ACS polymers Au最新文献

{"title":"Calculating Pairwise Similarity of Polymer Ensembles via Earth Mover’s Distance","authors":"Jiale Shi,&nbsp;Dylan Walsh,&nbsp;Weizhong Zou,&nbsp;Nathan J. Rebello,&nbsp;Michael E. Deagen,&nbsp;Katharina A. Fransen,&nbsp;Xian Gao,&nbsp;Bradley D. Olsen* and Debra J. Audus*,&nbsp;","doi":"10.1021/acspolymersau.3c00029","DOIUrl":"10.1021/acspolymersau.3c00029","url":null,"abstract":"<p >Synthetic polymers, in contrast to small molecules and deterministic biomacromolecules, are typically ensembles composed of polymer chains with varying numbers, lengths, sequences, chemistry, and topologies. While numerous approaches exist for measuring pairwise similarity among small molecules and sequence-defined biomacromolecules, accurately determining the pairwise similarity between two polymer ensembles remains challenging. This work proposes the earth mover’s distance (EMD) metric to calculate the pairwise similarity score between two polymer ensembles. EMD offers a greater resolution of chemical differences between polymer ensembles than the averaging method and provides a quantitative numeric value representing the pairwise similarity between polymer ensembles in alignment with chemical intuition. The EMD approach for assessing polymer similarity enhances the development of accurate chemical search algorithms within polymer databases and can improve machine learning techniques for polymer design, optimization, and property prediction.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"4 1","pages":"66–76"},"PeriodicalIF":0.0,"publicationDate":"2024-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00029","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139439376","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":"Trimethylsilanol Cleaves Stable Azaylides As Revealed by Unfolding of Robust “Staudinger” Single-Chain Nanoparticles","authors":"Agustín Blázquez-Martín,&nbsp;Sebastián Bonardd,&nbsp;Ester Verde-Sesto,&nbsp;Arantxa Arbe and José A. Pomposo*,&nbsp;","doi":"10.1021/acspolymersau.3c00046","DOIUrl":"10.1021/acspolymersau.3c00046","url":null,"abstract":"<p >Herein, we disclose a unique and selective reagent for the cleavage of stable azaylides prepared by the nonhydrolysis Staudinger reaction, enabling the on-demand unfolding of robust single-chain nanoparticles (SCNPs). SCNPs with promising use in catalysis, nanomedicine, and sensing are obtained through intrachain folding of discrete synthetic polymer chains. The unfolding of SCNPs involving reversible interactions triggered by a variety of external stimuli (e.g., pH, temperature, light, and redox potential) or substances (e.g., competitive reagents, solvents, and anions) is well known. Conversely, methods for the unfolding (i.e., intrachain disassembly) of SCNPs with stronger covalent interactions are scarce. We show that trimethylsilanol (Me₃SiOH) triggers the efficient unfolding of robust “Staudinger” SCNPs with stable azaylide (−N═P−) moieties as intrachain cross-linking units showing exceptional stability toward water, air, and CS₂, a standard reagent for azaylides. As a consequence, Me₃SiOH arises as a rare, exceptional, and valuable reagent for the cleavage of stable azaylides prepared by the nonhydrolysis Staudinger reaction.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"4 2","pages":"140–148"},"PeriodicalIF":0.0,"publicationDate":"2024-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00046","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139422943","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":"3D Printable Modular Soft Elastomers from Physically Cross-linked Homogeneous Associative Polymers","authors":"Myoeum Kim,&nbsp;Shifeng Nian,&nbsp;Daniel A. Rau,&nbsp;Baiqiang Huang,&nbsp;Jinchang Zhu,&nbsp;Guillaume Freychet,&nbsp;Mikhail Zhernenkov and Li-Heng Cai*,&nbsp;","doi":"10.1021/acspolymersau.3c00021","DOIUrl":"10.1021/acspolymersau.3c00021","url":null,"abstract":"<p >Three-dimensional (3D) printing of elastomers enables the fabrication of many technologically important structures and devices. However, there remains a critical need for the development of reprocessable, solvent-free, soft elastomers that can be printed without the need for post-treatment. Herein, we report modular soft elastomers suitable for direct ink writing (DIW) printing by physically cross-linking associative polymers with a high fraction of reversible bonds. We designed and synthesized linear-associative-linear (LAL) triblock copolymers; the middle block is an associative polymer carrying amide groups that form double hydrogen bonding, and the end blocks aggregate to hard glassy domains that effectively act as physical cross-links. The amide groups do not aggregate to nanoscale clusters and only slow down polymer dynamics without changing the shape of the linear viscoelastic spectra; this enables molecular control over energy dissipation by varying the fraction of the associative groups. Increasing the volume fraction of the end linear blocks increases the network stiffness by more than 100 times without significantly compromising the extensibility. We created elastomers with Young’s moduli ranging from 8 kPa to 8 MPa while maintaining the tensile breaking strain around 150%. Using a high-temperature DIW printing platform, we transformed our elastomers to complex, highly deformable 3D structures without involving any solvent or post-print processing. Our elastomers represent the softest melt reprocessable materials for DIW printing. The developed LAL polymers synergize emerging homogeneous associative polymers with a high fraction of reversible bonds and classical block copolymer self-assembly to form a dual-cross-linked network, providing a versatile platform for the modular design and development of soft melt reprocessable elastomeric materials for practical applications.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"4 2","pages":"98–108"},"PeriodicalIF":0.0,"publicationDate":"2024-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00021","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139093639","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":"Effect of Polymer Gel Elasticity on Complex Coacervate Phase Behavior","authors":"Kathryn G. Wilcox,&nbsp;Kai R. Yamagami,&nbsp;Brittany K. Roopnarine,&nbsp;Adam Linscott and Svetlana Morozova*,&nbsp;","doi":"10.1021/acspolymersau.3c00027","DOIUrl":"10.1021/acspolymersau.3c00027","url":null,"abstract":"<p >Gels are key materials in biological systems such as tissues and may control biocondensate formation and structure. To further understand the effects of elastic environments on biomacromolecular assembly, we have investigated the phase behavior and radii of complex coacervate droplets in polyacrylamide (PAM) networks as a function of gel modulus. Poly-<span>l</span>-lysine (PLL) and sodium hyaluronate (HA) complex coacervate phases were prepared in PAM gels with moduli varying from 0.035 to 15.0 kPa. The size of the complex coacervate droplets is reported from bright-field microscopy and confocal fluorescence microscopy. Overall, the complex coacervate droplet volume decreases inversely with the modulus. Fluorescence microscopy is also used to determine the phase behavior and concentration of fluorescently tagged HA in the complex coacervate phases as a function of ionic strength (100–270 mM). We find that the critical ionic strength and complex coacervate stability are nonmonotonic as a function of the network modulus and that the local gel concentration can be used to control phase behavior and complex coacervate droplet size scale. By understanding how elastic environments influence simple electrostatic assembly, we can further understand how biomacromolecules exist in complex, crowded, and elastic cellular environments.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"4 2","pages":"109–119"},"PeriodicalIF":0.0,"publicationDate":"2023-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00027","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139053132","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":"Carborane-Containing Polymers: Synthesis, Properties, and Applications","authors":"Xinyi Zhang,&nbsp;Louis M. Rendina* and Markus Müllner*,&nbsp;","doi":"10.1021/acspolymersau.3c00030","DOIUrl":"10.1021/acspolymersau.3c00030","url":null,"abstract":"<p >Carboranes are an important class of electron-delocalized icosahedral carbon–boron clusters with unique physical and chemical properties, which can offer various functions to polymers including enhanced heat-resistance, tuned electronic properties and hydrophobicity, special ability of dihydrogen bond formation, and thermal neutron capture. Carborane-containing polymers have been synthesized mainly by means of step-growth polymerizations of disubstituted carborane monomers, with chain-growth polymerizations of monosubstituted carborane monomers including ATRP, RAFT, and ROMP only utilized recently. Carborane-containing polymers may find application as harsh-environment resistant materials, ceramic precursors, fluorescent materials with tuned emissive properties, novel optoelectronic devices, potential BNCT agents, and drug carriers with low cytotoxicity. This review highlights carborane-containing polymer synthesis strategies and potential applications, showcasing the versatile properties and possibilities that this unique family of boron compounds can provide to the polymeric systems.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"4 1","pages":"7–33"},"PeriodicalIF":0.0,"publicationDate":"2023-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00030","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138680114","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":"Antimicrobial Peptide–Poly(ethylene glycol) Conjugates: Connecting Molecular Architecture, Solution Properties, and Functional Performance","authors":"Zixian Cui,&nbsp;Matthew A. Crawford,&nbsp;Blake A. Rumble,&nbsp;Megan M. Krogh,&nbsp;Molly A. Hughes and Rachel A. Letteri*,&nbsp;","doi":"10.1021/acspolymersau.3c00026","DOIUrl":"10.1021/acspolymersau.3c00026","url":null,"abstract":"<p >Antimicrobial peptides (AMPs) are promising alternatives to conventional antibiotics for treating infections caused by drug-resistant bacteria; yet, many peptides are limited by toxicity to eukaryotic cells and instability in biological environments. Conjugation to linear polymers that reduce cytotoxicity and improve stability, however, often decreases antimicrobial activity. In this work, we combine the biocompatibility advantages of poly(ethylene glycol) (PEG) with the efficacy merits of nonlinear polymer architectures that accommodate multiple AMPs per molecule. By conjugating a chemokine-derived AMP, stapled Ac-P9, to linear and star-shaped PEG with various arm numbers and lengths, we investigated the role of molecular architecture in solution properties (i.e., ζ-potential, size, and morphology) and performance (i.e., antimicrobial activity, hemolysis, and protease resistance). Linear, 4-arm, and 8-arm conjugates with 2–2.5 kDa PEG arms were found to form nanoscale structures in solution with lower ζ-potentials relative to the unconjugated AMP, suggesting that the polymer partially shields the cationic AMP. Reducing the length of the PEG arms of the 8-arm conjugate to 1.25 kDa appeared to better reveal the peptide, seen by the increased ζ-potential, and promote assembly into particles with a larger size and defined spherical morphology. The antimicrobial effects exerted by the short 8-arm conjugate rivaled that of the unconjugated peptide, and the AMP constituents of the short 8-arm conjugate were protected from proteolytic degradation. All other conjugates examined also imparted a degree of protease resistance, but exhibited some reduced level of antimicrobial activity as compared to the AMP alone. None of the conjugates caused significant cytotoxic effects, which bodes well for their future potential to treat infections. While enhancing proteolytic stability often comes with the cost of lower antimicrobial activity, we have found that presenting AMPs at high density on a neutral nonlinear polymer strikes a favorable balance, exhibiting both enhanced stability and high antimicrobial activity.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"4 1","pages":"45–55"},"PeriodicalIF":0.0,"publicationDate":"2023-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00026","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138632422","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":"One Pot Photomediated Formation of Electrically Conductive Hydrogels","authors":"Dan My Nguyen,&nbsp;Chun-Yuan Lo,&nbsp;Tianzheng Guo,&nbsp;Taewook Choi,&nbsp;Shalini Sundar,&nbsp;Zachary Swain,&nbsp;Yuhang Wu,&nbsp;Charles Dhong and Laure V. Kayser*,&nbsp;","doi":"10.1021/acspolymersau.3c00031","DOIUrl":"10.1021/acspolymersau.3c00031","url":null,"abstract":"<p >Electrically conductive hydrogels represent an innovative platform for the development of bioelectronic devices. While photolithography technologies have enabled the fabrication of complex architectures with high resolution, photoprinting conductive hydrogels is still a challenging task because the conductive polymer absorbs light which can outcompete photopolymerization of the insulating scaffold. In this study, we introduce an approach to synthesizing conductive hydrogels in one step. Our approach combines the simultaneous photo-cross-linking of a polymeric scaffold and the polymerization of 3,4-ethylene dioxythiophene (EDOT), without additional photocatalysts. This process involves the copolymerization of photo-cross-linkable coumarin-containing monomers with sodium styrenesulfonate to produce a water-soluble poly(styrenesulfonate-<i>co</i>-coumarin acrylate) (P(SS-<i>co</i>-CoumAc)) copolymer. Our findings reveal that optimizing the [SS]:[CoumAc] ratio at 100:5 results in hydrogels with the strain at break up to 16%. This mechanical resilience is coupled with an electronic conductivity of 9.2 S m^–1 suitable for wearable electronics. Furthermore, the conductive hydrogels can be photopatterned to achieve micrometer-sized structures with high resolution. The photo-cross-linked hydrogels are used as electrodes to record stable and reliable surface electromyography (sEMG) signals. These novel photo-cross-linkable polymers combined with one-pot PEDOT (poly-EDOT) polymerization open possibilities for rapidly prototyping complex bioelectronic devices and creating custom-designed interfaces between electronics and biological systems.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"4 1","pages":"34–44"},"PeriodicalIF":0.0,"publicationDate":"2023-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00031","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138555348","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":"Navigating the Expansive Landscapes of Soft Materials: A User Guide for High-Throughput Workflows","authors":"Erin C. Day,&nbsp;Supraja S. Chittari,&nbsp;Matthew P. Bogen and Abigail S. Knight*,&nbsp;","doi":"10.1021/acspolymersau.3c00025","DOIUrl":"10.1021/acspolymersau.3c00025","url":null,"abstract":"<p >Synthetic polymers are highly customizable with tailored structures and functionality, yet this versatility generates challenges in the design of advanced materials due to the size and complexity of the design space. Thus, exploration and optimization of polymer properties using combinatorial libraries has become increasingly common, which requires careful selection of synthetic strategies, characterization techniques, and rapid processing workflows to obtain fundamental principles from these large data sets. Herein, we provide guidelines for strategic design of macromolecule libraries and workflows to efficiently navigate these high-dimensional design spaces. We describe synthetic methods for multiple library sizes and structures as well as characterization methods to rapidly generate data sets, including tools that can be adapted from biological workflows. We further highlight relevant insights from statistics and machine learning to aid in data featurization, representation, and analysis. This Perspective acts as a “user guide” for researchers interested in leveraging high-throughput screening toward the design of multifunctional polymers and predictive modeling of structure–property relationships in soft materials.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"3 6","pages":"406–427"},"PeriodicalIF":0.0,"publicationDate":"2023-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00025","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138547766","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":"Surface-Initiated PET-RAFT via the Z-Group Approach","authors":"Sai Dileep Kumar Seera,&nbsp; and ,&nbsp;Christian W. Pester*,&nbsp;","doi":"10.1021/acspolymersau.3c00028","DOIUrl":"10.1021/acspolymersau.3c00028","url":null,"abstract":"<p >Surface-initiated reversible addition–fragmentation chain transfer (SI-RAFT) is a user-friendly and versatile approach for polymer brush engineering. For SI-RAFT, synthetic strategies follow either surface-anchoring of radical initiators (e.g., azo compounds) or anchoring RAFT chain transfer agents (CTAs) onto a substrate. The latter can be performed via the R-group or Z-group of the CTA, with the previous scientific focus in literature skewed heavily toward work on the R-group approach. This contribution investigates the alternative: a Z-group approach toward light-mediated SI photoinduced electron transfer RAFT (SI-PET-RAFT) polymerization. An appropriate RAFT CTA is synthesized, immobilized onto SiO₂, and its ability to control the growth (and chain extension) of polymer brushes in both organic and aqueous environments is investigated with different acrylamide and methacrylate monomers. O₂ tolerance allows Z-group SI-PET-RAFT to be performed under ambient conditions, and patterning surfaces through photolithography is illustrated. Polymer brushes are characterized via X-ray photoelectron spectroscopy (XPS), ellipsometry, and water contact angle measurements. An examination of polymer brush grafting density showed variation from 0.01 to 0.16 chains nm^–2. Notably, in contrast to the R-group SI-RAFT approach, this chemical approach allows the growth of intermittent layers of polymer brushes underneath the top layer without changing the properties of the outermost surface.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"3 6","pages":"428–436"},"PeriodicalIF":0.0,"publicationDate":"2023-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00028","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138528591","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":"Intermediate Polymer Relaxation Explains the Anomalous Rheology of Nanocomposites with Ultrasmall Attractive POSS Nanoparticles","authors":"Walter W. Young,&nbsp; and ,&nbsp;Reika Katsumata*,&nbsp;","doi":"10.1021/acspolymersau.3c00020","DOIUrl":"10.1021/acspolymersau.3c00020","url":null,"abstract":"<p >The rheological properties of entangled polymers loaded with very small, strongly attractive polyhedral oligomeric silsesquioxane (POSS) fillers differ from that of nanocomposites with larger fillers by (1) the shorter breadth of the entanglement plateau and (2) the relatively unchanged terminal viscosity with increasing POSS loading. Although such anomalous rheological properties can rewrite the property–processing map of materials (e.g., high glass transition temperature and low viscosity), their mechanism remains unclear. In this study, we report that polymer relaxations on intermediate time scales between α and entire-chain relaxation, so-called “slower processes”, are responsible for this unusual rheological behavior of poly(2-vinylpyridine)/octa(aminophenyl)silsesquioxane (P2VP/OAPS) nanocomposites. To uncover the effects of entanglements on the nanocomposite dynamics, rheometry is used for variable matrix molecular weights. Results show a systematic change in the rheological response, which is independent of the molecular weight, and in turn, the presence of entanglements. This supports a physical interpretation that a slower process dominates the rheological response of the material at intermediate frequencies on length scales larger than the segment length or the OAPS diameter, while the underlying physical time scales associated with the entanglement relaxation remain unchanged. Such insights are anticipated to assist the future rational design of other highly attractive and ultrasmall nanoparticles that enable a fine-tuned rheological response of nanocomposites across multiple length scales.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"3 6","pages":"466–474"},"PeriodicalIF":0.0,"publicationDate":"2023-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00020","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138528616","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}