A series of water soluble aliphatic hyperbranched poly(amido amine)s(PAMAMs) with the same or similar chemical structure of poly(amido amine) dendrimer was successfully synthesized from commercially available AB and C...A series of water soluble aliphatic hyperbranched poly(amido amine)s(PAMAMs) with the same or similar chemical structure of poly(amido amine) dendrimer was successfully synthesized from commercially available AB and C_n types of monomers by one-pot polymerization via the couple-monomer methodology(CMM). The AB type monomer used in this paper was methyl acrylate, and C_n monomers were multi-amino compounds such as ethylenediamine(EDA), diethylenetriamine(DETA), triethylenetetraamine(TETA), tetraethylenepentaamine(TEPA) and pentaethylenehexamine(PEHA). The reaction mechanism was investigated by means of the mass spectra of the reaction intermediates. Adjusting the feed ratio of AB to C_n, hyperbranched polymers with different terminal groups and properties were obtained. FTIR, NMR, DSC, and TGA were used to characterize the polymers. It was found that the polymers′ properties such as solubility, thermal behaviour and encapsulation capability varied with changing the feed ratio of AB to C_n. Benzoyl and palmitoyl groups were introduced into these macromolecules by acidylation to form amphiphilic hyperbranched polymers which have a high capability to encapsulate water soluble dyes such as Congo red. It is expected that the hyperbranched PAMAMs can play an important role in the industrial applications, such as coatings, cross-linking and phase-transferring agents because of their versatility and availability.展开更多
A cationic gene delivery vector, guanidinylated disulfide-containing poly(amido amine)(CARCBA), was synthesized by Michael addition reaction between N,N′-cystaminebisacrylamide(CBA) and guanidine hydrochloride(CAR). ...A cationic gene delivery vector, guanidinylated disulfide-containing poly(amido amine)(CARCBA), was synthesized by Michael addition reaction between N,N′-cystaminebisacrylamide(CBA) and guanidine hydrochloride(CAR). Gel permeation chromatography(GPC) was used to evaluate the molecular weight of synthesized CAR-CBA. Polyethyleneimine(PEI) with molecular weight of 25 kDa was adopted as a reference, and polyethylene glycols(PEG) with different molecular weights were used to establish a standard curve for determining the molecular weight of CAR-CBA. The effects of two critical factors, namely columns and eluents,on the molecular weight measurement of CAR-CBA were investigated to optimize the GPC quantitative method. The results showed that Ultrahydrogel columns(120, 250) and HAc–NaAc(0.5 M, pH 4.5) buffer solution were the optimal column and GPC eluent, respectively.The molecular weight of the synthesized CAR-CBA was analyzed by the optimized GPC method and determined to be 24.66 kDa.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
This paper reports the production of glycopolymers via a simple and flexible method.A novel glycopolymer with a hyperbranched poly(amido amine) core and a sugar shell (HPAA-GLc) was synthesized by using thiol-ene clic...This paper reports the production of glycopolymers via a simple and flexible method.A novel glycopolymer with a hyperbranched poly(amido amine) core and a sugar shell (HPAA-GLc) was synthesized by using thiol-ene click reaction via facile one-pot method.Hyperbranched poly(amido amine) with vinyl terminals was first synthesized by Michael addition polymerization of N,N'-methylene bisacrylamide (MBA) with 1-(2-aminoethyl) piperazine (AEPZ).Subsequently,thiol-ene click reaction between vinyl units of hyperbranched poly(amido amine) and thio-glucose was performed in situ.Based on the NMR result,all the vinyl groups reacted with thiol-glucose in 120 min.Strong photoluminescence emission was observed from the aqueous solution of HPAA-GLc.展开更多
文章采用超支化聚合物聚酰胺胺(HPAMAM)和氧化石墨烯(graghene oxide,GO),通过真空抽滤自组装的方法制备了仿贝壳复合材料,并对其用京尼平进行了适当的交联。采用透射电子显微镜(transmission electron microscope,TEM)对GO进行了表征,...文章采用超支化聚合物聚酰胺胺(HPAMAM)和氧化石墨烯(graghene oxide,GO),通过真空抽滤自组装的方法制备了仿贝壳复合材料,并对其用京尼平进行了适当的交联。采用透射电子显微镜(transmission electron microscope,TEM)对GO进行了表征,采用红外光谱(infrared spectroscopy,IR)、扫描电子显微镜(scanning electron microscope,SEM)、X-射线衍射仪(X-ray diffraction,XRD)和电子万能试验机对HPAMAM/GO复合膜的结构和力学性能进行了表征。结果表明:HPAMAM/GO复合膜呈现出类似于贝壳的"砖"和"泥浆"排列的层状结构;随HPAMAM在复合膜中质量分数的提高,复合膜的延展性不断提高;在交联后,G-HPAMAM/GO复合膜的力学性能显著提高,拉伸强度约为150 MPa;复合膜保持了很高的韧性,其断裂伸长率高达10%以上。因此HPAMAM在构筑高强高韧仿贝壳复合材料方面具有非常高的研究价值。展开更多
文摘A series of water soluble aliphatic hyperbranched poly(amido amine)s(PAMAMs) with the same or similar chemical structure of poly(amido amine) dendrimer was successfully synthesized from commercially available AB and C_n types of monomers by one-pot polymerization via the couple-monomer methodology(CMM). The AB type monomer used in this paper was methyl acrylate, and C_n monomers were multi-amino compounds such as ethylenediamine(EDA), diethylenetriamine(DETA), triethylenetetraamine(TETA), tetraethylenepentaamine(TEPA) and pentaethylenehexamine(PEHA). The reaction mechanism was investigated by means of the mass spectra of the reaction intermediates. Adjusting the feed ratio of AB to C_n, hyperbranched polymers with different terminal groups and properties were obtained. FTIR, NMR, DSC, and TGA were used to characterize the polymers. It was found that the polymers′ properties such as solubility, thermal behaviour and encapsulation capability varied with changing the feed ratio of AB to C_n. Benzoyl and palmitoyl groups were introduced into these macromolecules by acidylation to form amphiphilic hyperbranched polymers which have a high capability to encapsulate water soluble dyes such as Congo red. It is expected that the hyperbranched PAMAMs can play an important role in the industrial applications, such as coatings, cross-linking and phase-transferring agents because of their versatility and availability.
基金Project supported by the Key Subject of Shanghai Municipal Education Commission(No.J50704)the Natural Science Foundation of Shanghai City(No.16ZR1435700)~~
基金the National Natural Science Foundation of China for financial support(No.81373335)
文摘A cationic gene delivery vector, guanidinylated disulfide-containing poly(amido amine)(CARCBA), was synthesized by Michael addition reaction between N,N′-cystaminebisacrylamide(CBA) and guanidine hydrochloride(CAR). Gel permeation chromatography(GPC) was used to evaluate the molecular weight of synthesized CAR-CBA. Polyethyleneimine(PEI) with molecular weight of 25 kDa was adopted as a reference, and polyethylene glycols(PEG) with different molecular weights were used to establish a standard curve for determining the molecular weight of CAR-CBA. The effects of two critical factors, namely columns and eluents,on the molecular weight measurement of CAR-CBA were investigated to optimize the GPC quantitative method. The results showed that Ultrahydrogel columns(120, 250) and HAc–NaAc(0.5 M, pH 4.5) buffer solution were the optimal column and GPC eluent, respectively.The molecular weight of the synthesized CAR-CBA was analyzed by the optimized GPC method and determined to be 24.66 kDa.
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supported by the National Natural Science Foundation of China (20874093,50973102)
文摘This paper reports the production of glycopolymers via a simple and flexible method.A novel glycopolymer with a hyperbranched poly(amido amine) core and a sugar shell (HPAA-GLc) was synthesized by using thiol-ene click reaction via facile one-pot method.Hyperbranched poly(amido amine) with vinyl terminals was first synthesized by Michael addition polymerization of N,N'-methylene bisacrylamide (MBA) with 1-(2-aminoethyl) piperazine (AEPZ).Subsequently,thiol-ene click reaction between vinyl units of hyperbranched poly(amido amine) and thio-glucose was performed in situ.Based on the NMR result,all the vinyl groups reacted with thiol-glucose in 120 min.Strong photoluminescence emission was observed from the aqueous solution of HPAA-GLc.
文摘文章采用超支化聚合物聚酰胺胺(HPAMAM)和氧化石墨烯(graghene oxide,GO),通过真空抽滤自组装的方法制备了仿贝壳复合材料,并对其用京尼平进行了适当的交联。采用透射电子显微镜(transmission electron microscope,TEM)对GO进行了表征,采用红外光谱(infrared spectroscopy,IR)、扫描电子显微镜(scanning electron microscope,SEM)、X-射线衍射仪(X-ray diffraction,XRD)和电子万能试验机对HPAMAM/GO复合膜的结构和力学性能进行了表征。结果表明:HPAMAM/GO复合膜呈现出类似于贝壳的"砖"和"泥浆"排列的层状结构;随HPAMAM在复合膜中质量分数的提高,复合膜的延展性不断提高;在交联后,G-HPAMAM/GO复合膜的力学性能显著提高,拉伸强度约为150 MPa;复合膜保持了很高的韧性,其断裂伸长率高达10%以上。因此HPAMAM在构筑高强高韧仿贝壳复合材料方面具有非常高的研究价值。
