Preparation and Characterization of pH Responsive Complex Micelles with Dynamic Boronate Cross-Linking

2019 ◽  
Vol 944 ◽  
pp. 557-564
Author(s):  
Jia Ming Xu ◽  
Dan Yue Wang ◽  
Han Tong ◽  
Xiao Ze Jiang ◽  
Mei Fang Zhu
Keyword(s):  
Ethylene Glycol ◽  
Phenylboronic Acid ◽  
Proton Nuclear Magnetic Resonance ◽  
Cross Linking ◽  
Ph Responsive ◽  
Poly Ethylene Glycol ◽  
Boronate Ester ◽  
H Nmr ◽  
Poly Ethylene ◽  
Complex Micelles

Two kinds of diblock copolymers containing glucose and phenylboronic acid moieties, respectively, poly (ethylene glycol)-b-poly (gluconamidoethyl methacrylate) (PEG-b-PGAMA) and poly (ethylene glycol)-b-poly (2-aminoethyl methacrylate-co-3-nitrophenyboronic acid methacrylate) (PEG-b-P(AMA-co-NPBMA)) were synthesized via atom transfer radical polymerization (ATRP) and post polymerization modification (PPM). Well-defined structure and narrow molecular weight distribution of the polymers were confirmed by proton Nuclear Magnetic Resonance (1H NMR) and Gel Permeation Chromatography (GPC). Based on the cross-linking between the diol groups of the glycopolymer and phenylboronic acid under physiological pH (7.4), complex micelles composed of PEG outer shell and boronate ester cross-linking core with a hydrodynamic diameter around 20nm were formed. Morphology, size and assembly behavior of the complex micelles were investigated by 1H NMR, transmission electron microscopy (TEM) and dynamic light scattering (DLS). The results showed the formation/cleavage of boronate ester linkage is reversible upon the variation of solution pH, the complex micelles displayed pH sentiveties of assembling/disassembling behavior. Above pH 7.4, stable spherical micelles can be formed, whereas pH less than 5.5, the micelles dissociated into unimers. Therefore, such pH-responsive micelles based on dynamic complexation of phenyl boronate bonds are expected to be applied to pH-responsive nanodrug carriers

Synthesis and Self-Assembly of Well-Defined pH-Responsive Block Glycopolymers

2015 ◽  
Vol 815 ◽  
pp. 359-366 ◽  
Author(s):  
Qing Yun Yu ◽  
Lu Bin Lin ◽  
Xue Yu Xing ◽  
Hai Liang Dong ◽  
Xiao Ze Jiang ◽  
...  
Keyword(s):  
Ethylene Glycol ◽  
Self Assembly ◽  
Phenylboronic Acid ◽  
Proton Nuclear Magnetic Resonance ◽  
Similar Degree ◽  
Random Structure ◽  
Ph Responsive ◽  
Poly Ethylene Glycol ◽  
Ethyl Methacrylate ◽  
Poly Ethylene

Two pH-responsive block glycopolymers, poly (ethylene glycol)-b-Poly (2- (diethylamino) ethyl methacrylate-co-2-gluconamidoethyl methacrylate) (PEG113-b-P(DEA55-co-GAMA12)) and poly (ethylene glycol)-b-poly (2-(diethylamino) ethyl methacrylate)-b-poly (2-gluconamido ethyl methacrylate) (PEG113-b-PDEA55-b-PGAMA15), were synthesized via atom transfer radical polymerization (ATRP) by directly or successively polymerization of GAMA and DEA monomers using a PEG-based macroinitiator, respectively, without protecting group chemistry. Those block glycopolymers were confirmed by proton Nuclear Magnetic Resonance (1H NMR) and Gel Permeation Chromatography (GPC), and their self-assembly behaviors were characterized by Transmission Electron Microscopy (TEM), Dynamic Light Scattering (DLS) and Zeta-potential. The results show both synthetic block glycopolymers were dissolved molecularly in aqueous solution at acidic pH (such as pH 3), thus it can reversibly convert to be two-layer micelles comprising DEA and GAMA cores, PEG coronas with size of around 50 nm, or micelles comprising DEA cores, GAMA and PEG outer coronas with bigger size of 70 nm for PEG113-b- P(DEA55-co-GAMA12) and PEG113-b-PDEA55-b-PGAMA15), respectively, at basic condition. Both glycopolymers have the micellization process at middle pH (pH 6-8), but possess different isoelectric points (pIs) (at pH 8.0 and 7.8) for their pH responsive block of PEG113-b-P(DEA55-co-GAMA12) and PEG113-b-PDEA55-b-PGAMA15 with DEA-co-GAMA random structure or DEA chain only, respectively. This study not only reveals the self-assembly of pH responsive block glycopolymers with different architectures by fixing similar degree polymerization (DP) of their blocks, but also provides a tool to investigate pH induced dynamic covalent interaction between glycopolymers and phenylboronic acid derivatives or a light for designing novel drug delivery carriers.

pH-Responsive Hyperbranched Copolymers from One-Pot RAFT Copolymerization of Propylacrylic Acid and Poly(ethylene glycol diacrylate)

2012 ◽  
Vol 77 ◽  
pp. 333-342 ◽  
Author(s):  
Hong Yun Tai ◽  
Craig L. Duvall ◽  
Patrick S. Stayton ◽  
Alan S. Hoffman ◽  
Wen Xin Wang
Keyword(s):  
Ethylene Glycol ◽  
Proton Nuclear Magnetic Resonance ◽  
Therapeutic Drug ◽  
Copolymer Composition ◽  
Ph Responsive ◽  
Poly Ethylene Glycol ◽  
One Pot ◽  
Glycol Diacrylate ◽  
Monomer Feed ◽  
Poly Ethylene

pH-Responsive polymers have attracted much attention for biotechnology applications as carriers or matrix to facilitate intracellular or extracellular therapeutic drug delivery and release. In this paper, we report the development of new pH-responsive and hyperbranched copolymers with potential for such applications. These pH-responsive hyperbranched copolymers were synthesized via one pot reversible addition-fragmentation chain transfer (RAFT) copolymerization of propylacrylic acid (PAA) and a branching co-monomer poly(ethylene glycol diacrylate) (PEGDA) (Mn=258 Da) at the monomer feed molar ratios [PAA]0/[PEGDA]0 = 99/1, 90/10 and 80/20. The resultant poly(PAA-PEGDA) copolymers were characterized by Proton Nuclear Magnetic Resonance (1H NMR) and Gel Permeation Chromatography (GPC) to obtain the molecular weight, copolymer composition and degree of acrylate functionality. The hydrodynamic dimensions of these copolymers at pH range between 5.0 and 7.4 were studied using Dynamic Light Scattering technique (DLS). Moreover, these hyperbranched copolymers demonstrated composition- and size-dependent membrane disruptive properties by red blood cell hemolysis assay. Poly(PAA-PEGDA) with the copolymer composition [PAA]/[PEGDA]= 68/32, obtained from the copolymerization at the monomer feed molar ratio [PAA]0/[PEGDA]0 = 99/1, demonstrated significant membrane disruptive activity.

Cross-linking of cellulose and poly(ethylene glycol) with citric acid

2015 ◽  
Vol 90 ◽  
pp. 21-24 ◽  
Author(s):  
Pamela de Cuadro ◽  
Tiina Belt ◽  
Katri S. Kontturi ◽  
Mehedi Reza ◽  
Eero Kontturi ◽  
...  
Keyword(s):  
Citric Acid ◽  
Ethylene Glycol ◽  
Cross Linking ◽  
Poly Ethylene Glycol ◽  
Poly Ethylene

One-shot synthesis and solution properties of ROS/pH responsive methoxy poly(ethylene glycol)-b-polycarbonate

2019 ◽  
Vol 10 (17) ◽  
pp. 2143-2151 ◽  
Author(s):  
Yan Zhang ◽  
Yue Xu ◽  
Chao Wei ◽  
Chuanhao Sun ◽  
Bingkun Yan ◽  
...  
Keyword(s):  
Ethylene Glycol ◽  
Tertiary Amine ◽  
Solution Properties ◽  
Ph Responsive ◽  
Poly Ethylene Glycol ◽  
Amine Groups ◽  
Poly Ethylene

A one-shot method was employed to synthesize ROS/pH responsive methoxy poly(ethylene glycol)-b-polycarbonate (mPEG-b-poly(MN-co-MSe)) with the selenide and tertiary amine groups situated on the backbone.

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