ACS polymers Au最新文献

{"title":"Synthesis of Degradable Polysulfamides via Sulfur(VI) Fluoride Exchange Click Polymerization of AB-Type Monomers","authors":"Jiun Wei Wu,&nbsp;Ryan W. Kulow,&nbsp;McKenna J. Redding,&nbsp;Alexander J. Fine,&nbsp;Scott M. Grayson and Quentin Michaudel*,&nbsp;","doi":"10.1021/acspolymersau.2c00060","DOIUrl":"10.1021/acspolymersau.2c00060","url":null,"abstract":"<p >Polysulfamides are the −SO₂– analogues of polyureas and form an intriguing family of polymers containing hydrogen-bond donor and acceptor groups. However, unlike polyureas, their physical properties are mostly unknown because of the scarcity of synthetic methods to access such polymers. Herein, we report an expedient synthesis of AB monomers for the synthesis of polysulfamides via Sulfur(VI) Fluoride Exchange (SuFEx) click polymerization. Upon optimization of the step-growth process, a variety of polysulfamides were isolated and characterized. The versatility of the SuFEx polymerization allowed structural modulation of the main chain through the incorporation of aliphatic or aromatic amines. While all synthesized polymers presented high thermal stability via thermogravimetric analysis, the glass-transition temperature and crystallinity were shown to be highly tied to the structure of the backbone between repeating sulfamide units through differential scanning calorimetry and powder X-ray diffraction. Careful analysis via matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and X-ray crystallography also revealed the formation of macrocyclic oligomers during the polymerization of one AB monomer. Finally, two protocols were developed to efficiently degrade all synthesized polysulfamides through either chemical recycling for polymers derived from aromatic amines or oxidative upcycling for those based on aliphatic amines.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"3 3","pages":"259–266"},"PeriodicalIF":0.0,"publicationDate":"2023-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/8a/9a/lg2c00060.PMC10273414.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9706644","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}

{"title":"Quo Vadis Carbanionic Polymerization?","authors":"Konstantinos Ntetsikas,&nbsp;Viko Ladelta,&nbsp;Saibal Bhaumik and Nikos Hadjichristidis*,&nbsp;","doi":"10.1021/acspolymersau.2c00058","DOIUrl":"10.1021/acspolymersau.2c00058","url":null,"abstract":"<p >Living anionic polymerization will soon celebrate 70 years of existence. This living polymerization is considered the mother of all living and controlled/living polymerizations since it paved the way for their discovery. It provides methodologies for synthesizing polymers with absolute control of the essential parameters that affect polymer properties, including molecular weight, molecular weight distribution, composition and microstructure, chain-end/in-chain functionality, and architecture. This precise control of living anionic polymerization generated tremendous fundamental and industrial research activities, developing numerous important commodity and specialty polymers. In this Perspective, we present the high importance of living anionic polymerization of vinyl monomers by providing some examples of its significant achievements, presenting its current status, giving several insights into where it is going (Quo Vadis) and what the future holds for this powerful synthetic method. Furthermore, we attempt to explore its advantages and disadvantages compared to controlled/living radical polymerizations, the main competitors of living carbanionic polymerization.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"3 2","pages":"158–181"},"PeriodicalIF":0.0,"publicationDate":"2022-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/1b/b3/lg2c00058.PMC10103213.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9322891","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}

{"title":"ACS Polymers Au Recognizes 2022 Rising Stars in Polymers","authors":"Arthi Jayaraman*,&nbsp; and ,&nbsp;Harm-Anton Klok*,&nbsp;","doi":"10.1021/acspolymersau.2c00065","DOIUrl":"https://doi.org/10.1021/acspolymersau.2c00065","url":null,"abstract":"Dr. Shrayesh N. Patel is currently an Assistant Professor in the Pritzker School of Molecular Engineering at the University of Chicago. He holds a joint appointment in the Chemical Sciences and Engineering Division at Argonne National Lab, and is also a member of the Joint Center for Energy Storage Research (JCESR) − a DOE Energy Innovation Hub. Dr. Patel completed his undergraduate degree at the Georgia Institute of Technology in Chemical and Biomolecular Engineering in 2007, then received his Ph.D. in Chemical Engineering from the University of California, Berkeley in 2013 under the supervision of Dr. Nitash P. Balsara. Before joining the University of Chicago, he was a postdoctoral research associate in the Materials Research Laboratory at the University of California, Santa Barbara under the supervision of Dr. Michael Chabinyc and Dr. Edward Kramer. Dr. Patel’s research interests focus on enabling polymers for sustainable energy systems through fundamental understanding of charge and mass transport, relevant to energy storage and conversion devices such as lithium-ion and beyond lithium-ion batteries, redox flow batteries, and thermoelectrics. Overall, his research expertise lies at the interface of polymer science and engineering, electrochemistry, and organic electronics. You can learn about his group’s research by visiting: https://pme. uchicago.edu/group/patel-group. His Article for this issue is titled “Structure−Transport Properties Governing the Interplay in Humidity-Dependent Mixed Ionic and Electronic Conduction of Conjugated Polyelectrolytes”. Article DOI:10.1021/acspolymersau. 2c00005.","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"2 6","pages":"387–391"},"PeriodicalIF":0.0,"publicationDate":"2022-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.2c00065","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71562412","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}

{"title":"Enabling the Polymer Circular Economy: Innovations in Photoluminescent Labeling of Plastic Waste for Enhanced Sorting","authors":"Ryan R. Larder*,&nbsp; and ,&nbsp;Fiona L. Hatton*,&nbsp;","doi":"10.1021/acspolymersau.2c00040","DOIUrl":"10.1021/acspolymersau.2c00040","url":null,"abstract":"<p >It is widely accepted that moving from a linear to circular economy for plastics will be beneficial to reduce plastic pollution in our environment and to prevent loss of material value. However, challenges within the sorting of plastic waste often lead to contaminated waste streams that can devalue recyclates and hinder reprocessing. Therefore, the improvement of the sorting of plastic waste can lead to dramatic improvements in recyclate quality and enable circularity for plastics. Here, we discuss current sorting methods for plastic waste and review labeling techniques to enable enhanced sorting of plastic recyclates. Photoluminescent-based labeling is discussed in detail, including UV–vis organic and inorganic photoluminescent markers, infrared up-conversion, and X-ray fluorescent markers. Methods of incorporating labels within packaging, such as extrusion, surface coatings, and incorporation within external labels are also discussed. Additionally, we highlight some practical models for implementing some of the sorting techniques and provide an outlook for this growing field of research.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"3 2","pages":"182–201"},"PeriodicalIF":0.0,"publicationDate":"2022-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.2c00040","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9318465","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}

{"title":"Gelation Dynamics during Photo-Cross-Linking of Polymer Nanocomposite Hydrogels","authors":"Michael C. Burroughs,&nbsp;Tracy H. Schloemer,&nbsp;Daniel N. Congreve and Danielle J. Mai*,&nbsp;","doi":"10.1021/acspolymersau.2c00051","DOIUrl":"10.1021/acspolymersau.2c00051","url":null,"abstract":"<p >Embedding nanomaterials into polymer hydrogels enables the design of functional materials with tailored chemical, mechanical, and optical properties. Nanocapsules that protect interior cargo and disperse readily through a polymeric matrix have drawn particular interest for their ability to integrate chemically incompatible systems and to further expand the parameter space for polymer nanocomposite hydrogels. The properties of polymer nanocomposite hydrogels depend on the material composition and processing route, which were explored systematically in this work. The gelation kinetics of network-forming polymer solutions with and without silica-coated nanocapsules bearing polyethylene glycol (PEG) surface ligands were investigated using <i>in situ</i> dynamic rheology measurements. Network-forming polymers comprised either 4-arm or 8-arm star PEG with terminal anthracene groups, which dimerize upon irradiation with ultraviolet (UV) light. The PEG-anthracene solutions exhibited rapid gel formation upon UV exposure (365 nm); gel formation was observed as a crossover from liquid-like to solid-like behavior during <i>in situ</i> small-amplitude oscillatory shear rheology. This crossover time was non-monotonic with polymer concentration. Far below the overlap concentration (<i>c</i>/<i>c</i>* ≪ 1), spatially separated PEG-anthracene molecules were subject to forming intramolecular loops over intermolecular cross-links, thereby slowing the gelation process. Near the polymer overlap concentration (<i>c</i>/<i>c</i>* ∼ 1), rapid gelation was attributed to the ideal proximity of anthracene end groups from neighboring polymer molecules. Above the overlap concentration (<i>c</i>/<i>c</i>* &gt; 1), increased solution viscosities hindered molecular diffusion, thereby reducing the frequency of dimerization reactions. Adding nanocapsules to PEG-anthracene solutions resulted in faster gelation than nanocapsule-free PEG-anthracene solutions with equivalent effective polymer concentrations. The final elastic modulus of nanocomposite hydrogels increased with nanocapsule volume fraction, signifying synergistic mechanical reinforcement by nanocapsules despite not being cross-linked into the polymer network. Overall, these findings quantify the impact of nanocapsule addition on the gelation kinetics and mechanical properties of polymer nanocomposite hydrogels, which are promising materials for applications in optoelectronics, biotechnology, and additive manufacturing.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"3 2","pages":"217–227"},"PeriodicalIF":0.0,"publicationDate":"2022-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.2c00051","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9318464","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}

{"title":"Entropic Mixing of Ring/Linear Polymer Blends","authors":"Gary S. Grest*,&nbsp;Ting Ge,&nbsp;Steven J. Plimpton,&nbsp;Michael Rubinstein and Thomas C. O’Connor*,&nbsp;","doi":"10.1021/acspolymersau.2c00050","DOIUrl":"10.1021/acspolymersau.2c00050","url":null,"abstract":"<p >The topological constraints of nonconcatenated ring polymers force them to form compact loopy globular conformations with much lower entropy than unconstrained ideal rings. The closed-loop structure of ring polymers also enables them to be threaded by linear polymers in ring/linear blends, resulting in less compact ring conformations with higher entropy. This conformational entropy increase promotes mixing rings with linear polymers. Here, using molecular dynamics simulations for bead-spring chains, ring/linear blends are shown to be significantly more miscible than linear/linear blends and that there is an entropic mixing, negative χ, for ring/linear blends compared to linear/linear and ring/ring blends. In analogy with small angle neutron scattering, the static structure function <i>S</i>(<i>q</i>) is measured, and the resulting data are fit to the random phase approximation model to determine χ. In the limit that the two components are the same, χ = 0 for the linear/linear and ring/ring blends as expected, while χ &lt; 0 for the ring/linear blends. With increasing chain stiffness, χ for the ring/linear blends becomes more negative, varying reciprocally with the number of monomers between entanglements. Ring/linear blends are also shown to be more miscible than either ring/ring or linear/linear blends and stay in single phase for a wider range of increasing repulsion between the two components.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"3 2","pages":"209–216"},"PeriodicalIF":0.0,"publicationDate":"2022-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/07/5b/lg2c00050.PMC10103188.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9430205","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}

{"title":"Competitive Activation Experiments Reveal Significantly Different Mechanochemical Reactivity of Furan–Maleimide and Anthracene–Maleimide Mechanophores","authors":"Stella M. Luo,&nbsp;Ross W. Barber,&nbsp;Anna C. Overholts and Maxwell J. Robb*,&nbsp;","doi":"10.1021/acspolymersau.2c00047","DOIUrl":"10.1021/acspolymersau.2c00047","url":null,"abstract":"<p >During the past two decades, our understanding of mechanochemical reactivity has advanced considerably. Nevertheless, an incomplete knowledge of structure–activity relationships and the principles that govern mechanochemical transformations limits molecular design. The experimental development of mechanophores has thus benefited from simple computational tools like CoGEF, from which quantitative metrics like rupture force can be extracted to estimate reactivity. Furan–maleimide (FM) and anthracene–maleimide (AM) Diels–Alder adducts are widely studied mechanophores that undergo retro-Diels–Alder reactions upon mechanical activation in polymers. Despite possessing significantly different thermal stability, similar rupture forces predicted by CoGEF calculations suggest that these compounds exhibit similar mechanochemical reactivity. Here, we directly probe the relative mechanochemical reactivity of FM and AM adducts through competitive activation experiments. Ultrasound-induced mechanochemical activation of bis-adduct mechanophores comprising covalently tethered FM and AM subunits reveals pronounced selectivity─as high as ∼13:1─for reaction of the FM adduct compared to the AM adduct. Computational models provide insight into the greater reactivity of the FM mechanophore, indicating a more efficient mechanochemical coupling for the FM adduct compared to the AM adduct. The methodology employed here to directly interrogate the relative reactivity of two different mechanophores using a tethered bis-adduct configuration may be useful for other systems where more common sonication-based approaches are limited by poor sensitivity.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"3 2","pages":"202–208"},"PeriodicalIF":0.0,"publicationDate":"2022-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/ab/43/lg2c00047.PMC10103189.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9322893","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}

{"title":"A User’s Guide to Machine Learning for Polymeric Biomaterials","authors":"Travis A. Meyer,&nbsp;Cesar Ramirez,&nbsp;Matthew J. Tamasi and Adam J. Gormley*,&nbsp;","doi":"10.1021/acspolymersau.2c00037","DOIUrl":"10.1021/acspolymersau.2c00037","url":null,"abstract":"<p >The development of novel biomaterials is a challenging process, complicated by a design space with high dimensionality. Requirements for performance in the complex biological environment lead to difficult <i>a priori</i> rational design choices and time-consuming empirical trial-and-error experimentation. Modern data science practices, especially artificial intelligence (AI)/machine learning (ML), offer the promise to help accelerate the identification and testing of next-generation biomaterials. However, it can be a daunting task for biomaterial scientists unfamiliar with modern ML techniques to begin incorporating these useful tools into their development pipeline. This Perspective lays the foundation for a basic understanding of ML while providing a step-by-step guide to new users on how to begin implementing these techniques. A tutorial Python script has been developed walking users through the application of an ML pipeline using data from a real biomaterial design challenge based on group’s research. This tutorial provides an opportunity for readers to see and experiment with ML and its syntax in Python. The Google Colab notebook can be easily accessed and copied from the following URL: www.gormleylab.com/MLcolab</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"3 2","pages":"141–157"},"PeriodicalIF":0.0,"publicationDate":"2022-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/63/da/lg2c00037.PMC10103193.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9551321","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}

{"title":"Understanding and Modeling Polymers: The Challenge of Multiple Scales","authors":"F. Schmid","doi":"10.1021/acspolymersau.2c0004","DOIUrl":"https://doi.org/10.1021/acspolymersau.2c0004","url":null,"abstract":"Polymer materials have the characteristic feature that they are multiscale systems by definition. Already the description of a single molecules involves a multitude of different scales, and coopera-tive processes in polymer assemblies are governed by the interplay of these scales. Polymers have been among the first materials for which systematic multiscale techniques were developed, yet they continue to present extraordinary challenges for modellers. In this perspective, we review popular models that are used to describe polymers on different scales and discuss scale bridging strategies such as static and dynamic coarse-graining methods and multiresolution approaches. We close with a list of hard problems which still need to be solved in order to gain a comprehensive quantitative understanding of polymer systems on all scales.","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46851042","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}

{"title":"Understanding and Modeling Polymers: The Challenge of Multiple Scales","authors":"Friederike Schmid*,&nbsp;","doi":"10.1021/acspolymersau.2c00049","DOIUrl":"https://doi.org/10.1021/acspolymersau.2c00049","url":null,"abstract":"<p >Polymer materials are multiscale systems by definition. Already the description of a single macromolecule involves a multitude of scales, and cooperative processes in polymer assemblies are governed by their interplay. Polymers have been among the first materials for which systematic multiscale techniques were developed, yet they continue to present extraordinary challenges for modellers. In this Perspective, we review popular models that are used to describe polymers on different scales and discuss scale-bridging strategies such as static and dynamic coarse-graining methods and multiresolution approaches. We close with a list of hard problems which still need to be solved in order to gain a comprehensive quantitative understanding of polymer systems.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"3 1","pages":"28–58"},"PeriodicalIF":0.0,"publicationDate":"2022-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.2c00049","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49768376","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}