Pub Date : 2023-06-02DOI: 10.1080/10601325.2023.2216719
Nisa Demirbilek, Nergiz Cengiz, Tugce N. Gevrek
Abstract Polymers carrying different reactive groups that can be orthogonally functionalized are desirable for the design of multi-functionalizable materials. While several orthogonally functionalizable polymers have been reported, most of the work utilizes handles that are reactive toward different functional groups. However, examples of polymers that are orthogonally reactive toward molecules bearing the same functional group are rare. In this work, we report polymeric materials that can be sequentially functionalized using different amine-bearing molecules. Herein, we synthesized isocyanate and epoxide group containing copolymers, and investigated their sequential functionalization with amine-containing molecules. We show that such copolymers can be first functionalized with a particular amine-bearing molecule at room temperature, using conjugation through the isocyanate group. Thereafter, a different amine-containing molecule can be attached through the epoxy-amine reaction at 65 °C. Chemical characterizations of parent and subsequently functionalized copolymers were done by 1H NMR and FTIR spectroscopy techniques, to establish orthogonal functionalization. Additionally, the epoxide side chains were utilized as surface anchoring group after the functionalization of the polymer via isocyanate-amine reaction. This straightforward approach for obtaining orthogonally reactive amine-functionalizable copolymers, and surfaces derived thereof, would be attractive materials for various biomedical applications. Graphical abstract
{"title":"Pendant isocyanate and epoxide-containing copolymers: synthesis, sequential dual-functionalization with amines, and surface modifications","authors":"Nisa Demirbilek, Nergiz Cengiz, Tugce N. Gevrek","doi":"10.1080/10601325.2023.2216719","DOIUrl":"https://doi.org/10.1080/10601325.2023.2216719","url":null,"abstract":"Abstract Polymers carrying different reactive groups that can be orthogonally functionalized are desirable for the design of multi-functionalizable materials. While several orthogonally functionalizable polymers have been reported, most of the work utilizes handles that are reactive toward different functional groups. However, examples of polymers that are orthogonally reactive toward molecules bearing the same functional group are rare. In this work, we report polymeric materials that can be sequentially functionalized using different amine-bearing molecules. Herein, we synthesized isocyanate and epoxide group containing copolymers, and investigated their sequential functionalization with amine-containing molecules. We show that such copolymers can be first functionalized with a particular amine-bearing molecule at room temperature, using conjugation through the isocyanate group. Thereafter, a different amine-containing molecule can be attached through the epoxy-amine reaction at 65 °C. Chemical characterizations of parent and subsequently functionalized copolymers were done by 1H NMR and FTIR spectroscopy techniques, to establish orthogonal functionalization. Additionally, the epoxide side chains were utilized as surface anchoring group after the functionalization of the polymer via isocyanate-amine reaction. This straightforward approach for obtaining orthogonally reactive amine-functionalizable copolymers, and surfaces derived thereof, would be attractive materials for various biomedical applications. Graphical abstract","PeriodicalId":16228,"journal":{"name":"Journal of Macromolecular Science, Part A","volume":"29 1","pages":"505 - 514"},"PeriodicalIF":0.0,"publicationDate":"2023-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76744090","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 : 2023-05-31DOI: 10.1080/10601325.2023.2212732
Dongdong Wang, Na Xu, Yang Guo, Dan Wang, Yongzhong Liang
Abstract In contrast to the typical template-based multistep approach for constructing multi-functional mesoporous hollow silica nanocomposites (MHSN), a simple and template-free fabricate system has been developed to develop versatile mesoporous hollow silica nanocapsules (OSNs) encompassing together isopentyl acetate (IsA) solution and AuNPs. This new material has tiny and homogeneous particle sizes (∼82 nm), a large surface area (535 m2 g−1), and remarkable colloidal durability in water. The oil-phase IsA with high volatility and a low boiling point (142 °C) is critical in building bulky hollow cavities from structural strategy. It allows the IsA@OSNs to become an effective development mediator in the ablation of high-intensity focused ultrasound (HIFU) treatment. Furthermore, the distinctive satellite-like dispersion of Gold (AuNPs) on the silica shell provided IsA@OSNs with outstanding magnetic resonance imaging (MRI) contrasts in A549 lung cells in vitro and in vivo. Furthermore, such unique theranostics agents have excellent systemic toxicity, which promises well for promising clinical use in MRI-piloted HIFU treatment. Graphical Abstract
{"title":"Synergic fabrication of hybrid nanocapsules gold-organosilica for MRI-guided photothermal-enhanced synergistic effect chemodynamic lung cancer therapy","authors":"Dongdong Wang, Na Xu, Yang Guo, Dan Wang, Yongzhong Liang","doi":"10.1080/10601325.2023.2212732","DOIUrl":"https://doi.org/10.1080/10601325.2023.2212732","url":null,"abstract":"Abstract In contrast to the typical template-based multistep approach for constructing multi-functional mesoporous hollow silica nanocomposites (MHSN), a simple and template-free fabricate system has been developed to develop versatile mesoporous hollow silica nanocapsules (OSNs) encompassing together isopentyl acetate (IsA) solution and AuNPs. This new material has tiny and homogeneous particle sizes (∼82 nm), a large surface area (535 m2 g−1), and remarkable colloidal durability in water. The oil-phase IsA with high volatility and a low boiling point (142 °C) is critical in building bulky hollow cavities from structural strategy. It allows the IsA@OSNs to become an effective development mediator in the ablation of high-intensity focused ultrasound (HIFU) treatment. Furthermore, the distinctive satellite-like dispersion of Gold (AuNPs) on the silica shell provided IsA@OSNs with outstanding magnetic resonance imaging (MRI) contrasts in A549 lung cells in vitro and in vivo. Furthermore, such unique theranostics agents have excellent systemic toxicity, which promises well for promising clinical use in MRI-piloted HIFU treatment. Graphical Abstract","PeriodicalId":16228,"journal":{"name":"Journal of Macromolecular Science, Part A","volume":"163 1","pages":"492 - 504"},"PeriodicalIF":0.0,"publicationDate":"2023-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86794666","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 : 2023-05-26DOI: 10.1080/10601325.2023.2212707
M. Otaki, Ryo Miyashita, H. Goto
Abstract Electro-optically active low-bandgap conjugated copolymers were obtained by electrochemical polymerization (EP) in cholesteric liquid crystal (CLC). We prepared CLC electrolyte mixture blends of monomers, and electrochemically polymerized for obtaining conjugated copolymer with optical activity, in which the structure of the CLC is transferred, from achiral monomers on a CLC template. In addition, this copolymer showed a narrow bandgap and a significant red shift of the absorption band compared to the homopolymer. The optical rotatory dispersion (ORD) indicates that the polymer is chiroptically active and that the optical rotation can be tuned via redox. The guest monomers used for the EP in liquid crystal (LC) require solubility in the host LC and a rod-like structure, limiting their structural design. This technique has the advantage that complex synthesis of monomers is no required, and simple composition of monomers can be used to prepare copolymer films in a convenient manner by blending various monomers. This method expands the design range of optically active electrochromic devices based on conjugated polymers with pleochroic properties. Graphical Abstract
{"title":"Monomer blended electrochemical polymerization in chiral liquid crystals to produce electro-optically active copolymer","authors":"M. Otaki, Ryo Miyashita, H. Goto","doi":"10.1080/10601325.2023.2212707","DOIUrl":"https://doi.org/10.1080/10601325.2023.2212707","url":null,"abstract":"Abstract Electro-optically active low-bandgap conjugated copolymers were obtained by electrochemical polymerization (EP) in cholesteric liquid crystal (CLC). We prepared CLC electrolyte mixture blends of monomers, and electrochemically polymerized for obtaining conjugated copolymer with optical activity, in which the structure of the CLC is transferred, from achiral monomers on a CLC template. In addition, this copolymer showed a narrow bandgap and a significant red shift of the absorption band compared to the homopolymer. The optical rotatory dispersion (ORD) indicates that the polymer is chiroptically active and that the optical rotation can be tuned via redox. The guest monomers used for the EP in liquid crystal (LC) require solubility in the host LC and a rod-like structure, limiting their structural design. This technique has the advantage that complex synthesis of monomers is no required, and simple composition of monomers can be used to prepare copolymer films in a convenient manner by blending various monomers. This method expands the design range of optically active electrochromic devices based on conjugated polymers with pleochroic properties. Graphical Abstract","PeriodicalId":16228,"journal":{"name":"Journal of Macromolecular Science, Part A","volume":"1 1","pages":"463 - 473"},"PeriodicalIF":0.0,"publicationDate":"2023-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81473492","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 : 2023-05-26DOI: 10.1080/10601325.2023.2216757
Yuqi Chen, Xuelian Wang, Zhuhang Lu, Cong Chang, Yueli Zhang, Bo Lu
Abstract Surface modification of hollow mesoporous silica nanoparticles (HMSNs) with unique advantages are highly promising for drug delivery and have emerged for effective cancer treatment. In this study, functionalized nanoparticles for targeting and dual-responsive release of loaded doxorubicin hydrochloride (DOX·HCL) and indocyanine green (ICG) (labeled as ID@HCH). In addition, chitosan (CS) was conjugated onto the HMSNs as capping agents and then dialdehyde hyaluronic acid (HDA) was modified to endow the ability to target the CD44 receptor. The characterizations demonstrated that nanocarriers have been successfully constructed with excellent drug loading capacity (DL) and drug entrapment efficiency (EE). The in vitro DOX control release displayed pH/enzyme-response properties owing to the pH-dependent swelling effect of chitosan and the HDA degraded by hyaluronidases (HAase). Moreover, the results of in vitro cell experiments proved that the ID@HCH could inhibit the cancer cells viability via accurately targeting HepG2 cells and chemotherapy combined with photodynamic therapy. This study demonstrated that ID@HCH is a new promising dual-responsive drug delivery system for chemotherapy and photodynamic therapy. Graphical Abstract
{"title":"Dual-responsive targeted hollow mesoporous silica nanoparticles for cancer photodynamic therapy and chemotherapy","authors":"Yuqi Chen, Xuelian Wang, Zhuhang Lu, Cong Chang, Yueli Zhang, Bo Lu","doi":"10.1080/10601325.2023.2216757","DOIUrl":"https://doi.org/10.1080/10601325.2023.2216757","url":null,"abstract":"Abstract Surface modification of hollow mesoporous silica nanoparticles (HMSNs) with unique advantages are highly promising for drug delivery and have emerged for effective cancer treatment. In this study, functionalized nanoparticles for targeting and dual-responsive release of loaded doxorubicin hydrochloride (DOX·HCL) and indocyanine green (ICG) (labeled as ID@HCH). In addition, chitosan (CS) was conjugated onto the HMSNs as capping agents and then dialdehyde hyaluronic acid (HDA) was modified to endow the ability to target the CD44 receptor. The characterizations demonstrated that nanocarriers have been successfully constructed with excellent drug loading capacity (DL) and drug entrapment efficiency (EE). The in vitro DOX control release displayed pH/enzyme-response properties owing to the pH-dependent swelling effect of chitosan and the HDA degraded by hyaluronidases (HAase). Moreover, the results of in vitro cell experiments proved that the ID@HCH could inhibit the cancer cells viability via accurately targeting HepG2 cells and chemotherapy combined with photodynamic therapy. This study demonstrated that ID@HCH is a new promising dual-responsive drug delivery system for chemotherapy and photodynamic therapy. Graphical Abstract","PeriodicalId":16228,"journal":{"name":"Journal of Macromolecular Science, Part A","volume":"54 1","pages":"474 - 483"},"PeriodicalIF":0.0,"publicationDate":"2023-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77625851","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 : 2023-05-23DOI: 10.1080/10601325.2023.2212731
T. Benhalima, H. Ferfera-Harrar, N. Saha, P. Sáha
Abstract In this study, initially synthesized magnetic nanoparticles modified with citrate ions (MNPs/m-MNPs) were entrapped in aluminum-carboxymethyl cellulose/dextran sulfate beads to form hybrid nanocomposites (m-MNPs-C/D0.5) using a simple two-pot method. Sodium dodecyl sulfate surfactant was employed to develop a porous interconnected structure. The synergistic effect of the hybrid nanocomposites was studied for the parametric adsorption of methylene blue dye pollutant. The swelling ability of hybrid hydrogels was also studied for different solution pH. The results clearly indicated that equilibrium was reached faster at about 3 h for the m-MNPs-loaded magnetic beads (m-MNPs-C/D0.5), whereas at 6 h for the MNPs-loaded beads (MNPs0.4-C/D0.5) and the unloaded simple ones (MNPs0-C/D0.5). Experimental data modeling of adsorption kinetics and isotherms as well as thermodynamic study showed a good correlation with pseudo-second order kinetic and Langmuir models while the adsorption process on magnetic beads was exothermic. The maximum adsorption capacity for MNPs0-C/D0.5 and the optimized m-MNPs0.3-C/D0.5 hydrogel were 380 and 529 mg g−1, respectively. Furthermore, all hydrogels were perfectly regenerated and then reused for five adsorption-desorption cycles without apparent loss of stability that confirms their consideration as alternative and effective adsorbents for wastewater treatment. The manufactured beads were characterized by scanning electron microscopy/energy dispersive X-Ray, dynamic light scattering, X-ray diffraction, thermogravimetric analysis, vibrating sample magnetometer and fourier-transform infrared spectroscopy. Graphical Abstract
在本研究中，采用简单的双锅法将初步合成的柠檬酸盐离子修饰磁性纳米颗粒(MNPs/m-MNPs)包埋在铝-羧甲基纤维素/葡聚糖硫酸微球中，形成混合纳米复合材料(m-MNPs- c /D0.5)。采用十二烷基硫酸钠表面活性剂制备多孔互联结构。研究了杂化纳米复合材料对亚甲基蓝染料污染物的协同吸附作用。结果表明，负载m- mnps的磁珠(m-MNPs-C/D0.5)在3 h左右达到平衡，负载mnps的磁珠(MNPs0.4-C/D0.5)和未负载MNPs0-C/D0.5的简单磁珠(MNPs0-C/D0.5)在6 h左右达到平衡。吸附动力学和等温线的实验数据建模以及热力学研究表明，磁珠吸附过程为放热过程，与拟二级动力学模型和Langmuir模型具有良好的相关性。MNPs0-C/D0.5和优化后的m-MNPs0.3-C/D0.5水凝胶的最大吸附量分别为380和529 mg g−1。此外，所有水凝胶都可以完全再生，然后在五次吸附-解吸循环中重复使用，而没有明显的稳定性损失，这证实了它们作为废水处理的替代有效吸附剂的考虑。采用扫描电镜/能量色散x射线、动态光散射、x射线衍射、热重分析、振动样品磁强计和傅里叶变换红外光谱对制备的微球进行了表征。图形抽象
{"title":"Fe3O4 imbuing carboxymethyl cellulose/dextran sulfate nanocomposite hydrogel beads: an effective adsorbent for methylene blue dye pollutant","authors":"T. Benhalima, H. Ferfera-Harrar, N. Saha, P. Sáha","doi":"10.1080/10601325.2023.2212731","DOIUrl":"https://doi.org/10.1080/10601325.2023.2212731","url":null,"abstract":"Abstract In this study, initially synthesized magnetic nanoparticles modified with citrate ions (MNPs/m-MNPs) were entrapped in aluminum-carboxymethyl cellulose/dextran sulfate beads to form hybrid nanocomposites (m-MNPs-C/D0.5) using a simple two-pot method. Sodium dodecyl sulfate surfactant was employed to develop a porous interconnected structure. The synergistic effect of the hybrid nanocomposites was studied for the parametric adsorption of methylene blue dye pollutant. The swelling ability of hybrid hydrogels was also studied for different solution pH. The results clearly indicated that equilibrium was reached faster at about 3 h for the m-MNPs-loaded magnetic beads (m-MNPs-C/D0.5), whereas at 6 h for the MNPs-loaded beads (MNPs0.4-C/D0.5) and the unloaded simple ones (MNPs0-C/D0.5). Experimental data modeling of adsorption kinetics and isotherms as well as thermodynamic study showed a good correlation with pseudo-second order kinetic and Langmuir models while the adsorption process on magnetic beads was exothermic. The maximum adsorption capacity for MNPs0-C/D0.5 and the optimized m-MNPs0.3-C/D0.5 hydrogel were 380 and 529 mg g−1, respectively. Furthermore, all hydrogels were perfectly regenerated and then reused for five adsorption-desorption cycles without apparent loss of stability that confirms their consideration as alternative and effective adsorbents for wastewater treatment. The manufactured beads were characterized by scanning electron microscopy/energy dispersive X-Ray, dynamic light scattering, X-ray diffraction, thermogravimetric analysis, vibrating sample magnetometer and fourier-transform infrared spectroscopy. Graphical Abstract","PeriodicalId":16228,"journal":{"name":"Journal of Macromolecular Science, Part A","volume":"3 1","pages":"442 - 461"},"PeriodicalIF":0.0,"publicationDate":"2023-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89962085","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 : 2023-05-22DOI: 10.1080/10601325.2023.2213699
Yao-Ying Chuang, J. Deka, W. Hsieh, S. Rwei, Jia-Wei Shiu, Tun-Fun Way
Abstract In this study, thermo and pH-sensitive multifunctional poly (N-isopropylacrylamide-co- N,N’-methylenebisacrylamide, Poly(NIPAAm-co-MBA) - (N-4-amino-2-methylene-4-oxobutanoic acid, IAM) named as (PNM@IAM) core-shell microgels are synthesized by inverse microemulsion polymerization technique using two monomers, N-isopropylacrylamide (NIPAAm) and N-4-amino-2-methylene-4-oxobutanoic acid (IAM). The formation of the microgels are confirmed by 1H nuclear magnetic resonance (1H NMR) and attenuated total reflection fourier transform infrared (ATR-FTIR) spectra. The light transmittance study shows that the microgels prepared at different concentrations and pHs exhibit different physical properties. The phase transition temperature is increased with the addition of IAM. Dynamic light scattering (DLS) analysis reveals that the swelling of the microgels at basic environment is due to the deprotonation of the weak acid groups in IAM. The metal ion chelating test shows that the core-shell PNM@IAM could effectively absorb metal ions in highly basic environment. The absorption and release of heavy metal ions from aqueous solution could be controlled by adjusting the pH of the reaction environment. Graphical Abstract
{"title":"Synthesis and characterization of PNM@IAM core-shell microgels through inverse emulsion polymerization and its application for heavy metal ions capture","authors":"Yao-Ying Chuang, J. Deka, W. Hsieh, S. Rwei, Jia-Wei Shiu, Tun-Fun Way","doi":"10.1080/10601325.2023.2213699","DOIUrl":"https://doi.org/10.1080/10601325.2023.2213699","url":null,"abstract":"Abstract In this study, thermo and pH-sensitive multifunctional poly (N-isopropylacrylamide-co- N,N’-methylenebisacrylamide, Poly(NIPAAm-co-MBA) - (N-4-amino-2-methylene-4-oxobutanoic acid, IAM) named as (PNM@IAM) core-shell microgels are synthesized by inverse microemulsion polymerization technique using two monomers, N-isopropylacrylamide (NIPAAm) and N-4-amino-2-methylene-4-oxobutanoic acid (IAM). The formation of the microgels are confirmed by 1H nuclear magnetic resonance (1H NMR) and attenuated total reflection fourier transform infrared (ATR-FTIR) spectra. The light transmittance study shows that the microgels prepared at different concentrations and pHs exhibit different physical properties. The phase transition temperature is increased with the addition of IAM. Dynamic light scattering (DLS) analysis reveals that the swelling of the microgels at basic environment is due to the deprotonation of the weak acid groups in IAM. The metal ion chelating test shows that the core-shell PNM@IAM could effectively absorb metal ions in highly basic environment. The absorption and release of heavy metal ions from aqueous solution could be controlled by adjusting the pH of the reaction environment. Graphical Abstract","PeriodicalId":16228,"journal":{"name":"Journal of Macromolecular Science, Part A","volume":"26 5 1","pages":"427 - 441"},"PeriodicalIF":0.0,"publicationDate":"2023-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89682844","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 : 2023-05-22DOI: 10.1080/10601325.2023.2212704
Amjad Ali, Adnan Murad Bhayo, A. Naveed, Tariq Aziz, N. Ahmad, Waqar Ahamad Qureshi, Adnan Younis, Jamile Mohammadi Moradian, M. Hassan, Muhammad Minhaj Qadri, Zhiqiang Fan, Li Guo
Abstract To understand how the silyl-bridged metallocene catalysts rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 behave against dienes under the same reaction condition because of its importance as a commercial polymerization catalyst and ethylene propylene diene monomers (EPDM). Adding diene depressed the catalytic activity, especially 5-ethylidene-2-norbornene (ENB) exerted the most substantial deactivation effect. Firstly, we examine the (ENB, vinyl norbornene (VNB) and 4-vinylcyclohexene (VCH)) non-conjugated and conjugated (isoprene (IP), butadiene (BD)) diene and address how polymerization catalysts behave against these dienes. For example, the catalytic activity was enhanced with IP and BD (3–3.3106 gm/mmolMt·h) compared to ENB, VNB and VCH. The VNB incorporation rate was prolonged (5.4 mol%), but with IP and BD, it was relatively moderate. E/P/IP and E/P/BD with higher incorporation of E produced a higher MW, which means that the chain transfer reaction with ethylene is slower than P. Secondly, we address how the dienes exocyclic and exocyclicπ bonds of non-conjugated and conjugated properties of IP and BD affect the kinetic measurements such as active centers [Zr]/[C*] fraction, EPDM chain propagation, termination, and isomerization. Finally, we compare [Zr]/[C*] and kpPE, kpP and kpDienes for different EPDM. After collecting these kinetic parameters, we can describe the mechanism’s intricacy and the existence of considerable catalyst dormancy with dienes under identical reaction conditions. Graphical Abstract
{"title":"Why only half of the added ansa-metallocene catalyst active in the E/P/diene polymerization: catalyst evaluation in terms of active center [Zr]/[C*] fraction and polymerization propagation rate constants","authors":"Amjad Ali, Adnan Murad Bhayo, A. Naveed, Tariq Aziz, N. Ahmad, Waqar Ahamad Qureshi, Adnan Younis, Jamile Mohammadi Moradian, M. Hassan, Muhammad Minhaj Qadri, Zhiqiang Fan, Li Guo","doi":"10.1080/10601325.2023.2212704","DOIUrl":"https://doi.org/10.1080/10601325.2023.2212704","url":null,"abstract":"Abstract To understand how the silyl-bridged metallocene catalysts rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 behave against dienes under the same reaction condition because of its importance as a commercial polymerization catalyst and ethylene propylene diene monomers (EPDM). Adding diene depressed the catalytic activity, especially 5-ethylidene-2-norbornene (ENB) exerted the most substantial deactivation effect. Firstly, we examine the (ENB, vinyl norbornene (VNB) and 4-vinylcyclohexene (VCH)) non-conjugated and conjugated (isoprene (IP), butadiene (BD)) diene and address how polymerization catalysts behave against these dienes. For example, the catalytic activity was enhanced with IP and BD (3–3.3106 gm/mmolMt·h) compared to ENB, VNB and VCH. The VNB incorporation rate was prolonged (5.4 mol%), but with IP and BD, it was relatively moderate. E/P/IP and E/P/BD with higher incorporation of E produced a higher MW, which means that the chain transfer reaction with ethylene is slower than P. Secondly, we address how the dienes exocyclic and exocyclicπ bonds of non-conjugated and conjugated properties of IP and BD affect the kinetic measurements such as active centers [Zr]/[C*] fraction, EPDM chain propagation, termination, and isomerization. Finally, we compare [Zr]/[C*] and kpPE, kpP and kpDienes for different EPDM. After collecting these kinetic parameters, we can describe the mechanism’s intricacy and the existence of considerable catalyst dormancy with dienes under identical reaction conditions. Graphical Abstract","PeriodicalId":16228,"journal":{"name":"Journal of Macromolecular Science, Part A","volume":"79 1","pages":"417 - 426"},"PeriodicalIF":0.0,"publicationDate":"2023-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79239266","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 : 2023-05-22DOI: 10.1080/10601325.2023.2211613
Xian-Zhao Wang, Jinshui Yao
Abstract In this study, several polyphenylacetylenes (PPAs) derivatives containing amino acid pendant groups were synthesized using a rhodium system catalyst (Rh(nbd)BPh4). The synthesized derivatives of PPAs included single chiral PPA with a single chiral center in the pendant groups and double chiral PPA' with two chiral centers in the pendant groups. The PPA and PPA' showed strong circular dichroism (CD) signals in the main chain absorption region of the UV-vis spectrum, while the monomer showed no CD signals. Furthermore, the PPA and PPA' with different chiral pendant groups showed different Cotton effects in the CD spectra. The results showed that these polymers existed in helical conformation, and the chiral center of the pendant groups affected the polymerization and helical structure of PPAs. Graphical Abstract
{"title":"Effect of amino acid pendant groups on the helical configuration of polyphenylacetylene","authors":"Xian-Zhao Wang, Jinshui Yao","doi":"10.1080/10601325.2023.2211613","DOIUrl":"https://doi.org/10.1080/10601325.2023.2211613","url":null,"abstract":"Abstract In this study, several polyphenylacetylenes (PPAs) derivatives containing amino acid pendant groups were synthesized using a rhodium system catalyst (Rh(nbd)BPh4). The synthesized derivatives of PPAs included single chiral PPA with a single chiral center in the pendant groups and double chiral PPA' with two chiral centers in the pendant groups. The PPA and PPA' showed strong circular dichroism (CD) signals in the main chain absorption region of the UV-vis spectrum, while the monomer showed no CD signals. Furthermore, the PPA and PPA' with different chiral pendant groups showed different Cotton effects in the CD spectra. The results showed that these polymers existed in helical conformation, and the chiral center of the pendant groups affected the polymerization and helical structure of PPAs. Graphical Abstract","PeriodicalId":16228,"journal":{"name":"Journal of Macromolecular Science, Part A","volume":"51 1","pages":"409 - 416"},"PeriodicalIF":0.0,"publicationDate":"2023-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90322884","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 Novel hydrophilic polymers consisting of fluorene modified by alkoxyl chain were designed and synthesized via radical polymerization from acrylic acid (PAAF) or acrylamide (PAMF) in the presence of azobisisobutyronitrile. All of these polymers were good water-soluble. The photophysical behaviors of the polymers and the selectivity and sensitivity to detection metal ions were studied by UV-visible and fluorescence spectroscopy technique, and some color changes were visible to the naked eye appeared. The PAMF fluorescent probe showed good selectivity and sensitivity to detection Fe3+ (2.4 × 10−7 mol/L) and PAAF exhibited good selectivity and sensitivity to detection Fe2+ (1.5 × 10−6 mol/L) and Cu2+ (5 × 10−7 mol/L) in water. Graphical Abstract
{"title":"A hydrophilic polymer based on alkoxyl chain modified fluorene: the novel fluorescence colorimetric sensor for Fe3+, Fe2+, and Cu2+ in aqueous media","authors":"C. Ma, Zihan Ma, Ziyuan He, Xianjian Wang, Longhao Zhao, Xuegang Chen","doi":"10.1080/10601325.2023.2210165","DOIUrl":"https://doi.org/10.1080/10601325.2023.2210165","url":null,"abstract":"Abstract Novel hydrophilic polymers consisting of fluorene modified by alkoxyl chain were designed and synthesized via radical polymerization from acrylic acid (PAAF) or acrylamide (PAMF) in the presence of azobisisobutyronitrile. All of these polymers were good water-soluble. The photophysical behaviors of the polymers and the selectivity and sensitivity to detection metal ions were studied by UV-visible and fluorescence spectroscopy technique, and some color changes were visible to the naked eye appeared. The PAMF fluorescent probe showed good selectivity and sensitivity to detection Fe3+ (2.4 × 10−7 mol/L) and PAAF exhibited good selectivity and sensitivity to detection Fe2+ (1.5 × 10−6 mol/L) and Cu2+ (5 × 10−7 mol/L) in water. Graphical Abstract","PeriodicalId":16228,"journal":{"name":"Journal of Macromolecular Science, Part A","volume":"9 1","pages":"397 - 408"},"PeriodicalIF":0.0,"publicationDate":"2023-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87280092","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 : 2023-05-11DOI: 10.1080/10601325.2023.2208607
D. Yigit, S. Hacioglu, M. Güllü, L. Toppare
Abstract Herein, three multifunctional 3',4'-bis(alkyloxy)-2,2':5',2"-terthiophene comprising monomers with different alkyl chains were electrochemically polymerized on an ITO electrode to obtain the polymers; poly(3',4'-dibutoxy-2,2':5',2"-terthiophene) (P1), poly(3',4'-bis(hexyloxy)-2,2':5',2"-terthiophene) (P2), and poly(3',4'-bis(octyloxy)-2,2':5',2"-terthiophene) (P3). Cyclic voltammetry and in situ spectroelectrochemical studies were performed for the polymers to investigate their oxidation potentials, HOMO/LUMO energy levels, band gaps (Egop), optical contrasts (T%), and switching times. All polymers had an optical band gap at around 1.8 and 1.9 eV and revealed different tones of red color in their neutral states and different tones of blue color in their oxidized states with similar electrochromic features. This means that the alteration of the alkyl chain lengths did not affect the band gap and the colors of the resulting polymers significantly. When P1, P2, and P3 were compared in terms of electrochromic contrast and switching studies, P1 had superior optical contrast and switching time values. P1 exhibited 51% optical contrast at 520 nm which is a rare and desired property for -conjugated conducting polymers in the visible region. P1, P2 and P3 conducting polymer films, which were also used for energy storage applications before, revealed promising electrochromic characters in this study, so these poly(3',4'-bis(alkyloxy)-2,2':5',2"-terthiophene) derivatives can be called as multifunctional next-generation materials. Graphical Abstract
{"title":"Electrochemical and optical properties of 3',4'-bis(alkyloxy)-2,2':5',2\"-terthiophene bearing multifunctional polymers: Effect of alkyl chain length on electrochromic properties","authors":"D. Yigit, S. Hacioglu, M. Güllü, L. Toppare","doi":"10.1080/10601325.2023.2208607","DOIUrl":"https://doi.org/10.1080/10601325.2023.2208607","url":null,"abstract":"Abstract Herein, three multifunctional 3',4'-bis(alkyloxy)-2,2':5',2\"-terthiophene comprising monomers with different alkyl chains were electrochemically polymerized on an ITO electrode to obtain the polymers; poly(3',4'-dibutoxy-2,2':5',2\"-terthiophene) (P1), poly(3',4'-bis(hexyloxy)-2,2':5',2\"-terthiophene) (P2), and poly(3',4'-bis(octyloxy)-2,2':5',2\"-terthiophene) (P3). Cyclic voltammetry and in situ spectroelectrochemical studies were performed for the polymers to investigate their oxidation potentials, HOMO/LUMO energy levels, band gaps (Egop), optical contrasts (T%), and switching times. All polymers had an optical band gap at around 1.8 and 1.9 eV and revealed different tones of red color in their neutral states and different tones of blue color in their oxidized states with similar electrochromic features. This means that the alteration of the alkyl chain lengths did not affect the band gap and the colors of the resulting polymers significantly. When P1, P2, and P3 were compared in terms of electrochromic contrast and switching studies, P1 had superior optical contrast and switching time values. P1 exhibited 51% optical contrast at 520 nm which is a rare and desired property for -conjugated conducting polymers in the visible region. P1, P2 and P3 conducting polymer films, which were also used for energy storage applications before, revealed promising electrochromic characters in this study, so these poly(3',4'-bis(alkyloxy)-2,2':5',2\"-terthiophene) derivatives can be called as multifunctional next-generation materials. Graphical Abstract","PeriodicalId":16228,"journal":{"name":"Journal of Macromolecular Science, Part A","volume":"21 1","pages":"384 - 396"},"PeriodicalIF":0.0,"publicationDate":"2023-05-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80843041","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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