Hao Xu , Harrison A. Mills , Shuyang Ye , Dwight S. Seferos
Precision polymers and oligomers are distinguished by their well-defined characteristics (e.g., chain length, monomer sequence). As a result, they have been leveraged in recent years to study numerous structure–property relationships ranging from photophysical characteristics to antimicrobial activity. However, the synthesis of precision polymers and oligomers often requires elaborate building blocks that are compatible with specific polymerization approaches. In most cases, these building blocks are neither recovered nor recycled, limiting the efficiency and sustainability of these synthetic methods. Herein, we report the first synthesis of a thiophene-bearing nickel(ii) external initiator that is used to synthesize modular and regioregular terthiophene. We then show that the halogenated terthiophene is a compatible building block in synthesizing precision oligothiophenes. This thiophene-bearing external initiator exhibits remarkable reactivity and stability through polymerization. Furthermore, we show that excess halogenated terthiophene can be recovered post-oligomerization and reused in subsequent syntheses. Overall, this work highlights the feasibility of synthesizing all-thiophene polymers using thiophene-bearing external initiators and recycling the modular terthiophene after oligomerization.
{"title":"Recyclable terthiophenes for synthesizing precision conjugated oligomers†","authors":"Hao Xu , Harrison A. Mills , Shuyang Ye , Dwight S. Seferos","doi":"10.1039/d4py00761a","DOIUrl":"10.1039/d4py00761a","url":null,"abstract":"<div><div>Precision polymers and oligomers are distinguished by their well-defined characteristics (<em>e.g.</em>, chain length, monomer sequence). As a result, they have been leveraged in recent years to study numerous structure–property relationships ranging from photophysical characteristics to antimicrobial activity. However, the synthesis of precision polymers and oligomers often requires elaborate building blocks that are compatible with specific polymerization approaches. In most cases, these building blocks are neither recovered nor recycled, limiting the efficiency and sustainability of these synthetic methods. Herein, we report the first synthesis of a thiophene-bearing nickel(<span>ii</span>) external initiator that is used to synthesize modular and regioregular terthiophene. We then show that the halogenated terthiophene is a compatible building block in synthesizing precision oligothiophenes. This thiophene-bearing external initiator exhibits remarkable reactivity and stability through polymerization. Furthermore, we show that excess halogenated terthiophene can be recovered post-oligomerization and reused in subsequent syntheses. Overall, this work highlights the feasibility of synthesizing all-thiophene polymers using thiophene-bearing external initiators and recycling the modular terthiophene after oligomerization.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 37","pages":"Pages 3814-3822"},"PeriodicalIF":4.1,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142170979","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bidentate N,N-ligands have played a vital role in the iron-mediated polymerization of 1,3-diene over the past few decades. In this work, iron complexes chelated with a 1,10-phenanthroline ligand modified with an electronic donating (thio)ether, diethylamine substituents at the 2-position, were synthesized and characterized. The presence of the donor promoted the catalytic activity by one-fold for isoprene polymerization, reaching the most active iron system (2.60 × 107 g mol−1 h−1) ever found so far. An elevated 3,4 selectivity of 69.9% with moderate syndiotacticity (rr: 60.2%) was achieved at −40 °C. The activity was heteroatom-dependent, with the catalyst bearing ether (1.20 × 107 g mol−1 h−1 –0.96 × 107 g mol−1 h−1) performing more actively than thiophenyl ether (Fe5, 0.89 × 107 g mol−1 h−1) and diethylamine (Fe6, 0.67 × 107 g mol−1 h−1) analogues. Polyisoprenes synthesized under various temperatures were pressed and molded to afford a new type of material with integrated excellent strength (breaking strength, 15.6 MPa) and toughness (elongation up to 589%). The thermal plasticity granted a good reprocessability with satisfactory property recovery after three cycles.
{"title":"Catalytic polymerization of isoprene using an ultrahigh active iron(ii) complex with an ortho-modified 1,10-phenanthroline ligand, access to a thermal plastic rubber†","authors":"Jiajia Ge , Binghui Chen , Dirong Gong","doi":"10.1039/d4py00576g","DOIUrl":"10.1039/d4py00576g","url":null,"abstract":"<div><div>Bidentate N,N-ligands have played a vital role in the iron-mediated polymerization of 1,3-diene over the past few decades. In this work, iron complexes chelated with a 1,10-phenanthroline ligand modified with an electronic donating (thio)ether, diethylamine substituents at the 2-position, were synthesized and characterized. The presence of the donor promoted the catalytic activity by one-fold for isoprene polymerization, reaching the most active iron system (2.60 × 10<sup>7</sup> g mol<sup>−1</sup> h<sup>−1</sup>) ever found so far. An elevated 3,4 selectivity of 69.9% with moderate syndiotacticity (rr: 60.2%) was achieved at −40 °C. The activity was heteroatom-dependent, with the catalyst bearing ether (1.20 × 10<sup>7</sup> g mol<sup>−1</sup> h<sup>−1</sup> –0.96 × 10<sup>7</sup> g mol<sup>−1</sup> h<sup>−1</sup>) performing more actively than thiophenyl ether (<strong>Fe5</strong>, 0.89 × 10<sup>7</sup> g mol<sup>−1</sup> h<sup>−1</sup>) and diethylamine (<strong>Fe6</strong>, 0.67 × 10<sup>7</sup> g mol<sup>−1</sup> h<sup>−1</sup>) analogues. Polyisoprenes synthesized under various temperatures were pressed and molded to afford a new type of material with integrated excellent strength (breaking strength, 15.6 MPa) and toughness (elongation up to 589%). The thermal plasticity granted a good reprocessability with satisfactory property recovery after three cycles.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 37","pages":"Pages 3751-3762"},"PeriodicalIF":4.1,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142042593","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kseniia M. Karnaukh , Shuyi Xie , Kai-Chieh Yang , Komal Komal , Rachel A. Segalman , Javier Read de Alaniz
Physically mixing two dissimilar polymers often results in a macroscopically segregated blend with poor optical clarity and mechanical properties. Previously, we demonstrated that chain end functionalization of immiscible polymer blends with oppositely paired acid and base groups leads to an ionic supramolecular block copolymer with electrostatically stabilized microdomains that suppress macroscopic phase separation. In this work, a functionalized polydimethylsiloxane with a photochromic diarylethene (DAE) end-group (PDMS-ω-DAE) is blended with a sulfonic acid end-functionalized polystyrene (PS-ω-SO3H), forming an ionic supramolecular block copolymer with tunable morphology by light. When the DAE is irradiated with UV light, it triggers an isomerization from the ring-opened (DAE–O) to the ring-closed (DAE–C) form. The light-induced conformational change in the chain-end group chemistry substantially alters the ionic junctions, leading to a phase structure difference in the solid-state from hexagonally packed cylinders (HEX) to lamellae (LAM). After UV radiation, the more localized positive charge on DAE–C led to stronger ionic bonds between the two dissimilar blocks, while the repulsion between adjacent DAE–C groups increased. The stronger electrostatic repulsion along the interface resulted in increased interfacial area per polymer chain and thus induced such phase transition. The light-induced phase transition of this system demonstrates that the ionic interactions can be tuned on-demand to create different morphologies from a single polymer blend.
{"title":"Photoinduced morphology change in ionic supramolecular block copolymer†","authors":"Kseniia M. Karnaukh , Shuyi Xie , Kai-Chieh Yang , Komal Komal , Rachel A. Segalman , Javier Read de Alaniz","doi":"10.1039/d4py00682h","DOIUrl":"10.1039/d4py00682h","url":null,"abstract":"<div><div>Physically mixing two dissimilar polymers often results in a macroscopically segregated blend with poor optical clarity and mechanical properties. Previously, we demonstrated that chain end functionalization of immiscible polymer blends with oppositely paired acid and base groups leads to an ionic supramolecular block copolymer with electrostatically stabilized microdomains that suppress macroscopic phase separation. In this work, a functionalized polydimethylsiloxane with a photochromic diarylethene (DAE) end-group (PDMS-<em>ω</em>-DAE) is blended with a sulfonic acid end-functionalized polystyrene (PS-<em>ω</em>-SO<sub>3</sub>H), forming an ionic supramolecular block copolymer with tunable morphology by light. When the DAE is irradiated with UV light, it triggers an isomerization from the ring-opened (DAE–O) to the ring-closed (DAE–C) form. The light-induced conformational change in the chain-end group chemistry substantially alters the ionic junctions, leading to a phase structure difference in the solid-state from hexagonally packed cylinders (HEX) to lamellae (LAM). After UV radiation, the more localized positive charge on DAE–C led to stronger ionic bonds between the two dissimilar blocks, while the repulsion between adjacent DAE–C groups increased. The stronger electrostatic repulsion along the interface resulted in increased interfacial area per polymer chain and thus induced such phase transition. The light-induced phase transition of this system demonstrates that the ionic interactions can be tuned on-demand to create different morphologies from a single polymer blend.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 37","pages":"Pages 3806-3813"},"PeriodicalIF":4.1,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142123624","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Qi Shao , Chang-Hui Wang , Han Gu , Xiao-Hong Zhou , Xuan Nie , Wei-Qiang Huang , Fan Gao , Fei Wang , Ye-Zi You
Tumour cells exhibit distinct metabolism to sustain their proliferation and survival, making targeting metabolic pathways an appealing option for tumour therapy. Glutamine metabolism plays a crucial role in fuelling tumour growth and modulating the tumour microenvironment. However, the clinical translation of glutamine metabolism-targeting therapies faces poor efficiency and systemic toxic effects. Here, we constructed biocompatible and functional polymer nanoparticles to deliver CRISPR-Cas9 into tumours for efficient and simultaneous gene editing, which can cut off two genes that express glutaminase (GLS1) and phosphoribosyl pyrophosphate amidotransferase (PPAT) to manipulate glutamine metabolism. The results demonstrated that genetic manipulation of glutamine metabolism significantly inhibited tumour development and metastasis while also favourably altering the tumour microenvironment. Importantly, this method improved antitumour immunity and promoted long-term immunological memory. This work highlights the potential of simultaneously targeting multiple glutamine metabolic pathways through gene editing, providing a promising strategy for cancer therapy.
{"title":"Targeting delivery of CRISPR systems into tumours to edit glutamine metabolism for cancer therapy by DPA-Zn-modified nanoparticles†","authors":"Qi Shao , Chang-Hui Wang , Han Gu , Xiao-Hong Zhou , Xuan Nie , Wei-Qiang Huang , Fan Gao , Fei Wang , Ye-Zi You","doi":"10.1039/d4py00591k","DOIUrl":"10.1039/d4py00591k","url":null,"abstract":"<div><div>Tumour cells exhibit distinct metabolism to sustain their proliferation and survival, making targeting metabolic pathways an appealing option for tumour therapy. Glutamine metabolism plays a crucial role in fuelling tumour growth and modulating the tumour microenvironment. However, the clinical translation of glutamine metabolism-targeting therapies faces poor efficiency and systemic toxic effects. Here, we constructed biocompatible and functional polymer nanoparticles to deliver CRISPR-Cas9 into tumours for efficient and simultaneous gene editing, which can cut off two genes that express glutaminase (GLS1) and phosphoribosyl pyrophosphate amidotransferase (PPAT) to manipulate glutamine metabolism. The results demonstrated that genetic manipulation of glutamine metabolism significantly inhibited tumour development and metastasis while also favourably altering the tumour microenvironment. Importantly, this method improved antitumour immunity and promoted long-term immunological memory. This work highlights the potential of simultaneously targeting multiple glutamine metabolic pathways through gene editing, providing a promising strategy for cancer therapy.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 37","pages":"Pages 3736-3750"},"PeriodicalIF":4.1,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142085300","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ke Wang , Meiyu Si , Xiaofang Liu , Zilong Wang , Guiyan Liu , Yongfei Zeng
A novel light/temperature/pH/CO2-quadruple responsive azobenzene functionalized homopolymer of poly[(E)-3,14-dimethyl-13-oxo-6,9,12-trioxa-3-azapentadec-14-en-1-yl 4-(phenyldiazenyl)benzoate] [P(Azo-N-EO2MA)] was prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization. The light-responsiveness of P(Azo-N-EO2MA) was demonstrated by examining the UV/vis absorption spectra under alternating UV/blue light irradiation or UV irradiation/heating conditions. P(Azo-N-EO2MA) has an upper critical solution temperature (UCST) in the co-solvent of n-butanol/water and a critical pH in aqueous solution. The effects of different molecular structures, molecular weights and concentrations on the UCST and critical pH were investigated. The response of P(Azo-N-EO2MA) to CO2 was demonstrated via the cyclic bubbling of CO2/N2 through a solution of P(Azo-N-EO2MA). Then, the interaction between the different response was explored. The critical micelle concentration (cmc) of P(Azo-N-EO2MA) was tested. Micelles of P(Azo-N-EO2MA) were prepared by self-assembly, and the morphology or size of the micelles can be changed by applying acid or irradiating with UV light. Finally, P(Azo-N-EO2MA) was applied to the preparation of rewritable paper, and it is proved that the rewritable paper has good cyclability, stability and high resolution during the process of “writing–erasing–writing” of different patterns. P(Azo-N-EO2MA) expands the types of multistimuli-responsive homopolymers available to researchers and has good prospects for applications in self-assembly, drug delivery and optical storage.
{"title":"Concise synthesis of a light/temperature/pH/CO2-quadruple responsive azobenzene functionalized homopolymer for reversible photopatterning†","authors":"Ke Wang , Meiyu Si , Xiaofang Liu , Zilong Wang , Guiyan Liu , Yongfei Zeng","doi":"10.1039/d4py00669k","DOIUrl":"10.1039/d4py00669k","url":null,"abstract":"<div><div>A novel light/temperature/pH/CO<sub>2</sub>-quadruple responsive azobenzene functionalized homopolymer of poly[(<em>E</em>)-3,14-dimethyl-13-oxo-6,9,12-trioxa-3-azapentadec-14-en-1-yl 4-(phenyldiazenyl)benzoate] [P(Azo-N-EO<sub>2</sub>MA)] was prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization. The light-responsiveness of P(Azo-N-EO<sub>2</sub>MA) was demonstrated by examining the UV/vis absorption spectra under alternating UV/blue light irradiation or UV irradiation/heating conditions. P(Azo-N-EO<sub>2</sub>MA) has an upper critical solution temperature (UCST) in the co-solvent of <em>n</em>-butanol/water and a critical pH in aqueous solution. The effects of different molecular structures, molecular weights and concentrations on the UCST and critical pH were investigated. The response of P(Azo-N-EO<sub>2</sub>MA) to CO<sub>2</sub> was demonstrated <em>via</em> the cyclic bubbling of CO<sub>2</sub>/N<sub>2</sub> through a solution of P(Azo-N-EO<sub>2</sub>MA). Then, the interaction between the different response was explored. The critical micelle concentration (cmc) of P(Azo-N-EO<sub>2</sub>MA) was tested. Micelles of P(Azo-N-EO<sub>2</sub>MA) were prepared by self-assembly, and the morphology or size of the micelles can be changed by applying acid or irradiating with UV light. Finally, P(Azo-N-EO<sub>2</sub>MA) was applied to the preparation of rewritable paper, and it is proved that the rewritable paper has good cyclability, stability and high resolution during the process of “writing–erasing–writing” of different patterns. P(Azo-N-EO<sub>2</sub>MA) expands the types of multistimuli-responsive homopolymers available to researchers and has good prospects for applications in self-assembly, drug delivery and optical storage.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 37","pages":"Pages 3795-3805"},"PeriodicalIF":4.1,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142101639","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Stimuli-responsive layered hydrogel actuators are highly attractive for broad applications in soft robots, intelligent devices, etc., owing to their softness, asymmetric responsiveness and deformability. However, current layered hydrogel actuators suffer from serious challenges such as tedious preparation, uncontrollable layer thickness and weak interfacial bonding force. Herein, we put forward a facile and highly efficient self-growing method to prepare a layered hydrogel actuator from a stiff hydrogel substrate by crafting l-ascorbic acid (Vc)-triggered interfacial radical polymerization. The redox reaction between Vc and confined Fe3+ in the stiff hydrogel substrate could produce Fe2+ catalysts, resulting in surface catalytically initiated radical polymerization (SCIRP) at room temperature. Various layered hydrogels were prepared rapidly and the thickness of the grown hydrogel layer can be accurately controlled. The obtained layered hydrogel exhibits asymmetric structural layers consisting of a dense layer and a porous layer, as well as a strong interfacial bonding force of about 250 N m−1 between the porous layer and the stiff substrate. Furthermore, a thermo-responsive layered hydrogel actuator was developed, which showed reversible underwater bending ability in response to temperature changes and can also be designed as a smart manipulator to capture objects underwater. This work provides a novel and feasible approach for the highly efficient and controllable preparation of layered hydrogel actuators, which will find promising applications in the fields of soft robots, intelligent devices, sensors and so on.
{"title":"A bioinspired layered hydrogel actuator vial-ascorbic acid-triggered interfacial self-growth from a stiff hydrogel†","authors":"Rongnian Xu , Yuxin Gao , Yingying Lai , Chengyan Zhang , Wenbo Jia , Qiangbing Wei","doi":"10.1039/d4py00848k","DOIUrl":"10.1039/d4py00848k","url":null,"abstract":"<div><div>Stimuli-responsive layered hydrogel actuators are highly attractive for broad applications in soft robots, intelligent devices, <em>etc</em>., owing to their softness, asymmetric responsiveness and deformability. However, current layered hydrogel actuators suffer from serious challenges such as tedious preparation, uncontrollable layer thickness and weak interfacial bonding force. Herein, we put forward a facile and highly efficient self-growing method to prepare a layered hydrogel actuator from a stiff hydrogel substrate by crafting <span>l</span>-ascorbic acid (Vc)-triggered interfacial radical polymerization. The redox reaction between Vc and confined Fe<sup>3+</sup> in the stiff hydrogel substrate could produce Fe<sup>2+</sup> catalysts, resulting in surface catalytically initiated radical polymerization (SCIRP) at room temperature. Various layered hydrogels were prepared rapidly and the thickness of the grown hydrogel layer can be accurately controlled. The obtained layered hydrogel exhibits asymmetric structural layers consisting of a dense layer and a porous layer, as well as a strong interfacial bonding force of about 250 N m<sup>−1</sup> between the porous layer and the stiff substrate. Furthermore, a thermo-responsive layered hydrogel actuator was developed, which showed reversible underwater bending ability in response to temperature changes and can also be designed as a smart manipulator to capture objects underwater. This work provides a novel and feasible approach for the highly efficient and controllable preparation of layered hydrogel actuators, which will find promising applications in the fields of soft robots, intelligent devices, sensors and so on.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 37","pages":"Pages 3787-3794"},"PeriodicalIF":4.1,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142085241","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rentuya Wu , Xiaosong Sun , Wenyue Dong , Yanwei Li , Qian Duan , Teng Fei
Using the Suzuki cross-coupling method, the tetraarylethylene-based conjugated polymers PT-F and PT-Cz were synthesized by reacting 9-(dibromomethylene)-9H-thioxanthene with (9,9-dihexyl-9H-fluorene-2,7-diyl)diboronic acid and 9-heptyl-3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole ester, respectively. PT-F and PT-Cz exhibit significant aggregation-induced emission (AIE) properties, with fluorescence quantum yields 184 times and 74 times higher in THF/H2O (2/8, v/v) than in pure THF, respectively, attributed to the introduction of the tetraarylethylene units. The sensing performance of the polymers towards 2,4,6-trinitrophenol (TNP) was investigated. The quenching constants for the detection of TNP based on PT-F and PT-Cz in THF/H2O (2/8, v/v) are 1.20 × 105 M−1 and 2.04 × 105 M−1, with detection limits of 0.12 μM and 0.07 μM, respectively. Moreover, PT-F and PT-Cz achieve selective detection and anti-interference detection of TNP against other common nitro-compounds and common ions. Furthermore, the spiking/recovery data show the recovery rates for TNP based on the two polymers in different water samples ranging from 93.20% to 107.80%, and the result is verified by a t-test.
{"title":"The synthesis of tetraarylethylene-based conjugated polymers for the application of fluorescence sensing towards nitroaromatics†","authors":"Rentuya Wu , Xiaosong Sun , Wenyue Dong , Yanwei Li , Qian Duan , Teng Fei","doi":"10.1039/d4py00821a","DOIUrl":"10.1039/d4py00821a","url":null,"abstract":"<div><div>Using the Suzuki cross-coupling method, the tetraarylethylene-based conjugated polymers <strong>PT-F</strong> and <strong>PT-Cz</strong> were synthesized by reacting 9-(dibromomethylene)-9<em>H</em>-thioxanthene with (9,9-dihexyl-9<em>H</em>-fluorene-2,7-diyl)diboronic acid and 9-heptyl-3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9<em>H</em>-carbazole ester, respectively. <strong>PT-F</strong> and <strong>PT-Cz</strong> exhibit significant aggregation-induced emission (AIE) properties, with fluorescence quantum yields 184 times and 74 times higher in THF/H<sub>2</sub>O (2/8, v/v) than in pure THF, respectively, attributed to the introduction of the tetraarylethylene units. The sensing performance of the polymers towards 2,4,6-trinitrophenol (TNP) was investigated. The quenching constants for the detection of TNP based on <strong>PT-F</strong> and <strong>PT-Cz</strong> in THF/H<sub>2</sub>O (2/8, v/v) are 1.20 × 10<sup>5</sup> M<sup>−1</sup> and 2.04 × 10<sup>5</sup> M<sup>−1</sup>, with detection limits of 0.12 μM and 0.07 μM, respectively. Moreover, <strong>PT-F</strong> and <strong>PT-Cz</strong> achieve selective detection and anti-interference detection of TNP against other common nitro-compounds and common ions. Furthermore, the spiking/recovery data show the recovery rates for TNP based on the two polymers in different water samples ranging from 93.20% to 107.80%, and the result is verified by a <em>t</em>-test.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 41","pages":"Pages 4221-4230"},"PeriodicalIF":4.1,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142313874","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jiyoung Park , Tugba G. Kucukkal , Jung-Min Oh , Steven J. Stuart , Stephen E. Creager , Gustavo Muñoz , Dennis W. Smith Jr.
We report a selective [2 + 2] cyclo-copolymerization of aryl trifluorovinyl ethers (TFVEs) toward segmented copolymers. Experimental and computational studies confirm that copolymerization of relatively electron-rich and electron-poor TFVE monomers results in segmented copolymers in a single polymerization. The effect of microstructures on post-sulfonation in the polymer backbones was also investigated.
{"title":"One-pot single-step copolymerization of aromatic trifluorovinyl ethers toward perfluorocyclobutyl (PFCB) segmented copolymers†","authors":"Jiyoung Park , Tugba G. Kucukkal , Jung-Min Oh , Steven J. Stuart , Stephen E. Creager , Gustavo Muñoz , Dennis W. Smith Jr.","doi":"10.1039/d4py00149d","DOIUrl":"10.1039/d4py00149d","url":null,"abstract":"<div><div>We report a selective [2 + 2] cyclo-copolymerization of aryl trifluorovinyl ethers (TFVEs) toward segmented copolymers. Experimental and computational studies confirm that copolymerization of relatively electron-rich and electron-poor TFVE monomers results in segmented copolymers in a single polymerization. The effect of microstructures on post-sulfonation in the polymer backbones was also investigated.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 39","pages":"Pages 3977-3982"},"PeriodicalIF":4.1,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141895636","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yuwei Zhang , Ce Xing , Zhibin Tian , Wanyi Zhao , Yongfeng Zhi , Lina Zhao , He Li
Covalent organic frameworks (COFs) possess versatile advantages, including their lightweight nature, exceptional stability, and having a well-defined π structure, rending them highly promising for fluorescence sensors. One of the most important factors for sensing is the presence of interaction sites, which previous research has not considered extensively. In this study, we present the synthesis of two emissive hydrazone-linked COFs (EH-COFs) under solvothermal conditions. The hydrazone linkages, which contain –NH single bond groups on the walls, reduce aggregation-caused fluorescence quenching, resulting in enhanced emission activity. Furthermore, the abundance of interaction sites (nitrogen and oxygen atoms) on the walls enables efficient interaction with guest molecules. Owing to these advantages, EH-COFs exhibited elevated sensitivity and selectivity, with low detection limits, for hydrazine sensing, ranking them among the top-performing fluorescence probes reported to date.
{"title":"Emissive covalent organic frameworks with abundant interaction sites for hydrazine sensing†","authors":"Yuwei Zhang , Ce Xing , Zhibin Tian , Wanyi Zhao , Yongfeng Zhi , Lina Zhao , He Li","doi":"10.1039/d4py00815d","DOIUrl":"10.1039/d4py00815d","url":null,"abstract":"<div><div>Covalent organic frameworks (COFs) possess versatile advantages, including their lightweight nature, exceptional stability, and having a well-defined π structure, rending them highly promising for fluorescence sensors. One of the most important factors for sensing is the presence of interaction sites, which previous research has not considered extensively. In this study, we present the synthesis of two emissive hydrazone-linked COFs (EH-COFs) under solvothermal conditions. The hydrazone linkages, which contain –NH single bond groups on the walls, reduce aggregation-caused fluorescence quenching, resulting in enhanced emission activity. Furthermore, the abundance of interaction sites (nitrogen and oxygen atoms) on the walls enables efficient interaction with guest molecules. Owing to these advantages, EH-COFs exhibited elevated sensitivity and selectivity, with low detection limits, for hydrazine sensing, ranking them among the top-performing fluorescence probes reported to date.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 39","pages":"Pages 4005-4010"},"PeriodicalIF":4.1,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/py/d4py00815d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142245881","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mingfa Guo , Yaning Wang , Zhenguang Li , Jielin Xu , Qian Chen , Jing Wu , Huaping Wang
Isosorbide polycarbonate (PIC) is a promising bio-based and ecofriendly alternative of the conventional bisphenol-A polycarbonate. Trace organic impurities existing in the isosorbide raw material is a significant factor impeding the high-quality (high molecular weight, good color and narrow polydispersity) production of PIC. In this work, a set of multifunctional polyol impurities were recognized as the major impurities, and then a so-called “reverse-addition” model protocol based on two kinds of polyols (glycerol and 2-deoxy-d-ribose) was established to systematically demonstrate their influences on the polymerization and properties of PIC. The presence of glycerol impurity significantly increases the transesterification rate and transesterification equilibrium time between isosorbide and diphenyl carbonate. Additionally, the hydroxyl end-groups of the isosorbide unit on PICs increased significantly due to the addition of glycerol which hindered the polymerization, resulting in a decrease in the viscosity-average molecular weight (Mη) of PIC by 30 754 g mol−1. In comparison, 2-deoxy-d-ribose impurity decreased the transesterification rate and prolonged the transesterification equilibrium time, inducing a ring-opening side reaction of isosorbide and eventually leading to the cross-linking of PIC, thus increasing the Mη of the polymer by 18 655 g mol−1. Moreover, both impurities can cause yellowing of PIC and 2-deoxy-d-ribose impurity has an even stronger effect than glycerol. This protocol holds great significance in advancing the quality control and industrial scale-up of isosorbide polycarbonate polymers and can also be an effective methodology for other polymer systems.
{"title":"Influence of polyol impurities on the transesterification kinetics, molecular structures and properties of isosorbide polycarbonate†","authors":"Mingfa Guo , Yaning Wang , Zhenguang Li , Jielin Xu , Qian Chen , Jing Wu , Huaping Wang","doi":"10.1039/d4py00840e","DOIUrl":"10.1039/d4py00840e","url":null,"abstract":"<div><div>Isosorbide polycarbonate (PIC) is a promising bio-based and ecofriendly alternative of the conventional bisphenol-A polycarbonate. Trace organic impurities existing in the isosorbide raw material is a significant factor impeding the high-quality (high molecular weight, good color and narrow polydispersity) production of PIC. In this work, a set of multifunctional polyol impurities were recognized as the major impurities, and then a so-called “reverse-addition” model protocol based on two kinds of polyols (glycerol and 2-deoxy-<span>d</span>-ribose) was established to systematically demonstrate their influences on the polymerization and properties of PIC. The presence of glycerol impurity significantly increases the transesterification rate and transesterification equilibrium time between isosorbide and diphenyl carbonate. Additionally, the hydroxyl end-groups of the isosorbide unit on PICs increased significantly due to the addition of glycerol which hindered the polymerization, resulting in a decrease in the viscosity-average molecular weight (<em>M</em><sub>η</sub>) of PIC by 30 754 g mol<sup>−1</sup>. In comparison, 2-deoxy-<span>d</span>-ribose impurity decreased the transesterification rate and prolonged the transesterification equilibrium time, inducing a ring-opening side reaction of isosorbide and eventually leading to the cross-linking of PIC, thus increasing the <em>M</em><sub>η</sub> of the polymer by 18 655 g mol<sup>−1</sup>. Moreover, both impurities can cause yellowing of PIC and 2-deoxy-<span>d</span>-ribose impurity has an even stronger effect than glycerol. This protocol holds great significance in advancing the quality control and industrial scale-up of isosorbide polycarbonate polymers and can also be an effective methodology for other polymer systems.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 41","pages":"Pages 4204-4220"},"PeriodicalIF":4.1,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142275888","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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