hydrophobic carbonate 5-methyl-5-benzyloxycarbonyl-1,3-dioxan-2-one (MTC-OBn) (<i>Đ</i> < 1.30) at (pseudo)first-order kinetic polymerization progression. End group definition of these polymers demonstrated by mass spectrometry underlines the absence of side reactions. For the active ester monomer 5-methyl-5-pentafluorophenyloxycarbonyl-1,3-dioxane-2-one (MTC-PFP) with elevated side chain reactivity, a cocatalysis system consisting of NHO and the Lewis acid magnesium iodide is required to retune the reactivity from side chains toward controlled ROP. Excellent definition of the products (<i>Đ</i> < 1.30) and mass spectrometry data demonstrate the feasibility of this cocatalyst approach, since MTC-PFP has thus far only been polymerized successfully using acidic catalysts with moderate control. The broad feasibility of our findings was further demonstrated by the synthesis of block copolymers for bioapplications and their successful nanoparticular assembly. High tolerability of NHO in vitro with concentrations ranging up to 400 μM (equivalent to 0.056 mg/mL) further emphasize the suitability as a catalyst for the synthesis of bioapplicable materials. The polycarbonate block copolymer mPEG<sub>44</sub>-<i>b</i>-poly(MTC-OBn) enables physical entrapment of hydrophobic dyes in sub-20 nm micelles, whereas the active ester block copolymer mPEG<sub>44</sub>-<i>b</i>-poly(MTC-PFP) is postfunctionalizable by covalent dye attachment. Both block copolymers thereby serve as platforms for physical or covalent modification of nanocarriers for drug delivery.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"2 5","pages":"371–379"},"PeriodicalIF":0.0,"publicationDate":"2022-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.2c00017","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71608806","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}
ACS polymers AuPub Date : 2022-07-22DOI: 10.1021/acspolymersau.2c00026
Glenn H. Fredrickson*, Shuyi Xie, Jerrick Edmund, My Linh Le, Dan Sun, Douglas J. Grzetic, Daniel L. Vigil, Kris T. Delaney, Michael L. Chabinyc and Rachel A. Segalman,
{"title":"Ionic Compatibilization of Polymers","authors":"Glenn H. Fredrickson*, Shuyi Xie, Jerrick Edmund, My Linh Le, Dan Sun, Douglas J. Grzetic, Daniel L. Vigil, Kris T. Delaney, Michael L. Chabinyc and Rachel A. Segalman, ","doi":"10.1021/acspolymersau.2c00026","DOIUrl":"10.1021/acspolymersau.2c00026","url":null,"abstract":"<p >The small specific entropy of mixing of high molecular weight polymers implies that most blends of dissimilar polymers are immiscible with poor physical properties. Historically, a wide range of compatibilization strategies have been pursued, including the addition of copolymers or emulsifiers or installing complementary reactive groups that can promote the <i>in situ</i> formation of block or graft copolymers during blending operations. Typically, such reactive blending exploits reversible or irreversible covalent or hydrogen bonds to produce the desired copolymer, but there are other options. Here, we argue that ionic bonds and electrostatic correlations represent an underutilized tool for polymer compatibilization and in tailoring materials for applications ranging from sustainable polymer alloys to organic electronics and solid polymer electrolytes. The theoretical basis for ionic compatibilization is surveyed and placed in the context of existing experimental literature and emerging classes of functional polymer materials. We conclude with a perspective on how electrostatic interactions might be exploited in plastic waste upcycling.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"2 5","pages":"299–312"},"PeriodicalIF":0.0,"publicationDate":"2022-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9576261/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"40576933","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}