ACS polymers Au最新文献_第6页

Influence of Metal Identity and Complex Nuclearity in Kumada Cross-Coupling Polymerizations with a Pyridine Diimine-Based Ligand Scaffold 用吡啶二胺配体支架进行 Kumada 交叉偶联聚合时金属特性和复合物核性的影响

ACS polymers Au Pub Date : 2023-11-08 DOI: 10.1021/acspolymersau.3c00022

Andrew J. King, Jiashu Wang, Tianchang Liu, Adharsh Raghavan, Neil C. Tomson* and Aleksandr V. Zhukhovitskiy*,

{"title":"Influence of Metal Identity and Complex Nuclearity in Kumada Cross-Coupling Polymerizations with a Pyridine Diimine-Based Ligand Scaffold","authors":"Andrew J. King, Jiashu Wang, Tianchang Liu, Adharsh Raghavan, Neil C. Tomson* and Aleksandr V. Zhukhovitskiy*, ","doi":"10.1021/acspolymersau.3c00022","DOIUrl":"10.1021/acspolymersau.3c00022","url":null,"abstract":"Cross-coupling polymerizations have fundamentally changed the field of conjugated polymers (CPs) by expanding the scope of accessible materials. Despite the prevalence of cross-coupling in CP synthesis, almost all polymerizations rely on mononuclear Ni or Pd catalysts. Here, we report a systematic exploration of mono- and dinuclear Fe and Ni precatalysts with a pyridine diimine ligand scaffold for Kumada cross-coupling polymerization of a donor thiophene and an acceptor benzotriazole monomers. We observe that variation of the metal identity from Ni to Fe produces contrasting polymerization mechanisms, while complex nuclearity has a minimal impact on reactivity. Specifically, Fe complexes appear to catalyze step-growth Kumada polymerizations and can readily access both Csp2–Csp3 and Csp2–Csp2 cross-couplings, while Ni complexes catalyze chain-growth polymerizations and predominantly Csp2–Csp2 cross-couplings. Thus, our work sheds light on important design parameters for transition metal complexes used in cross-coupling polymerizations, demonstrates the viability of iron catalysis in Kumada polymerization, and opens the door to novel polymer compositions.","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"3 6","pages":"475–481"},"PeriodicalIF":0.0,"publicationDate":"2023-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00022","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135340542","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}

引用次数: 0

Discrete Miktoarm Star Block Copolymers with Tailored Molecular Architecture 具有定制分子结构的离散 Miktoarm 星型嵌段共聚物

ACS polymers Au Pub Date : 2023-10-13 DOI: 10.1021/acspolymersau.3c00017

Zhuang Ma, Zhongguo Liu, Tianyu Zheng, Zhanhui Gan, Rui Tan* and Xue-Hui Dong*,

{"title":"Discrete Miktoarm Star Block Copolymers with Tailored Molecular Architecture","authors":"Zhuang Ma, Zhongguo Liu, Tianyu Zheng, Zhanhui Gan, Rui Tan* and Xue-Hui Dong*, ","doi":"10.1021/acspolymersau.3c00017","DOIUrl":"10.1021/acspolymersau.3c00017","url":null,"abstract":"Molecular architecture is a critical factor in regulating phase behaviors of the block copolymer and prompting the formation of unconventional nanostructures. This work meticulously designed a library of isomeric miktoarm star polymers with an architectural evolution from the linear-branched block copolymer to the miktoarm star block copolymer and to the star-like block copolymer (i.e., 3AB → 3(AB1)B2 → 3(AB)). All of the polymers have precise chemical composition and uniform chain length, eliminating inherent molecular uncertainties such as chain length distribution or architectural defects. The self-assembly behaviors were systematically studied and compared. Gradually increasing the relative length of the branched B1 block regulates the ratio between the bridge and loop configuration and effectively releases packing frustration in the formation of the spherical or cylindrical structures, leading to a substantial deflection of phase boundaries. Complex structures, such as Frank–Kasper phases, were captured at a surprisingly higher volume fraction. Rationally regulating the molecular architecture offers rich possibilities to tune the packing symmetry of block copolymers.","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"3 6","pages":"457–465"},"PeriodicalIF":0.0,"publicationDate":"2023-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00017","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135855366","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}

引用次数: 0

Engineering an All-Biobased Solvent- and Styrene-Free Curable Resin 设计一种全生物基不含溶剂和苯乙烯的可固化树脂

ACS polymers Au Pub Date : 2023-10-03 DOI: 10.1021/acspolymersau.3c00015

Samson Afewerki*, and , Ulrica Edlund*,

{"title":"Engineering an All-Biobased Solvent- and Styrene-Free Curable Resin","authors":"Samson Afewerki*,  and , Ulrica Edlund*, ","doi":"10.1021/acspolymersau.3c00015","DOIUrl":"10.1021/acspolymersau.3c00015","url":null,"abstract":"The sustainable production of polymers and materials derived from renewable feedstocks such as biomass is vital to addressing the current climate and environmental challenges. In particular, finding a replacement for current widely used curable resins containing undesired components with both health and environmental issues, such as bisphenol-A and styrene, is of great interest and vital for a sustainable society. In this work, we disclose the preparation and fabrication of an all-biobased curable resin. The devised resin consists of a polyester component based on fumaric acid, itaconic acid, 2,5-furandicarboxylic acid, 1,4-butanediol, and reactive diluents acting as both solvents and viscosity enhancers. Importantly, the complete process was performed solvent-free, thus promoting its industrial applications. The cured biobased resin demonstrates very good thermal properties (stable up to 415 °C), the ability to resist deformation based on the high Young’s modulus of ∼775 MPa, and chemical resistance based on the swelling index and gel content. We envision the disclosed biobased resin having tailorable properties suitable for industrial applications.","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"3 6","pages":"447–456"},"PeriodicalIF":0.0,"publicationDate":"2023-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00015","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135695612","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}

引用次数: 0

Highly Stretchable Stress–Strain Sensor from Elastomer Nanocomposites with Movable Cross-links and Ketjenblack 可移动交联弹性体纳米复合材料和Ketjenblack的高拉伸应力应变传感器。

ACS polymers Au Pub Date : 2023-09-11 DOI: 10.1021/acspolymersau.3c00010

Ryohei Ikura, Kota Kajimoto, Junsu Park, Shunsuke Murayama, Yusei Fujiwara, Motofumi Osaki, Tomohiro Suzuki, Hidenori Shirakawa, Yujiro Kitamura, Hiroaki Takahashi, Yasumasa Ohashi, Seiji Obata, Akira Harada, Yuka Ikemoto, Yuta Nishina*, Yasutomo Uetsuji*, Go Matsuba* and Yoshinori Takashima*,

{"title":"Highly Stretchable Stress–Strain Sensor from Elastomer Nanocomposites with Movable Cross-links and Ketjenblack","authors":"Ryohei Ikura, Kota Kajimoto, Junsu Park, Shunsuke Murayama, Yusei Fujiwara, Motofumi Osaki, Tomohiro Suzuki, Hidenori Shirakawa, Yujiro Kitamura, Hiroaki Takahashi, Yasumasa Ohashi, Seiji Obata, Akira Harada, Yuka Ikemoto, Yuta Nishina*, Yasutomo Uetsuji*, Go Matsuba* and Yoshinori Takashima*, ","doi":"10.1021/acspolymersau.3c00010","DOIUrl":"10.1021/acspolymersau.3c00010","url":null,"abstract":"Practical applications like very thin stress–strain sensors require high strength, stretchability, and conductivity, simultaneously. One of the approaches is improving the toughness of the stress–strain sensing materials. Polymeric materials with movable cross-links in which the polymer chain penetrates the cavity of cyclodextrin (CD) demonstrate enhanced strength and stretchability, simultaneously. We designed two approaches that utilize elastomer nanocomposites with movable cross-links and carbon filler (ketjenblack, KB). One approach is mixing SC (a single movable cross-network material), a linear polymer (poly(ethyl acrylate), PEA), and KB to obtain their composite. The electrical resistance increases proportionally with tensile strain, leading to the application of this composite as a stress–strain sensor. The responses of this material are stable for over 100 loading and unloading cycles. The other approach is a composite made with KB and a movable cross-network elastomer for knitting dissimilar polymers (KP), where movable cross-links connect the CD-modified polystyrene (PSCD) and PEA. The obtained composite acts as a highly sensitive stress–strain sensor that exhibits an exponential increase in resistance with increasing tensile strain due to the polymer dethreading from the CD rings. The designed preparations of highly repeatable or highly responsive stress–strain sensors with good mechanical properties can help broaden their application in electrical devices.","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"3 5","pages":"394–405"},"PeriodicalIF":0.0,"publicationDate":"2023-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00010","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41241532","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}

引用次数: 0

Unraveling the Glass-like Dynamic Heterogeneity in Ring Polymer Melts: From Semiflexible to Stiff Chain 解开环状聚合物熔体中的玻璃状动态异质性：从半柔性链到刚性链

ACS polymers Au Pub Date : 2023-08-22 DOI: 10.1021/acspolymersau.3c00013

Shota Goto, Kang Kim* and Nobuyuki Matubayasi*,

{"title":"Unraveling the Glass-like Dynamic Heterogeneity in Ring Polymer Melts: From Semiflexible to Stiff Chain","authors":"Shota Goto, Kang Kim* and Nobuyuki Matubayasi*, ","doi":"10.1021/acspolymersau.3c00013","DOIUrl":"10.1021/acspolymersau.3c00013","url":null,"abstract":"Ring polymers are an intriguing class of polymers with unique physical properties, and understanding their behavior is important for developing accurate theoretical models. In this study, we investigate the effect of chain stiffness and monomer density on the static and dynamic behaviors of ring polymer melts using molecular dynamics simulations. Our first focus is on the non-Gaussian parameter of center-of-mass displacement as a measure of dynamic heterogeneity, which is commonly observed in glass-forming liquids. We find that the non-Gaussianity in the displacement distribution increases with the monomer density and stiffness of the polymer chains, suggesting that excluded volume interactions between centers of mass have a strong effect on the dynamics of ring polymers. We then analyze the relationship between the radius of gyration and monomer density for semiflexible and stiff ring polymers. Our results indicate that the relationship between the two varies with chain stiffness, which can be attributed to the competition between repulsive forces inside the ring and from adjacent rings. Finally, we study the dynamics of bond-breakage virtually connected between the centers of mass of rings to analyze the exchanges of intermolecular networks of bonds. Our results demonstrate that the dynamic heterogeneity of bond-breakage is coupled with the non-Gaussianity in ring polymer melts, highlighting the importance of the bond-breaking method in determining the intermolecular dynamics of ring polymer melts. Overall, our study sheds light on the factors that govern the dynamic behaviors of ring polymers.","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"3 6","pages":"437–446"},"PeriodicalIF":0.0,"publicationDate":"2023-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00013","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41410851","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}

引用次数: 0

Improved Elastic Recovery from ABC Triblock Terpolymers ABC三嵌段三元聚合物弹性恢复性能的改进。

ACS polymers Au Pub Date : 2023-07-18 DOI: 10.1021/acspolymersau.3c00012

Kaitlin R. Albanese, Jacob R. Blankenship, Timothy Quah, Amy Zhang, Kris T. Delaney, Glenn H. Fredrickson, Christopher M. Bates* and Craig J. Hawker*,

{"title":"Improved Elastic Recovery from ABC Triblock Terpolymers","authors":"Kaitlin R. Albanese, Jacob R. Blankenship, Timothy Quah, Amy Zhang, Kris T. Delaney, Glenn H. Fredrickson, Christopher M. Bates* and Craig J. Hawker*, ","doi":"10.1021/acspolymersau.3c00012","DOIUrl":"10.1021/acspolymersau.3c00012","url":null,"abstract":"The promise of ABC triblock terpolymers for improving the mechanical properties of thermoplastic elastomers is demonstrated by comparison with symmetric ABA/CBC analogs having similar molecular weights and volume fraction of B and A/C domains. The ABC architecture enhances elasticity (up to 98% recovery over 10 cycles) in part through essentially full chain bridging between discrete hard domains leading to the minimization of mechanically unproductive loops. In addition, the unique phase space of ABC triblocks also enables the fraction of hard-block domains to be higher (fhard ≈ 0.4) while maintaining elasticity, which is traditionally only possible with non-linear architectures or highly asymmetric ABA triblock copolymers. These advantages of ABC triblock terpolymers provide a tunable platform to create materials with practical applications while improving our fundamental understanding of chain conformation and structure–property relationships in block copolymers.","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"3 5","pages":"376–382"},"PeriodicalIF":0.0,"publicationDate":"2023-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00012","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41241533","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}

引用次数: 0

Clickable Polyprolines from Azido-proline N-Carboxyanhydride 叠氮-脯氨酸n -羧酸氢化物的可点击聚脯氨酸

ACS polymers Au Pub Date : 2023-07-16 DOI: 10.1021/acspolymersau.3c00011

Rachel E. Detwiler, Thomas J. McPartlon, Clara S. Coffey and Jessica R. Kramer*,

{"title":"Clickable Polyprolines from Azido-proline N-Carboxyanhydride","authors":"Rachel E. Detwiler, Thomas J. McPartlon, Clara S. Coffey and Jessica R. Kramer*, ","doi":"10.1021/acspolymersau.3c00011","DOIUrl":"https://doi.org/10.1021/acspolymersau.3c00011","url":null,"abstract":"Polyproline is a material of great interest in biomedicine due to its helical scaffold of structural importance in collagen and mucins and its ability to gel and to change conformations in response to temperature. Appending of function-modulating chemical groups to such a material is desirable to diversify potential applications. Here, we describe the synthesis of high-molecular-weight homo, block, and statistical polymers of azide-functionalized proline. The azide groups served as moieties for highly efficient click-grafting, as stabilizers of the polyproline PPII helix, and as modulators of thermoresponsiveness. Saccharides and ethylene glycol were utilized to explore small-molecule grafting, and glutamate polymers were utilized to form polyelectrolyte bottlebrush architectures. Secondary structure effects of both the azide and click modifications, as well as lower critical solution temperature behavior, were characterized. The polyazidoprolines and click products were well tolerated by live human cells and are expected to find use in diverse biomedical applications.","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"3 5","pages":"383–393"},"PeriodicalIF":0.0,"publicationDate":"2023-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00011","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49768385","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}

引用次数: 0

On the Importance of Mental Health in STEM 论心理健康在STEM中的重要性

ACS polymers Au Pub Date : 2023-06-21 DOI: 10.1021/acspolymersau.2c00062

Christian W. Pester*, Gina Noh* and Andi Fu,

引用次数: 0

Stabilizing Polymer Coatings Alter the Protein Corona of DNA Origami and Can Be Engineered to Bias the Cellular Uptake 稳定聚合物涂层改变DNA折纸的蛋白质电晕并可被工程化以偏置细胞吸收

ACS polymers Au Pub Date : 2023-06-07 DOI: 10.1021/acspolymersau.3c00009

Hugo J. Rodríguez-Franco, Jorieke Weiden and Maartje M. C. Bastings*,

{"title":"Stabilizing Polymer Coatings Alter the Protein Corona of DNA Origami and Can Be Engineered to Bias the Cellular Uptake","authors":"Hugo J. Rodríguez-Franco, Jorieke Weiden and Maartje M. C. Bastings*, ","doi":"10.1021/acspolymersau.3c00009","DOIUrl":"10.1021/acspolymersau.3c00009","url":null,"abstract":"With DNA-based nanomaterials being designed for applications in cellular environments, the need arises to accurately understand their surface interactions toward biological targets. As for any material exposed to protein-rich cell culture conditions, a protein corona will establish around DNA nanoparticles, potentially altering the a-priori designed particle function. Here, we first set out to identify the protein corona around DNA origami nanomaterials, taking into account the application of stabilizing block co-polymer coatings (oligolysine-1kPEG or oligolysine-5kPEG) widely used to ensure particle integrity. By implementing a label-free methodology, the distinct polymer coating conditions show unique protein profiles, predominantly defined by differences in the molecular weight and isoelectric point of the adsorbed proteins. Interestingly, none of the applied coatings reduced the diversity of the proteins detected within the specific coronae. We then biased the protein corona through pre-incubation with selected proteins and show significant changes in the cell uptake. Our study contributes to a deeper understanding of the complex interplay between DNA nanomaterials, proteins, and cells at the bio-interface.","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"3 4","pages":"344–353"},"PeriodicalIF":0.0,"publicationDate":"2023-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/07/37/lg3c00009.PMC10416322.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"10002037","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}

引用次数: 0

Sequence Patterning, Morphology, and Dispersity in Single-Chain Nanoparticles: Insights from Simulation and Machine Learning 单链纳米颗粒的序列模式、形态和分散性:来自模拟和机器学习的见解

ACS polymers Au Pub Date : 2023-06-05 DOI: 10.1021/acspolymersau.3c00007

Roshan A. Patel, Sophia Colmenares and Michael A. Webb*,

{"title":"Sequence Patterning, Morphology, and Dispersity in Single-Chain Nanoparticles: Insights from Simulation and Machine Learning","authors":"Roshan A. Patel, Sophia Colmenares and Michael A. Webb*, ","doi":"10.1021/acspolymersau.3c00007","DOIUrl":"10.1021/acspolymersau.3c00007","url":null,"abstract":"Single-chain nanoparticles (SCNPs) are intriguing materials inspired by proteins that consist of a single precursor polymer chain that has collapsed into a stable structure. In many prospective applications, such as catalysis, the utility of a single-chain nanoparticle will intricately depend on the formation of a mostly specific structure or morphology. However, it is not generally well understood how to reliably control the morphology of single-chain nanoparticles. To address this knowledge gap, we simulate the formation of 7680 distinct single-chain nanoparticles from precursor chains that span a wide range of, in principle, tunable patterning characteristics of cross-linking moieties. Using a combination of molecular simulation and machine learning analyses, we show how the overall fraction of functionalization and blockiness of cross-linking moieties biases the formation of certain local and global morphological characteristics. Importantly, we illustrate and quantify the dispersity of morphologies that arise due to the stochastic nature of collapse from a well-defined sequence as well as from the ensemble of sequences that correspond to a given specification of precursor parameters. Moreover, we also examine the efficacy of precise sequence control in achieving morphological outcomes in different regimes of precursor parameters. Overall, this work critically assesses how precursor chains might be feasibly tailored to achieve given SCNP morphologies and provides a platform to pursue future sequence-based design.","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"3 3","pages":"284–294"},"PeriodicalIF":0.0,"publicationDate":"2023-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/c7/df/lg3c00007.PMC10273411.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"10019459","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}

引用次数: 0