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        Biodegradable pH- and Temperature-Sensitive Multiblock Copolymer Hydrogels Based on Poly(amino-ester urethane)s

        Yongtai Zheng,Chaoliang He,Cong Truc Huynh,이두성 한국고분자학회 2010 Macromolecular Research Vol.18 No.10

        A novel pH- and temperature-responsive multiblock copolymer consisting of poly(ethylene glycol) (PEG) and poly(amino-ester urethane) (PAEU) is reported. First, a biodegradable monomer, bis-1,4-(hydroxyethyl)piperazine mono-lactate (HEP mono-lactate), was synthesized by the ring-opening polymerization of D,L-lactide (LA) using HEP and Sn(Oct)2 as an initiator and catalyst, respectively. The multiblock copolymers were synthesized further from PEG, HEP, HEP mono-lactate, and 1,6-diisocyanatohexamethylene (HDI) in the presence of dibutyltin dilaurate as a catalyst. The resulting copolymers were characterized by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FTIR), and gel permeation chromatography (GPC). At pH 6.8 or higher, the copolymer aqueous solutions showed gel-to-sol transitions with increasing temperature, and the gel window covered the physiological conditions. After a subcutaneous injection of the multiblock copolymer solution into SD rats, a soft gel was formed in a short time. The degradability of the copolymer was adjusted by varying the LA content in the PAEU block.

      • KCI등재

        pH-Responsive Drug Delivery Systems Based on Clickable Poly(L-glutamic acid)-Grafted Comb Copolymers

        Jianxun Ding,Xuesi Chen,Chaoliang He,Chunsheng Xiao,Jie Chen,Xiuli Zhuang 한국고분자학회 2012 Macromolecular Research Vol.20 No.3

        Five pH-responsive alkyne-poly(2-aminoethyl methacrylate)-graft-poly(L-glutamic acid) (alkyne-PAMA-g-PLGA) comb copolymers were synthesized through the ring-opening polymerization (ROP) of γ-benzyl-L-glutamate N-carboxyanhydride (BLG NCA) and the subsequent deprotection of benzyl group from BLG unit. The chemical structures of copolymers were confirmed by proton nuclear magnetic resonance spectra (1H NMR) and Fourier transform infrared spectroscopy (FTIR). The pyrene-probe-based fluorescence technique and transmission electron microscopy (TEM) measurements revealed that the comb copolymers could spontaneously self-assemble into micellar or vesicular nanoparticles in phosphate buffered saline (PBS) at pH 7.4. Doxorubicin (DOX), an anthracycline anticancer drug, was loaded into nanoparticles as a model anticancer drug. The in vitro release results showed that the release behaviors could be altered by adjusting the composition of the comb copolymer and pH of the release medium. In vitro methyl thiazolyl tetrazolium (MTT) assays demonstrated that the copolymers were biocompatible,and DOX-loaded nanoparticles showed effective inhibition of cellular proliferation. Hemolysis tests indicated that the copolymers were also hemocompatible, and that the presence of the copolymers could reduce the hemolysis ratio (HR) of the DOX significantly. In addition, the comb copolymers could be modified through versatile Cu(I)-catalyzed “click chemistry” between the terminal alkyne group and azide-modified functional agents. These properties indicate that the pH-responsive clickable comb copolymers are promising candidates for multifunctional nanocarriers in cancer diagnosis and therapy.

      • KCI등재

        pH- and Temperature-Sensitive PCL-Grafted Poly(β-amino ester)- Poly(ethylene glycol)-Poly(β-amino ester) Copolymer Hydrogels

        Yongtai Zheng,Minh Khanh Nguyen,Chaoliang He,Cong Truc Huynh,이두성 한국고분자학회 2010 Macromolecular Research Vol.18 No.11

        A series of poly(ε-caprolactone)-grafted poly(β-amino ester)-poly(ethylene glycol)-poly(β-amino ester)((PAE-g-PCL)-PEG-(PAE-g-PCL)) copolymers were designed and synthesized for use in injectable pH- and temperature-sensitive hydrogels. First, PEG diacrylate was synthesized and used as a macroinitiator, and the chain was extended by 4,4 trimethylene dipiperidine (TMDP), 3-amino-1-propanol and diacrylate monomers (1,4-butanediol diacrylate (BDA), and 1,6-hexanediol diacrylate (HDA)) to obtain the triblock copolymers (PAE-PEG-PAE). Poly (ε-caprolactone) was then grafted to the pendant OH groups of the resulting PAE-PEG-PAE by ring opening polymerization. The PAE-PEG-PAE and (PAE-g-PCL)-PEG-(PAE-g-PCL) copolymers were characterized by 1H nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography. The phase diagram was measured using the tube inverting method. At pH 6.6 or higher, the (PAE-g-PCL)-PEG-(PAE-g-PCL) copolymer solutions (30 wt%) displayed sol-gel-sol transitions with increasing temperature. The viscosity of the graft copolymer solutions was determined as a function of temperature by dynamic mechanical analysis. In addition, after the subcutaneous injection of the polymer solution (30 wt%, pH 6.4) into a rat, a gel formed within a short time, suggesting biomedical applications.

      • SCIESCOPUSKCI등재

        Thermo-/pH-dual responsive properties of hyperbranched polyethylenimine grafted by phenylalanine

        Chen, Jie,Xia, Jialiang,Tian, Huayu,Tang, Zhaohui,He, Chaoliang,Chen, Xuesi 대한약학회 2014 Archives of Pharmacal Research Vol.37 No.1

        Novel thermo- and pH-dual responsive amphiphilic copolymers were synthesized based on hyperbranched polyethylenimine (PEI) by grafting $\small{L}$-phenylalanine. The phenylalanine-modified PEI exhibited lower cytotoxicity than commercial PEI. These copolymers showed the phenomena of phase transitions in response to pH and temperature. The dilute copolymer solution at lower pH displayed the higher LCST. Furthermore, LCST increased with the increasing of phenylalanine grafting density. LCST of these copolymers were tunable from 7.2 to $59.6^{\circ}C$ by the degree of amidation and pH of solution. DLS and TEM experiments certified that the copolymer chains aggregated to form small size particles as increasing the temperature above LCST. For these reasons, the obtained smart copolymers were considered to be potential gene/drug carriers in biomedical field.

      • KCI등재

        Thermo-/pH-dual responsive properties of hyperbranched polyethylenimine grafted by phenylalanine

        Jie Chen,Jialiang Xia,Huayu Tian,Zhaohui Tang,Chaoliang He,Xuesi Chen 대한약학회 2014 Archives of Pharmacal Research Vol.37 No.1

        Novel thermo- and pH-dual responsiveamphiphilic copolymers were synthesized based on hyperbranchedpolyethylenimine (PEI) by grafting L-phenylalanine. The phenylalanine-modified PEI exhibited lowercytotoxicity than commercial PEI. These copolymersshowed the phenomena of phase transitions in response topH and temperature. The dilute copolymer solution atlower pH displayed the higher LCST. Furthermore, LCSTincreased with the increasing of phenylalanine graftingdensity. LCST of these copolymers were tunable from 7.2to 59.6 C by the degree of amidation and pH of solution. DLS and TEM experiments certified that the copolymerchains aggregated to form small size particles as increasingthe temperature above LCST. For these reasons, theobtained smart copolymers were considered to be potentialgene/drug carriers in biomedical field.

      • KCI등재

        Selection of reference genes for Harmonia axyridis (Coleoptera: Coccinellidae) feeding on different diets

        Chao Liang,Shipeng Han,Hui Han,Feng Zhao,Yunzhuan He 한국응용곤충학회 2019 Journal of Asia-Pacific Entomology Vol.22 No.4

        The selection of a stable reference gene is vital to gene expression studies and to improving the accuracy of RTqPCR data. With the deep research on the artificial feed of the Harmonia axyridis, there is an increasing need to evaluate the effects of feed on insects at the molecular level. To identify a reference gene to assess the expression of related genes in Harmonia axyridis (Pallas), ensure the reliability of target gene expression analysis using realtime PCR. Especially for H. axyridis were fed Rhopalosiphum padi (L.) or an artificial diet. In this study, the expression profiles of nine candidate reference genes, including 28SrRNA, 18SrRNA, RPS23, EF1, Actin, ATPase, GAPDH, UBI, RPL13 from different H. axyridis tissues (head, thorax, wing, leg, ovary, and fat body) were investigated. The stability of the nine candidate genes was assessed using geNorm, NormFinder, BestKeeper and RefFinder software, and a comprehensive analysis showed that EF1 is a suitable reference gene for eating different diets of different organizations from H. axyridis. 28SrRNA, 18SrRNA, and RPS23 can also be used as reference genes, but Actin, ATPase, RPL13 are not suitable as an internal reference gene

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