A porous organic polymer named FC-POP was facilely synthesized with extraordinary porosity and excellent stability. Further covalent incorporation of various amines including single amine group, multi-amine groups of ...A porous organic polymer named FC-POP was facilely synthesized with extraordinary porosity and excellent stability. Further covalent incorporation of various amines including single amine group, multi-amine groups of diethylenediamine （DETA）, and poly-amine groups of polyethylenimine （PEI） to the network gave rise to task-specific modification of the microenvironments to make them more suitable for CO2 capture. As a result, significant boost of CO2 adsorption capacity of 4.5 mmol/g （for FC-POP-CH2DETA, 273 K, 1 bar） and the CO2/N2 selectivity of 736.1 （for FC- POP-CH2PEI） were observed after the post-synthesis amine modifications. Furthermore, these materials can be regener- ated in elevated temperature under vacuum without apparent loss of CO2 adsorption capacity.展开更多
A review of methods for the anionic synthesis of well-defined, amine-functionalized polymers using imines as functionalizing agents is provided. The disparate results in the literature regarding functionalizations wit...A review of methods for the anionic synthesis of well-defined, amine-functionalized polymers using imines as functionalizing agents is provided. The disparate results in the literature regarding functionalizations with N -(benzylidene)trimethylsilylamine to form primary amine functionalized polymers are discussed; the efficiency of functionalization depends on the molecular weight of the polymeric organolithium(PLi). Efficient functionalizations are observed for PLi with n>10 000 g/mol. The poor functionalization yields using ketimines with enolizable hydrogens is explained. The use of N -trimethylsilyldiphenylcarbimide as a quantitative primary amine functionalizing reagent is described. Recent results on the anionic synthesis of secondary amine-functionalized polymers using N -(benzylidene)methylamine as the functionalization agent are presented.展开更多
Hyperbranched poly(amine-ester) (HBPAE) was synthesized via pseudo-one-step process between trimethylolpropane as a core molecule and N, N-diethylol-3-amine methylpropionate as the AB2 branched monomer. The prepared p...Hyperbranched poly(amine-ester) (HBPAE) was synthesized via pseudo-one-step process between trimethylolpropane as a core molecule and N, N-diethylol-3-amine methylpropionate as the AB2 branched monomer. The prepared polymer was analyzed by IR, GPC, 1H-NMR and thermal analysis (TGA and DSC). The performance of the polymer in cement was tested by measuring the effect of 1, 3 and 5 wt% of HBPAE solutions on the properties of Ordinary Portland Cement. Water of consistency, setting times, bulk density, apparent porosity, compressive strength and combined water content of the polymer/cement pastes were studied. The results showed that water of consistency and apparent porosity decreased while setting times, compressive strength, combined water and bulk density increased with the polymer addition.展开更多
Guanidinylated bioresponsive poly(amido amine)s polymers, CAR-CBA and CHL-CBA, weresynthesized by Michael-type addition reaction between guanidine hydrochloride(CAR) orchlorhexidine(CHL) and N,N-cystaminebisacrylamide...Guanidinylated bioresponsive poly(amido amine)s polymers, CAR-CBA and CHL-CBA, weresynthesized by Michael-type addition reaction between guanidine hydrochloride(CAR) orchlorhexidine(CHL) and N,N-cystaminebisacrylamide(CBA). Previous studies have shownthat both polymers had high transfection efficiencies as gene delivery carriers. In this study,we investigated the nucleolus localization abilities and cellular internalization pathways ofthese two polymers in gene delivery. Each polymer condensed plasmid DNA(p DNA) andformed nanoparticle complexes, and then their transfection studies were performed inMCF-7 cells. Both complexes were found enriched in nucleolus after cellular transfection,and their transfection efficiencies were significantly improved when transfection was per-formed on MCF-7 cells arrested at M phase. The transfection efficiency of CAR-CBA-pDNAwas inhibited by chlorpromazine, and cell endosomes were disrupted after being exposedto CAR-CBA-pDNA. In regards to CHL-CBA-pDNA, its transfection efficiency was not affected by three types of endocytosis inhibitors used in the study, and CHL-CBA-pDNA showed no effect on endosomes. Cellular lactate dehydrogenase release and membrane morphology were changed after cells were transfected by the two complexes. The results indicated that both CAR-CBA and CHL-CBA polymers demonstrated good nucleolus localization abilities. It was beneficial for transfection when cells were arrested at M phase. CAR-CBA-pDNA cellular internalization was involved with clathrin-mediated endocytosis pathway, and escaping from endosomal entrapment, while the cellular uptake of CHL-CBA-pDNA occurs via clathrin-and caveolae-independent mechanism.展开更多
Hypercrosslinked polymers(HCPs)with large surface areas,high intrinsic porosities and low production costs may be available platforms for iodine capture.However,the lack of iodine-philicity binding sites limits their ...Hypercrosslinked polymers(HCPs)with large surface areas,high intrinsic porosities and low production costs may be available platforms for iodine capture.However,the lack of iodine-philicity binding sites limits their adsorption capacity.Here we use vapor-phase postsynthetic amination strategy to introduce electron-donating amino groups into the prefabricated HCPs for enhancing their iodine capture performance.Through simple vapor-phase exposure,the halogen-containing HCPs can be grafted by amines through nucleophilic substitution toward chloro groups.Combining with the abundant amino groups and high porosities,the amino-functionalized porous polymers show substantially increased iodine adsorption capacity,about 221%as that of original one,accompanied by excellent recyclability.Mechanism investigations reveal the key roles of the electron-donor amino groups andπ-conjugated benzene rings along with structure characteristics of porous polymer frameworks in iodine capture.Moreover,this vapor-phase amination strategy shows good generality and can be extended to various amines,e.g.,ethylenediamine,1,3-diaminopropane and diethylenetriamine.Our work proves that this simple vapor-phase postsynthetic functionalization strategy may be applied in other porous polymers with wide application prospects in adsorption,separation and storage.展开更多
Copolyesters having secondary and tertiary amine salt groups in the main and side chains are prepared by chemoselective polymerization. These copolyesters are soluble in a 10% aqueous solution of poly(vinyl alcohol) ...Copolyesters having secondary and tertiary amine salt groups in the main and side chains are prepared by chemoselective polymerization. These copolyesters are soluble in a 10% aqueous solution of poly(vinyl alcohol) (PVA) at 90 degree C and act as plasticizer in the blend films cast from the solution. Only a glass transition temperature is observed for all these blends indicating the formation of compatible blends from these polyesters with PVA. These blends exhibit manifold characteristics such as ionic conductivity, complex formation with metal ions, absorption of moisture and color changes. The electric conductivity of the copolyesters and blends is in the range of 10** minus **6 Scm** minus **1. The blends with PVA forms complexes with Cu**2** plus and Co**2** plus . The coordination structure with two chelate rings is suggested for these polymer blend/metal complexes. (Author abstract) 10 Refs.展开更多
A triformylphloroglucinol-based AiB2-typed covalent organic polymer(TFG-BPTH)was successfully constructed by the condensation reaction of triformylphloroglucinol(TFG)and 2.5-bis(2-propynyloxy)terephthalo-hydrazide(BPT...A triformylphloroglucinol-based AiB2-typed covalent organic polymer(TFG-BPTH)was successfully constructed by the condensation reaction of triformylphloroglucinol(TFG)and 2.5-bis(2-propynyloxy)terephthalo-hydrazide(BPTH)under solvothermal conditions.The structure of the TFG-BPTH was confirmed by spectra tech-niques including FTIR and solid-state IC CP/MAS NMR spectroscopy.The mophological features of TFG-BPTH were analyzed using scanning electron microscopy(SEM)and transmission electron microscopy(TEM).The TFG-BPTH possessed good thermal and chemical stability,and exhibited good photocatalytic activity as a metal-free heterogeneous catalyst for oxidation of amines to valuable imines under visible light irradiation using O2 as greer oxidant.In addition,the catalyst could be readily recovered from the reaction mixture by simple filtration and reused for at least five cycles without any observable change in structure and catalytic activity.展开更多
Main observation and conclusion Ring-opening metathesis polymerization(ROMP)is a powerful toolbox in preparation of bottlebrush polymers for its high activity.However,the ROMP of macromonomers with repeating tertiary ...Main observation and conclusion Ring-opening metathesis polymerization(ROMP)is a powerful toolbox in preparation of bottlebrush polymers for its high activity.However,the ROMP of macromonomers with repeating tertiary amine groups,for example,poly(2-(dimethylamino)ethyl methacrylate)(PDMAEMA).展开更多
文摘A porous organic polymer named FC-POP was facilely synthesized with extraordinary porosity and excellent stability. Further covalent incorporation of various amines including single amine group, multi-amine groups of diethylenediamine （DETA）, and poly-amine groups of polyethylenimine （PEI） to the network gave rise to task-specific modification of the microenvironments to make them more suitable for CO2 capture. As a result, significant boost of CO2 adsorption capacity of 4.5 mmol/g （for FC-POP-CH2DETA, 273 K, 1 bar） and the CO2/N2 selectivity of 736.1 （for FC- POP-CH2PEI） were observed after the post-synthesis amine modifications. Furthermore, these materials can be regener- ated in elevated temperature under vacuum without apparent loss of CO2 adsorption capacity.
文摘A review of methods for the anionic synthesis of well-defined, amine-functionalized polymers using imines as functionalizing agents is provided. The disparate results in the literature regarding functionalizations with N -(benzylidene)trimethylsilylamine to form primary amine functionalized polymers are discussed; the efficiency of functionalization depends on the molecular weight of the polymeric organolithium(PLi). Efficient functionalizations are observed for PLi with n>10 000 g/mol. The poor functionalization yields using ketimines with enolizable hydrogens is explained. The use of N -trimethylsilyldiphenylcarbimide as a quantitative primary amine functionalizing reagent is described. Recent results on the anionic synthesis of secondary amine-functionalized polymers using N -(benzylidene)methylamine as the functionalization agent are presented.
文摘Hyperbranched poly(amine-ester) (HBPAE) was synthesized via pseudo-one-step process between trimethylolpropane as a core molecule and N, N-diethylol-3-amine methylpropionate as the AB2 branched monomer. The prepared polymer was analyzed by IR, GPC, 1H-NMR and thermal analysis (TGA and DSC). The performance of the polymer in cement was tested by measuring the effect of 1, 3 and 5 wt% of HBPAE solutions on the properties of Ordinary Portland Cement. Water of consistency, setting times, bulk density, apparent porosity, compressive strength and combined water content of the polymer/cement pastes were studied. The results showed that water of consistency and apparent porosity decreased while setting times, compressive strength, combined water and bulk density increased with the polymer addition.
基金supported by National Natural Science Foundation of China (Grant no. 81373335)
文摘Guanidinylated bioresponsive poly(amido amine)s polymers, CAR-CBA and CHL-CBA, weresynthesized by Michael-type addition reaction between guanidine hydrochloride(CAR) orchlorhexidine(CHL) and N,N-cystaminebisacrylamide(CBA). Previous studies have shownthat both polymers had high transfection efficiencies as gene delivery carriers. In this study,we investigated the nucleolus localization abilities and cellular internalization pathways ofthese two polymers in gene delivery. Each polymer condensed plasmid DNA(p DNA) andformed nanoparticle complexes, and then their transfection studies were performed inMCF-7 cells. Both complexes were found enriched in nucleolus after cellular transfection,and their transfection efficiencies were significantly improved when transfection was per-formed on MCF-7 cells arrested at M phase. The transfection efficiency of CAR-CBA-pDNAwas inhibited by chlorpromazine, and cell endosomes were disrupted after being exposedto CAR-CBA-pDNA. In regards to CHL-CBA-pDNA, its transfection efficiency was not affected by three types of endocytosis inhibitors used in the study, and CHL-CBA-pDNA showed no effect on endosomes. Cellular lactate dehydrogenase release and membrane morphology were changed after cells were transfected by the two complexes. The results indicated that both CAR-CBA and CHL-CBA polymers demonstrated good nucleolus localization abilities. It was beneficial for transfection when cells were arrested at M phase. CAR-CBA-pDNA cellular internalization was involved with clathrin-mediated endocytosis pathway, and escaping from endosomal entrapment, while the cellular uptake of CHL-CBA-pDNA occurs via clathrin-and caveolae-independent mechanism.
基金financially supported by National Natural Science Foundation of China(No.22178143)Guangdong Basic and Applied Basic Research Foundation(Nos.2021A1515110365 and2020B1515120036)+3 种基金Natural Science Foundation of Anhui Higher Education Institutions(No.2023AH050168)Innovation and Entrepreneurship Training Program for China College Students(No.202310878049)Director Foundation of Anhui Province Engineering Laboratory of Advanced Building Materials(No.JZCL2305ZR)Ph.D.Startup Foundation of Anhui Jianzhu University(No.2023QDZ34)。
文摘Hypercrosslinked polymers(HCPs)with large surface areas,high intrinsic porosities and low production costs may be available platforms for iodine capture.However,the lack of iodine-philicity binding sites limits their adsorption capacity.Here we use vapor-phase postsynthetic amination strategy to introduce electron-donating amino groups into the prefabricated HCPs for enhancing their iodine capture performance.Through simple vapor-phase exposure,the halogen-containing HCPs can be grafted by amines through nucleophilic substitution toward chloro groups.Combining with the abundant amino groups and high porosities,the amino-functionalized porous polymers show substantially increased iodine adsorption capacity,about 221%as that of original one,accompanied by excellent recyclability.Mechanism investigations reveal the key roles of the electron-donor amino groups andπ-conjugated benzene rings along with structure characteristics of porous polymer frameworks in iodine capture.Moreover,this vapor-phase amination strategy shows good generality and can be extended to various amines,e.g.,ethylenediamine,1,3-diaminopropane and diethylenetriamine.Our work proves that this simple vapor-phase postsynthetic functionalization strategy may be applied in other porous polymers with wide application prospects in adsorption,separation and storage.
文摘Copolyesters having secondary and tertiary amine salt groups in the main and side chains are prepared by chemoselective polymerization. These copolyesters are soluble in a 10% aqueous solution of poly(vinyl alcohol) (PVA) at 90 degree C and act as plasticizer in the blend films cast from the solution. Only a glass transition temperature is observed for all these blends indicating the formation of compatible blends from these polyesters with PVA. These blends exhibit manifold characteristics such as ionic conductivity, complex formation with metal ions, absorption of moisture and color changes. The electric conductivity of the copolyesters and blends is in the range of 10** minus **6 Scm** minus **1. The blends with PVA forms complexes with Cu**2** plus and Co**2** plus . The coordination structure with two chelate rings is suggested for these polymer blend/metal complexes. (Author abstract) 10 Refs.
基金Supported by the National Natural Science Foundation of China(No.51703076).
文摘A triformylphloroglucinol-based AiB2-typed covalent organic polymer(TFG-BPTH)was successfully constructed by the condensation reaction of triformylphloroglucinol(TFG)and 2.5-bis(2-propynyloxy)terephthalo-hydrazide(BPTH)under solvothermal conditions.The structure of the TFG-BPTH was confirmed by spectra tech-niques including FTIR and solid-state IC CP/MAS NMR spectroscopy.The mophological features of TFG-BPTH were analyzed using scanning electron microscopy(SEM)and transmission electron microscopy(TEM).The TFG-BPTH possessed good thermal and chemical stability,and exhibited good photocatalytic activity as a metal-free heterogeneous catalyst for oxidation of amines to valuable imines under visible light irradiation using O2 as greer oxidant.In addition,the catalyst could be readily recovered from the reaction mixture by simple filtration and reused for at least five cycles without any observable change in structure and catalytic activity.
基金This work was supported by the National Natural Science Foundation of China(No.52073201).
文摘Main observation and conclusion Ring-opening metathesis polymerization(ROMP)is a powerful toolbox in preparation of bottlebrush polymers for its high activity.However,the ROMP of macromonomers with repeating tertiary amine groups,for example,poly(2-(dimethylamino)ethyl methacrylate)(PDMAEMA).
