ACS polymers AuPub Date : 2025-05-29eCollection Date: 2025-06-11DOI: 10.1021/acspolymersau.5c00020
Yanpu Yao, Xiaofan Yang, Cansu Aydogan, James Town, William Pointer, David M Haddleton
{"title":"Co(II)-Mediated Catalytic Chain Transfer Polymerization (CCTP) Carried Out Under Flow Reaction Conditions and Introducing a New Method for Online GPC Monitoring.","authors":"Yanpu Yao, Xiaofan Yang, Cansu Aydogan, James Town, William Pointer, David M Haddleton","doi":"10.1021/acspolymersau.5c00020","DOIUrl":"10.1021/acspolymersau.5c00020","url":null,"abstract":"<p><p>We report an investigation into the thermally induced catalytic chain transfer polymerization (CCTP) using bis-[(difluoroboryl)-dimethylglyoximato] cobalt-(II) (CoBF) as a chain transfer agent in three different flow reactors: (1) a cascade of continuous stirred-tank reactors (CSTRs), (2) a simple tubular flow reactor, and (3) a Corning Advanced Flow Reactor (AFR). Systematic variations in monomer type, temperature, and stirring rate were employed to investigate their effects on the polymerization process. In the CSTR cascade, higher polymerization rates and conversions were observed without compromising reaction control. Comparative analyses between the flow systems and conventional batch reactions were performed to assess the performance of CoBF under these different reaction conditions. All reactor designs proved successful in carrying out CCTP, and this chemistry is well-suited to continuous production under different flow conditions. The applicability of the reaction system was further verified with successful CCTP of glycidyl methacrylate, and the reproducibility was confirmed by using online continuous GPC.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"5 3","pages":"311-322"},"PeriodicalIF":4.7,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12163948/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144303761","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 : 2025-05-28DOI: 10.1021/acspolymersau.5c0002010.1021/acspolymersau.5c00020
Yanpu Yao, Xiaofan Yang, Cansu Aydogan, James Town, William Pointer and David M. Haddleton*,
{"title":"Co(II)-Mediated Catalytic Chain Transfer Polymerization (CCTP) Carried Out Under Flow Reaction Conditions and Introducing a New Method for Online GPC Monitoring","authors":"Yanpu Yao, Xiaofan Yang, Cansu Aydogan, James Town, William Pointer and David M. Haddleton*, ","doi":"10.1021/acspolymersau.5c0002010.1021/acspolymersau.5c00020","DOIUrl":"https://doi.org/10.1021/acspolymersau.5c00020https://doi.org/10.1021/acspolymersau.5c00020","url":null,"abstract":"<p >We report an investigation into the thermally induced catalytic chain transfer polymerization (CCTP) using bis[(difluoroboryl)dimethylglyoximato] cobalt(II) (CoBF) as a chain transfer agent in three different flow reactors: (1) a cascade of continuous stirred-tank reactors (CSTRs), (2) a simple tubular flow reactor, and (3) a Corning Advanced Flow Reactor (AFR). Systematic variations in monomer type, temperature, and stirring rate were employed to investigate their effects on the polymerization process. In the CSTR cascade, higher polymerization rates and conversions were observed without compromising reaction control. Comparative analyses between the flow systems and conventional batch reactions were performed to assess the performance of CoBF under these different reaction conditions. All reactor designs proved successful in carrying out CCTP, and this chemistry is well-suited to continuous production under different flow conditions. The applicability of the reaction system was further verified with successful CCTP of glycidyl methacrylate, and the reproducibility was confirmed by using online continuous GPC.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"5 3","pages":"311–322 311–322"},"PeriodicalIF":4.7,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.5c00020","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144252924","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 : 2025-05-01DOI: 10.1021/acspolymersau.5c0001010.1021/acspolymersau.5c00010
Ioana Luca, Mădălina Georgiana Albu Kaya*, Irina Titorencu*, Cristina-Elena Dinu-Pîrvu, Maria Minodora Marin, Lăcrămioara Popa, Ana-Maria Rosca, Aurora Antoniac, Valentina Anuta, Răzvan Mihai Prisada, Durmus Alpaslan Kaya and Mihaela Violeta Ghica,
{"title":"Influence of Mucoadhesive Polymers on Physicochemical Features and Biocompatibility of Collagen Wafers","authors":"Ioana Luca, Mădălina Georgiana Albu Kaya*, Irina Titorencu*, Cristina-Elena Dinu-Pîrvu, Maria Minodora Marin, Lăcrămioara Popa, Ana-Maria Rosca, Aurora Antoniac, Valentina Anuta, Răzvan Mihai Prisada, Durmus Alpaslan Kaya and Mihaela Violeta Ghica, ","doi":"10.1021/acspolymersau.5c0001010.1021/acspolymersau.5c00010","DOIUrl":"https://doi.org/10.1021/acspolymersau.5c00010https://doi.org/10.1021/acspolymersau.5c00010","url":null,"abstract":"<p >The aim of this study was to develop and characterize some freeze-dried wafers based on collagen and two mucoadhesive polymers, namely, hydroxypropyl methylcellulose (HPMC) and Carbomer 940 (CBM). The wafers were obtained by lyophilization of the corresponding hydrogels, which were evaluated by circular dichroism in order to investigate mucoadhesive polymers’ influence on collagen’s secondary structure. The obtained freeze-dried wafers were characterized by FT-IR spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), contact angle measurements, and water uptake capacity. Furthermore, biocompatibility assessment was performed by evaluating the impact of freeze-dried wafer extracts on cell viability, morphology, and migration capacity. Circular dichroism showed more significant changes in the secondary structure of collagen associated with the addition of Carbomer 940. The FT-IR spectra displayed specific peaks for collagen and the two mucoadhesive polymers. SEM images illustrated a microporous structure for both collagen and Carbomer 940, while HPMC displayed a more sheet-like structure. The addition of HPMC increased the thermal stability of collagen, while Carbomer 940 had a negative impact on the samples’ thermal stability. Contact angle measurements and water uptake capacity showed good hydrophilicity of the wafers. Except for CBM 100%, all samples supported the viability of human fibroblasts and did not have any inhibitory effect on cell migration capacity, demonstrating good biocompatibility, which is an essential attribute in developing drug delivery supports intended for mucosal applications.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"5 3","pages":"282–297 282–297"},"PeriodicalIF":4.7,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.5c00010","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144252995","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 : 2025-05-01eCollection Date: 2025-06-11DOI: 10.1021/acspolymersau.5c00010
Ioana Luca, Mădălina Georgiana Albu Kaya, Irina Titorencu, Cristina-Elena Dinu-Pîrvu, Maria Minodora Marin, Lăcrămioara Popa, Ana-Maria Rosca, Aurora Antoniac, Valentina Anuta, Răzvan Mihai Prisada, Durmus Alpaslan Kaya, Mihaela Violeta Ghica
{"title":"Influence of Mucoadhesive Polymers on Physicochemical Features and Biocompatibility of Collagen Wafers.","authors":"Ioana Luca, Mădălina Georgiana Albu Kaya, Irina Titorencu, Cristina-Elena Dinu-Pîrvu, Maria Minodora Marin, Lăcrămioara Popa, Ana-Maria Rosca, Aurora Antoniac, Valentina Anuta, Răzvan Mihai Prisada, Durmus Alpaslan Kaya, Mihaela Violeta Ghica","doi":"10.1021/acspolymersau.5c00010","DOIUrl":"10.1021/acspolymersau.5c00010","url":null,"abstract":"<p><p>The aim of this study was to develop and characterize some freeze-dried wafers based on collagen and two mucoadhesive polymers, namely, hydroxypropyl methylcellulose (HPMC) and Carbomer 940 (CBM). The wafers were obtained by lyophilization of the corresponding hydrogels, which were evaluated by circular dichroism in order to investigate mucoadhesive polymers' influence on collagen's secondary structure. The obtained freeze-dried wafers were characterized by FT-IR spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), contact angle measurements, and water uptake capacity. Furthermore, biocompatibility assessment was performed by evaluating the impact of freeze-dried wafer extracts on cell viability, morphology, and migration capacity. Circular dichroism showed more significant changes in the secondary structure of collagen associated with the addition of Carbomer 940. The FT-IR spectra displayed specific peaks for collagen and the two mucoadhesive polymers. SEM images illustrated a microporous structure for both collagen and Carbomer 940, while HPMC displayed a more sheet-like structure. The addition of HPMC increased the thermal stability of collagen, while Carbomer 940 had a negative impact on the samples' thermal stability. Contact angle measurements and water uptake capacity showed good hydrophilicity of the wafers. Except for CBM 100%, all samples supported the viability of human fibroblasts and did not have any inhibitory effect on cell migration capacity, demonstrating good biocompatibility, which is an essential attribute in developing drug delivery supports intended for mucosal applications.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"5 3","pages":"282-297"},"PeriodicalIF":4.7,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12163946/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144303766","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":"Competing Effects of Plasticization and Miscibility on the Structure and Dynamics of Natural Rubber: A Comparative Study on Bio and Commercial Plasticizers.","authors":"Luca Lenzi, Itziar Mas-Giner, Micaela Degli Esposti, Davide Morselli, Marianella Hernández Santana, Paola Fabbri","doi":"10.1021/acspolymersau.5c00009","DOIUrl":"10.1021/acspolymersau.5c00009","url":null,"abstract":"<p><p>Plasticizers are essential for improving the processability and flexibility of rubber compounds by reducing viscosity, aiding filler dispersion, and softening the rubber matrix. Traditionally, petroleum-based phthalate esters like dioctyl phthalate (DOP) and dibutyl phthalate (DBP) have been widely used for these purposes. However, these plasticizers pose significant challenges, including migration from the rubber over time, which can lower performance and raise environmental and health concerns. This study investigates the competing effects of plasticization and miscibility on the structure and dynamics of natural rubber (NR) and epoxidized natural rubber (ENR) when plasticized with glycerol trilevulinate (GT), a biobased plasticizer, and tris-(2-ethylhexyl) trimellitate (TOTM), a petroleum-derived plasticizer. Results show that GT accelerates vulcanization and reduces reversion risks, promoting faster curing and greater flexibility in the rubber network. In contrast, TOTM delays vulcanization and increases reversion, while forming a more rigid cross-linked network. Structurally, GT promotes longer sulfur bridges and strain-induced crystallization in NR, while TOTM favors the formation of shorter sulfur bonds and a more homogeneous network structure. In terms of miscibility, GT is fully miscible with ENR, improving segmental mobility, but shows partial miscibility in NR, restricting chain dynamics as evidenced by Broadband Dielectric Spectroscopy. These findings highlight GT as a potential sustainable alternative to petroleum-derived commercial plasticizers, offering promising advantages for high-performance, biobased rubber applications.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"5 3","pages":"298-310"},"PeriodicalIF":4.7,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12163945/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144303762","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 : 2025-04-24DOI: 10.1021/acspolymersau.5c0000910.1021/acspolymersau.5c00009
Luca Lenzi, Itziar Mas-Giner, Micaela Degli Esposti, Davide Morselli*, Marianella Hernández Santana* and Paola Fabbri,
{"title":"Competing Effects of Plasticization and Miscibility on the Structure and Dynamics of Natural Rubber: A Comparative Study on Bio and Commercial Plasticizers","authors":"Luca Lenzi, Itziar Mas-Giner, Micaela Degli Esposti, Davide Morselli*, Marianella Hernández Santana* and Paola Fabbri, ","doi":"10.1021/acspolymersau.5c0000910.1021/acspolymersau.5c00009","DOIUrl":"https://doi.org/10.1021/acspolymersau.5c00009https://doi.org/10.1021/acspolymersau.5c00009","url":null,"abstract":"<p >Plasticizers are essential for improving the processability and flexibility of rubber compounds by reducing viscosity, aiding filler dispersion, and softening the rubber matrix. Traditionally, petroleum-based phthalate esters like dioctyl phthalate (DOP) and dibutyl phthalate (DBP) have been widely used for these purposes. However, these plasticizers pose significant challenges, including migration from the rubber over time, which can lower performance and raise environmental and health concerns. This study investigates the competing effects of plasticization and miscibility on the structure and dynamics of natural rubber (NR) and epoxidized natural rubber (ENR) when plasticized with glycerol trilevulinate (GT), a biobased plasticizer, and tris(2-ethylhexyl) trimellitate (TOTM), a petroleum-derived plasticizer. Results show that GT accelerates vulcanization and reduces reversion risks, promoting faster curing and greater flexibility in the rubber network. In contrast, TOTM delays vulcanization and increases reversion, while forming a more rigid cross-linked network. Structurally, GT promotes longer sulfur bridges and strain-induced crystallization in NR, while TOTM favors the formation of shorter sulfur bonds and a more homogeneous network structure. In terms of miscibility, GT is fully miscible with ENR, improving segmental mobility, but shows partial miscibility in NR, restricting chain dynamics as evidenced by Broadband Dielectric Spectroscopy. These findings highlight GT as a potential sustainable alternative to petroleum-derived commercial plasticizers, offering promising advantages for high-performance, biobased rubber applications.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"5 3","pages":"298–310 298–310"},"PeriodicalIF":4.7,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.5c00009","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144252972","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 : 2025-04-22DOI: 10.1021/acspolymersau.5c0001610.1021/acspolymersau.5c00016
Daisuke Shimoyama, Shunsuke Sato, Shunta Ohsawa, Shunta Irisawa, Motoko S. Asano* and Kotohiro Nomura*,
{"title":"End-Functionalized Biobased Aliphatic Polyesters Exhibiting Unique Emission/Thermal Properties","authors":"Daisuke Shimoyama, Shunsuke Sato, Shunta Ohsawa, Shunta Irisawa, Motoko S. Asano* and Kotohiro Nomura*, ","doi":"10.1021/acspolymersau.5c0001610.1021/acspolymersau.5c00016","DOIUrl":"https://doi.org/10.1021/acspolymersau.5c00016https://doi.org/10.1021/acspolymersau.5c00016","url":null,"abstract":"<p >The exclusive introduction of end groups into biobased aliphatic polyesters containing vinyl chain ends, prepared by ADMET polymerization of nonconjugated diene monomers, has been achieved by adopting olefin metathesis with a molybdenum-alkylidene catalyst followed by treatment with various aldehydes, and their quantitative introductions were confirmed by grafting PEG with certified <i>M</i><sub>n</sub> values. The end-functionalized polyesters demonstrated unique emission and thermal properties through an interaction of the end groups; both melting and crystallization temperatures are affected by the end groups as well as the <i>M</i><sub>n</sub> values.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"5 3","pages":"241–246 241–246"},"PeriodicalIF":4.7,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.5c00016","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144252970","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":"End-Functionalized Biobased Aliphatic Polyesters Exhibiting Unique Emission/Thermal Properties.","authors":"Daisuke Shimoyama, Shunsuke Sato, Shunta Ohsawa, Shunta Irisawa, Motoko S Asano, Kotohiro Nomura","doi":"10.1021/acspolymersau.5c00016","DOIUrl":"10.1021/acspolymersau.5c00016","url":null,"abstract":"<p><p>The exclusive introduction of end groups into biobased aliphatic polyesters containing vinyl chain ends, prepared by ADMET polymerization of nonconjugated diene monomers, has been achieved by adopting olefin metathesis with a molybdenum-alkylidene catalyst followed by treatment with various aldehydes, and their quantitative introductions were confirmed by grafting PEG with certified <i>M</i> <sub>n</sub> values. The end-functionalized polyesters demonstrated unique emission and thermal properties through an interaction of the end groups; both melting and crystallization temperatures are affected by the end groups as well as the <i>M</i> <sub>n</sub> values.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"5 3","pages":"241-246"},"PeriodicalIF":4.7,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12163942/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144303763","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}