Pub Date : 2023-08-14DOI: 10.1080/10601325.2023.2242409
Lu Zheng, Jiyan Ma, Jie Zhao
Abstract Patients with cervical cancer have a significant risk of tumor recurrence and metastasis. The discovery of effective treatments for cervical cancer is urgently needed. Poly(lactic-co-glycolic acid) (PLGA) was recently discovered to offer a promising therapeutic drug carrier. Hence, we developed dual-loaded PLGA nanoparticles (NPs) as a drug carrier to combat this problem with current chemotherapeutic drugs for cervical cancer. We engineered PLGA NPs with epidermal growth factor (EGF) functionalization and co-loaded them with SN-38 and perfluorocarbon (PC) to treat cervical cancer selectively. Cell counting kit-8 test results reveal that newly fabricated NPs effectively induce cell proliferation in cervical cancer cells. Further, flow cytometry, Hoechst 33342 staining and acridine orange and propidium iodide staining were used to determine the apoptosis of SN38/PC@EGF-PLGA NPs in HeLa and CaSki cells. And the release was pH-dependent when tested in vitro. Cervical cancer cells took up targeted SN38/PC@EGF-PLGA NPs at a greater rate than untargeted NPs. Furthermore, HeLa and CaSki cells were more sensitive to apoptosis induction and cell viability suppression when exposed to SN38/PC@EGF-PLGA NPs than nontargeted NPs. The findings of this study improve the exploration of SN38/PC@EGF-PLGA NPs in the new development of effective drug candidates for highly invasive cervical cancer in future. Graphical Abstract
{"title":"Fabrication of epidermal growth factor functionalized polymeric poly(lactic-co-glycolic acid) nanoparticles loaded SN-38 and perfluorocarbon for treatment and care: investigation of antiproliferative effects and apoptosis in cervical cancer cells","authors":"Lu Zheng, Jiyan Ma, Jie Zhao","doi":"10.1080/10601325.2023.2242409","DOIUrl":"https://doi.org/10.1080/10601325.2023.2242409","url":null,"abstract":"Abstract Patients with cervical cancer have a significant risk of tumor recurrence and metastasis. The discovery of effective treatments for cervical cancer is urgently needed. Poly(lactic-co-glycolic acid) (PLGA) was recently discovered to offer a promising therapeutic drug carrier. Hence, we developed dual-loaded PLGA nanoparticles (NPs) as a drug carrier to combat this problem with current chemotherapeutic drugs for cervical cancer. We engineered PLGA NPs with epidermal growth factor (EGF) functionalization and co-loaded them with SN-38 and perfluorocarbon (PC) to treat cervical cancer selectively. Cell counting kit-8 test results reveal that newly fabricated NPs effectively induce cell proliferation in cervical cancer cells. Further, flow cytometry, Hoechst 33342 staining and acridine orange and propidium iodide staining were used to determine the apoptosis of SN38/PC@EGF-PLGA NPs in HeLa and CaSki cells. And the release was pH-dependent when tested in vitro. Cervical cancer cells took up targeted SN38/PC@EGF-PLGA NPs at a greater rate than untargeted NPs. Furthermore, HeLa and CaSki cells were more sensitive to apoptosis induction and cell viability suppression when exposed to SN38/PC@EGF-PLGA NPs than nontargeted NPs. The findings of this study improve the exploration of SN38/PC@EGF-PLGA NPs in the new development of effective drug candidates for highly invasive cervical cancer in future. Graphical Abstract","PeriodicalId":16228,"journal":{"name":"Journal of Macromolecular Science, Part A","volume":"46 1","pages":"640 - 649"},"PeriodicalIF":0.0,"publicationDate":"2023-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82441857","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}
Pub Date : 2023-08-03DOI: 10.1080/10601325.2023.2242402
Meghna Ghoshal, Pampa Chowdhury, Arindam Khatua, Arnab Banerjee, Rhituparna Nandi, Priyadarsi De, A. Bisai
Abstract To prepare alanine containing amphiphilic block copolymers, herein, we have polymerized methyl methacrylate (MMA) by reversible addition-fragmentation chain transfer (RAFT) polymerization and further used it as macro chain transfer agent (macroCTA) for the synthesis of PMMA-b-P(Boc-L-Ala-HEMA) (Boc-L-Ala-HEMA = tert-butyloxycarbonyl-L-alanine methacryloyloxyethyl ester) diblock copolymers. The molar masses of the macroCTA and all block copolymers as well as the dispersity (Ð) of those polymers were measured by size exclusion chromatography (SEC). The Boc-group deprotection from the block copolymers was carried out in dichloromethane by using trifluoroacetic acid to produce amphiphilic PMMA-b-P(L-Ala-HEMA), and this successful deprotection was proved by 1H NMR spectroscopy. The micellar self-assembled nature of PMMA-b-P(L-Ala-HEMA) was confirmed using a variety of techniques, including dynamic light scattering (DLS), critical aggregation concentration (CAC) determination by fluorescence spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and 1H NMR spectroscopy. The hydrophobic pyrene-tagged estrone-based natural product (NP) was encapsulated in the micellar nanostructure, proven by fluorescence spectroscopy. This encapsulating power of the corresponding polymers makes them attractive candidates as drug delivery vehicles of natural products, as well as encapsulation and delivery of other hydrophobic drug/dye molecules. Graphical Abstract
{"title":"Side-chain alanine-based block copolymer as natural product delivery system","authors":"Meghna Ghoshal, Pampa Chowdhury, Arindam Khatua, Arnab Banerjee, Rhituparna Nandi, Priyadarsi De, A. Bisai","doi":"10.1080/10601325.2023.2242402","DOIUrl":"https://doi.org/10.1080/10601325.2023.2242402","url":null,"abstract":"Abstract To prepare alanine containing amphiphilic block copolymers, herein, we have polymerized methyl methacrylate (MMA) by reversible addition-fragmentation chain transfer (RAFT) polymerization and further used it as macro chain transfer agent (macroCTA) for the synthesis of PMMA-b-P(Boc-L-Ala-HEMA) (Boc-L-Ala-HEMA = tert-butyloxycarbonyl-L-alanine methacryloyloxyethyl ester) diblock copolymers. The molar masses of the macroCTA and all block copolymers as well as the dispersity (Ð) of those polymers were measured by size exclusion chromatography (SEC). The Boc-group deprotection from the block copolymers was carried out in dichloromethane by using trifluoroacetic acid to produce amphiphilic PMMA-b-P(L-Ala-HEMA), and this successful deprotection was proved by 1H NMR spectroscopy. The micellar self-assembled nature of PMMA-b-P(L-Ala-HEMA) was confirmed using a variety of techniques, including dynamic light scattering (DLS), critical aggregation concentration (CAC) determination by fluorescence spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and 1H NMR spectroscopy. The hydrophobic pyrene-tagged estrone-based natural product (NP) was encapsulated in the micellar nanostructure, proven by fluorescence spectroscopy. This encapsulating power of the corresponding polymers makes them attractive candidates as drug delivery vehicles of natural products, as well as encapsulation and delivery of other hydrophobic drug/dye molecules. Graphical Abstract","PeriodicalId":16228,"journal":{"name":"Journal of Macromolecular Science, Part A","volume":"55 1","pages":"650 - 659"},"PeriodicalIF":0.0,"publicationDate":"2023-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77172732","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}
Pub Date : 2023-07-26DOI: 10.1080/10601325.2023.2238775
Abbas Rezaei, Ahmad Hajitabaar-Firoozjaei, Hossein Behniafar
Abstract In this research, a new amphiphilic copolymer with an H-shaped macromolecular structure consisting of three hydrophobic blocks and two hydrophilic blocks were synthesized by a combination of ring-opening polymerization and click chemistry. The central chain and two of the side arms of the H-shaped structure were made of oxybutylene and hexanoate repeating units, respectively (hydrophobic segments). The remaining two side arms are made of oxyethylene repeating units (hydrophilic segments) that are connected to the rest of the structure through disulfide bonds. The prepared H-shaped macromolecules were characterized by elemental analysis (CHNS), FT-IR, and 1H-NMR techniques. Based on transmission electron microscopy (TEM) images, the amphiphilic nature of the H-shaped polymer allowed it to form spherical molecular assemblies with a mean diameter of about 80 nm. The critical micelle concentration (CMC) in an aqueous solution was determined using the fluorometric method (CMC = 4.76 × 10−3 mg/mL). According to the profiles obtained from dynamic light scattering (DLS), the resulting spherical micelles had a mean hydrodynamic diameter ( H ) of ∼95 nm with a low polydispersity index (PDI = 0.26). Graphical Abstract
{"title":"Synthesis and self-assembly of H-shaped amphiphilic block copolymer based on polyoxyethylene, polyoxybutylene, and poly(ε-caprolactone) units","authors":"Abbas Rezaei, Ahmad Hajitabaar-Firoozjaei, Hossein Behniafar","doi":"10.1080/10601325.2023.2238775","DOIUrl":"https://doi.org/10.1080/10601325.2023.2238775","url":null,"abstract":"Abstract In this research, a new amphiphilic copolymer with an H-shaped macromolecular structure consisting of three hydrophobic blocks and two hydrophilic blocks were synthesized by a combination of ring-opening polymerization and click chemistry. The central chain and two of the side arms of the H-shaped structure were made of oxybutylene and hexanoate repeating units, respectively (hydrophobic segments). The remaining two side arms are made of oxyethylene repeating units (hydrophilic segments) that are connected to the rest of the structure through disulfide bonds. The prepared H-shaped macromolecules were characterized by elemental analysis (CHNS), FT-IR, and 1H-NMR techniques. Based on transmission electron microscopy (TEM) images, the amphiphilic nature of the H-shaped polymer allowed it to form spherical molecular assemblies with a mean diameter of about 80 nm. The critical micelle concentration (CMC) in an aqueous solution was determined using the fluorometric method (CMC = 4.76 × 10−3 mg/mL). According to the profiles obtained from dynamic light scattering (DLS), the resulting spherical micelles had a mean hydrodynamic diameter ( H ) of ∼95 nm with a low polydispersity index (PDI = 0.26). Graphical Abstract","PeriodicalId":16228,"journal":{"name":"Journal of Macromolecular Science, Part A","volume":"18 1","pages":"591 - 598"},"PeriodicalIF":0.0,"publicationDate":"2023-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85399300","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}
Pub Date : 2023-07-21DOI: 10.1080/10601325.2023.2235389
S. Kumar, U. Tamboli, Varnitha Manikantan, Govindaraj Sri Varalakshmi, Aleyamma Alexander, Sivaraj Ramasamy, A. S. Pillai, I. V. Enoch
Abstract Magnetic nanomaterials of different compositions have been examined, focusing on the magnetic field-directed transport of drugs. The size, shape, surface modification and composition variations make every magnetic nanostructure a unique nanocarrier. In this work, we carry out a hydrothermal synthesis of novel manganese-cobalt co-incorporated magnetic ferrite nanoparticles. The particles are characterized using x-ray diffraction, transmission electron microscopy, thermogravimetry and x-ray photoelectron spectroscopy. The size of the nanoparticles is below 10 nm, and they are found to fall under the face-centered cubic system. The nanoparticles are coated with the β-cyclodextrin and folate co-tethered polyethylene glycol. Vibrating sample magnetometry reveals the soft ferromagnetic nature of the nanoparticles with a saturation magnetization value of 28.11 emu g−1 for the coated nanoparticles. The polymer on the nanoparticles allows the loading of the drug feasible, and the encapsulation efficiency is ∼93%. The in vitro release of the drug is monitored and it is observed that the release occurs over 130 h. The cytotoxicity of the free- and camptothecin-loaded manganese-ferrite nanocarrier on breast cancer cell lines is investigated. The IC50 value of the drug-loaded nanocarrier is 2.22 µg mL−1 which is significantly lower than that of the free drug. The drug-encapsulated nanocarrier releases the cargo slowly and continuously and shows increased efficacy, which represents the significance of the nanocarrier. The results present the designed nanomaterial as a suitable anticancer drug vehicle. Graphical Abstract
{"title":"Designed ultrafine polymer-coated manganese-cobalt ferrite nanoparticles loaded with anticancer drug: efficacy enhancement through host:guest complexation on the polymer surface","authors":"S. Kumar, U. Tamboli, Varnitha Manikantan, Govindaraj Sri Varalakshmi, Aleyamma Alexander, Sivaraj Ramasamy, A. S. Pillai, I. V. Enoch","doi":"10.1080/10601325.2023.2235389","DOIUrl":"https://doi.org/10.1080/10601325.2023.2235389","url":null,"abstract":"Abstract Magnetic nanomaterials of different compositions have been examined, focusing on the magnetic field-directed transport of drugs. The size, shape, surface modification and composition variations make every magnetic nanostructure a unique nanocarrier. In this work, we carry out a hydrothermal synthesis of novel manganese-cobalt co-incorporated magnetic ferrite nanoparticles. The particles are characterized using x-ray diffraction, transmission electron microscopy, thermogravimetry and x-ray photoelectron spectroscopy. The size of the nanoparticles is below 10 nm, and they are found to fall under the face-centered cubic system. The nanoparticles are coated with the β-cyclodextrin and folate co-tethered polyethylene glycol. Vibrating sample magnetometry reveals the soft ferromagnetic nature of the nanoparticles with a saturation magnetization value of 28.11 emu g−1 for the coated nanoparticles. The polymer on the nanoparticles allows the loading of the drug feasible, and the encapsulation efficiency is ∼93%. The in vitro release of the drug is monitored and it is observed that the release occurs over 130 h. The cytotoxicity of the free- and camptothecin-loaded manganese-ferrite nanocarrier on breast cancer cell lines is investigated. The IC50 value of the drug-loaded nanocarrier is 2.22 µg mL−1 which is significantly lower than that of the free drug. The drug-encapsulated nanocarrier releases the cargo slowly and continuously and shows increased efficacy, which represents the significance of the nanocarrier. The results present the designed nanomaterial as a suitable anticancer drug vehicle. Graphical Abstract","PeriodicalId":16228,"journal":{"name":"Journal of Macromolecular Science, Part A","volume":"157 1","pages":"580 - 590"},"PeriodicalIF":0.0,"publicationDate":"2023-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76625390","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}
Pub Date : 2023-07-04DOI: 10.1080/10601325.2023.2230271
Sumana Pal, P. Chowdhury, Nandagopal Bar, Arindam Ray, Debrupa Biswas, G. Das
Abstract Here, an attempt has been made to synthesize a high-quality fluorescent oligo(2,4-diaminotoluene) suitable for the development of a probe. The work introduces a new unique type of template (i.e., cage made of water-alcohol co-solvents) for oligomer containing 5–6 repeating units with remarkable water solubility and strong photoluminescence. Almost 16-fold enhancement of fluorescence properties compared to analogously structured polymer reported earlier has been achieved through aggregation-induced emission (AIE). Modern techniques like FTIR, NMR, PXRD, TGA, DTG, MALDI-TOF MS, SEM, TEM, SAED, and DLS are used to confirm the formation of the desired oligomer. Due to the high quantum yield (0.49), narrow emission band (full width at half maximum = 45 nm), and suitable chemical structure, the oligomer could be used as a potential fluorescent chemo-sensor for arsenic species. The reproducible LOD (2.47 mM) and wide LDR (0–100 mM) values along with robustness make the system highly relevant as an analytical tool. The structure, spectral properties, and sensing abilities of the oligomer have been understood in the light of computational chemistry. Graphical Abstract
本文试图合成一种高质量的荧光低聚物(2,4-二氨基甲苯)，适合于探针的开发。本文介绍了一种新型独特的含有5-6个重复单元的低聚物模板(即水-醇共溶剂笼)，具有显著的水溶性和强的光致发光性。与先前报道的类似结构聚合物相比，通过聚集诱导发射(AIE)实现了几乎16倍的荧光特性增强。现代技术如FTIR, NMR, PXRD, TGA, DTG, MALDI-TOF, MS, SEM, TEM, SAED和DLS被用来确认所需低聚物的形成。由于高量子产率(0.49)、窄发射带(半峰全宽= 45 nm)和合适的化学结构，该低聚物可作为砷种的荧光化学传感器。可重复的LOD (2.47 mM)和宽LDR (0-100 mM)值以及鲁棒性使该系统作为分析工具具有很高的相关性。从计算化学的角度了解了该低聚物的结构、光谱性质和传感能力。图形抽象
{"title":"Improved version of oligo(2,4-diaminotoluene): synthesis, characterization, understanding, and application","authors":"Sumana Pal, P. Chowdhury, Nandagopal Bar, Arindam Ray, Debrupa Biswas, G. Das","doi":"10.1080/10601325.2023.2230271","DOIUrl":"https://doi.org/10.1080/10601325.2023.2230271","url":null,"abstract":"Abstract Here, an attempt has been made to synthesize a high-quality fluorescent oligo(2,4-diaminotoluene) suitable for the development of a probe. The work introduces a new unique type of template (i.e., cage made of water-alcohol co-solvents) for oligomer containing 5–6 repeating units with remarkable water solubility and strong photoluminescence. Almost 16-fold enhancement of fluorescence properties compared to analogously structured polymer reported earlier has been achieved through aggregation-induced emission (AIE). Modern techniques like FTIR, NMR, PXRD, TGA, DTG, MALDI-TOF MS, SEM, TEM, SAED, and DLS are used to confirm the formation of the desired oligomer. Due to the high quantum yield (0.49), narrow emission band (full width at half maximum = 45 nm), and suitable chemical structure, the oligomer could be used as a potential fluorescent chemo-sensor for arsenic species. The reproducible LOD (2.47 mM) and wide LDR (0–100 mM) values along with robustness make the system highly relevant as an analytical tool. The structure, spectral properties, and sensing abilities of the oligomer have been understood in the light of computational chemistry. Graphical Abstract","PeriodicalId":16228,"journal":{"name":"Journal of Macromolecular Science, Part A","volume":"1 1","pages":"568 - 579"},"PeriodicalIF":0.0,"publicationDate":"2023-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82979480","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}
Abstract Bilirubin is an important biomarker of jaundice, and the quantitative detection of bilirubin is of great significance in the diagnosis and prevention of early jaundice. In this paper, Fe3+ quenched conjugated polymer nanoparticles were used as a "turn-off-on" fluorescence platform to detect bilirubin for the first time. The CPNsPBMC-COOH were prepared through a nanoprecipitation method based on polystyrene maleic anhydride and PBMC, a conjugated polymer synthesized by our research group. The fluorescence of CPNsPBMC-COOH can be efficiently quenched closely to 95% by Fe3+. The optimized fluorescence platform was obtained (CPNsPBMC-COOH: 10 μg/mL, Fe3+: 4.5 μM). The platform to detect bilirubin has a higher sensitivity with a 5 nM of LOD. The detection range was in the 1.32–26.68 μM, which can cover the concentration of bilirubin in normal adult serum (<25 μM). Moreover, the stoichiometries and binding constants of CPNsPBMC-COOH, bilirubin, and Fe3+ are obtained. The binding ability is better for bilirubin and Fe3+. The static quenching mode is found by the absorption spectra and the fluorescence lifetimes. Lastly, this method has obtained satisfactory results in real biological samples (mouse serum and mouse plasma). This work can be used for daily rapid clinical bilirubin detection. Graphical Abstract
{"title":"A sensitive “turn-off-on” fluorescence platform for bilirubin detection based on conjugated polymer nanoparticles and ferric ions","authors":"Jia-zhen Li, Qiu-bo Wang, Xian Zhang, Qian Lu, Zhibin Yang, Xiaoxia Cai","doi":"10.1080/10601325.2023.2227279","DOIUrl":"https://doi.org/10.1080/10601325.2023.2227279","url":null,"abstract":"Abstract Bilirubin is an important biomarker of jaundice, and the quantitative detection of bilirubin is of great significance in the diagnosis and prevention of early jaundice. In this paper, Fe3+ quenched conjugated polymer nanoparticles were used as a \"turn-off-on\" fluorescence platform to detect bilirubin for the first time. The CPNsPBMC-COOH were prepared through a nanoprecipitation method based on polystyrene maleic anhydride and PBMC, a conjugated polymer synthesized by our research group. The fluorescence of CPNsPBMC-COOH can be efficiently quenched closely to 95% by Fe3+. The optimized fluorescence platform was obtained (CPNsPBMC-COOH: 10 μg/mL, Fe3+: 4.5 μM). The platform to detect bilirubin has a higher sensitivity with a 5 nM of LOD. The detection range was in the 1.32–26.68 μM, which can cover the concentration of bilirubin in normal adult serum (<25 μM). Moreover, the stoichiometries and binding constants of CPNsPBMC-COOH, bilirubin, and Fe3+ are obtained. The binding ability is better for bilirubin and Fe3+. The static quenching mode is found by the absorption spectra and the fluorescence lifetimes. Lastly, this method has obtained satisfactory results in real biological samples (mouse serum and mouse plasma). This work can be used for daily rapid clinical bilirubin detection. Graphical Abstract","PeriodicalId":16228,"journal":{"name":"Journal of Macromolecular Science, Part A","volume":"1 1","pages":"557 - 567"},"PeriodicalIF":0.0,"publicationDate":"2023-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87063020","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}
Abstract Sulfur-containing ABA-type polycarbonate triblock copolymers were synthesized via sequential copolymerization of propylene oxide (PO) and carbon dioxide (CO2), followed by propylene oxide (PO) and phthalic thioanhydride (PTA) in the presence of water and Salen-Metal catalysts. The reaction was catalyzed using Salen-Co(III)-Cl/[PPN]Cl and Salen-Cr(III)-Cl/[PPN]Cl catalyst systems. The content of thioester units in the copolymer chain could be adjusted by varying the feed ratios of PTA. These triblock polymers displayed a higher refractive index, reaching up to 1.561. Graphical abstract
{"title":"Synthesis of sulfur-containing polycarbonate block copolymers via Salen-metal catalyzed copolymerization of CO2, propylene oxide, and phthalic thioanhydride","authors":"Shujuan Lu, Qingyun Ge, Chaogang Fan, Xinqiang Wang, Yunqi Chen, Shaohui Lin, Qinmin Pan","doi":"10.1080/10601325.2023.2218405","DOIUrl":"https://doi.org/10.1080/10601325.2023.2218405","url":null,"abstract":"Abstract Sulfur-containing ABA-type polycarbonate triblock copolymers were synthesized via sequential copolymerization of propylene oxide (PO) and carbon dioxide (CO2), followed by propylene oxide (PO) and phthalic thioanhydride (PTA) in the presence of water and Salen-Metal catalysts. The reaction was catalyzed using Salen-Co(III)-Cl/[PPN]Cl and Salen-Cr(III)-Cl/[PPN]Cl catalyst systems. The content of thioester units in the copolymer chain could be adjusted by varying the feed ratios of PTA. These triblock polymers displayed a higher refractive index, reaching up to 1.561. Graphical abstract","PeriodicalId":16228,"journal":{"name":"Journal of Macromolecular Science, Part A","volume":"75 1","pages":"484 - 491"},"PeriodicalIF":0.0,"publicationDate":"2023-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73418630","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}
Pub Date : 2023-06-26DOI: 10.1080/10601325.2023.2227651
Gokhan Sagdic, U. Gunay
Abstract In this work, a rapid polymerization method was combined with thiol-para-fluoro (TPF) “click” post-polymerization modification (PPM) strategy. To this end, a reactive monomer, namely bis((perfluorophenyl)methyl) but-2-ynedioate, was specifically designed and used in the synthesis of polythioether via thiol-Michael addition reaction by using 1,6-hexanedithiol (HDT) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as a catalyst, and the reaction proceeded at room temperature for 5 min to give the pristine polythioether P0. This polymer was then used as a platform to perform PPM with various thiol compounds. The PPM reactions showed quantitative efficiency in 4 h with moderate to high yields. All modified polymers were analyzed with 1H, 13C, and 19F NMR analyses, and molecular weights were calculated by using GPC. It is believed that combining such polymerization and PPM reactions can be a very useful tool to obtain polymers having different structures for different purposes. Hence, this work introduces a new type of polymer backbone that can be rapidly prepared and undergo a relatively fast PPM. Graphical Abstract
{"title":"Post-polymerization modification of pentafluorophenyl-functionalized polythioether via thiol-para-fluoro click reaction","authors":"Gokhan Sagdic, U. Gunay","doi":"10.1080/10601325.2023.2227651","DOIUrl":"https://doi.org/10.1080/10601325.2023.2227651","url":null,"abstract":"Abstract In this work, a rapid polymerization method was combined with thiol-para-fluoro (TPF) “click” post-polymerization modification (PPM) strategy. To this end, a reactive monomer, namely bis((perfluorophenyl)methyl) but-2-ynedioate, was specifically designed and used in the synthesis of polythioether via thiol-Michael addition reaction by using 1,6-hexanedithiol (HDT) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as a catalyst, and the reaction proceeded at room temperature for 5 min to give the pristine polythioether P0. This polymer was then used as a platform to perform PPM with various thiol compounds. The PPM reactions showed quantitative efficiency in 4 h with moderate to high yields. All modified polymers were analyzed with 1H, 13C, and 19F NMR analyses, and molecular weights were calculated by using GPC. It is believed that combining such polymerization and PPM reactions can be a very useful tool to obtain polymers having different structures for different purposes. Hence, this work introduces a new type of polymer backbone that can be rapidly prepared and undergo a relatively fast PPM. Graphical Abstract","PeriodicalId":16228,"journal":{"name":"Journal of Macromolecular Science, Part A","volume":"220 1","pages":"548 - 556"},"PeriodicalIF":0.0,"publicationDate":"2023-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76994549","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}
Pub Date : 2023-06-18DOI: 10.1080/10601325.2023.2222012
A. Nandi, U. Basak, D. P. Chatterjee
Abstract Electroactive polymers (EAPs) have the interesting property of generation and flow of charges and possess exciting tunable optoelectronic properties by incorporating side chains via ‘grafting’ from the backbone chain retaining its properties and importing new properties from the grafted chains. The graft copolymers of EAPs exhibit exciting tunable optoelectronic properties by varying external stimuli like pH, temperature, ions, surfactants, light etc. Grafting of two main electroactive polymers e.g. polythiophene (PT) and poly(vinylidene fluoride) (PVDF) have spurred significant research attention and the controlled grafting has been made using atom transfer radical polymerization (ATRP) technique with suitable catalyst/ligand systems. Few examples of grafting of PT and PVDF by RAFT polymerization are also described. This feature article delineates controlled grafting of different stimuli-responsive polymers on polythiophene and PVDF backbone highlighting their optoelectronic properties, useful for making chemical/biological sensors, logic gates and antifouling/antibacterial membranes. Interactions of the grafted chains with the external physical or chemical stimuli (like pH, temperature, photoirradiation, ions, surfactants, etc.) significantly alter the backbone conformation both in solution and solid state. This leads to changes in conjugation length of the backbone chain, hence tunes the band gap varying the optoelectronic properties useful for fabrication of stimuli dependent sensors and modulation of membrane pore size suitable for antifouling and antibacterial membranes. Graphical Abstract
{"title":"Controlled grafting of polythiophene and poly(vinylidene fluoride)","authors":"A. Nandi, U. Basak, D. P. Chatterjee","doi":"10.1080/10601325.2023.2222012","DOIUrl":"https://doi.org/10.1080/10601325.2023.2222012","url":null,"abstract":"Abstract Electroactive polymers (EAPs) have the interesting property of generation and flow of charges and possess exciting tunable optoelectronic properties by incorporating side chains via ‘grafting’ from the backbone chain retaining its properties and importing new properties from the grafted chains. The graft copolymers of EAPs exhibit exciting tunable optoelectronic properties by varying external stimuli like pH, temperature, ions, surfactants, light etc. Grafting of two main electroactive polymers e.g. polythiophene (PT) and poly(vinylidene fluoride) (PVDF) have spurred significant research attention and the controlled grafting has been made using atom transfer radical polymerization (ATRP) technique with suitable catalyst/ligand systems. Few examples of grafting of PT and PVDF by RAFT polymerization are also described. This feature article delineates controlled grafting of different stimuli-responsive polymers on polythiophene and PVDF backbone highlighting their optoelectronic properties, useful for making chemical/biological sensors, logic gates and antifouling/antibacterial membranes. Interactions of the grafted chains with the external physical or chemical stimuli (like pH, temperature, photoirradiation, ions, surfactants, etc.) significantly alter the backbone conformation both in solution and solid state. This leads to changes in conjugation length of the backbone chain, hence tunes the band gap varying the optoelectronic properties useful for fabrication of stimuli dependent sensors and modulation of membrane pore size suitable for antifouling and antibacterial membranes. Graphical Abstract","PeriodicalId":16228,"journal":{"name":"Journal of Macromolecular Science, Part A","volume":"10 1","pages":"525 - 547"},"PeriodicalIF":0.0,"publicationDate":"2023-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76376840","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}
Pub Date : 2023-06-05DOI: 10.1080/10601325.2023.2216722
M. Yu, Ruize Gao, L. Qi, Yuanrong Sun, Lele Cheng, Zhonghao Mei, Ming-Xia Sun, Zeyu Sun
Abstract Large tow carbon fiber (LTCF) has excellent performance and low cost. However, there are still many difficulties in the application of LTCFs, among which the problem of interfacial penetration is mainly solved. Building interfaces with sizing structures of fiber composites is an effective approach to achieve high performance. In this article, a water-based epoxy sizing agent suitable for LTCF fiber thermoset composites was studied. A comparison of the five LTCFs in this study shows that the wettability and contact angle of the sized LTCFs are significantly improved. In addition, the interfacial shear strength (IFSS) and interlaminar shear strength (ILSS) increased from 52.3 to 71.0 MPa (35%) and 36.4 to 54.6 MPa (50%), respectively. Compared with other imported LTCFs, domestic large-size LTCFs have a wide variety and a large number of surface functional groups, thereby improving their wettability and covalent bonding with the resin matrix. This work has reference significance for the practical application and industrial production of LTCFRP. Graphical abstract
{"title":"Large-tow carbon fibers coated an aqueous epoxy sizing agent to enhance interfacial interactions","authors":"M. Yu, Ruize Gao, L. Qi, Yuanrong Sun, Lele Cheng, Zhonghao Mei, Ming-Xia Sun, Zeyu Sun","doi":"10.1080/10601325.2023.2216722","DOIUrl":"https://doi.org/10.1080/10601325.2023.2216722","url":null,"abstract":"Abstract Large tow carbon fiber (LTCF) has excellent performance and low cost. However, there are still many difficulties in the application of LTCFs, among which the problem of interfacial penetration is mainly solved. Building interfaces with sizing structures of fiber composites is an effective approach to achieve high performance. In this article, a water-based epoxy sizing agent suitable for LTCF fiber thermoset composites was studied. A comparison of the five LTCFs in this study shows that the wettability and contact angle of the sized LTCFs are significantly improved. In addition, the interfacial shear strength (IFSS) and interlaminar shear strength (ILSS) increased from 52.3 to 71.0 MPa (35%) and 36.4 to 54.6 MPa (50%), respectively. Compared with other imported LTCFs, domestic large-size LTCFs have a wide variety and a large number of surface functional groups, thereby improving their wettability and covalent bonding with the resin matrix. This work has reference significance for the practical application and industrial production of LTCFRP. Graphical abstract","PeriodicalId":16228,"journal":{"name":"Journal of Macromolecular Science, Part A","volume":"10 1","pages":"515 - 523"},"PeriodicalIF":0.0,"publicationDate":"2023-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82409466","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}
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