Oxidation-Responsive Aliphatic Polycarbonates from N-Substituted   Eight-Membered Cyclic Carbonate: Synthesis and Degradation Study

doi:10.1002/marc.201700400

CORC > 北京大学 > 化学与分子工程学院

	Oxidation-Responsive Aliphatic Polycarbonates from N-Substituted Eight-Membered Cyclic Carbonate: Synthesis and Degradation Study
	Qiu, Fang-Yi ; Yu, Li ; Du, Fu-Sheng ; Li, Zi-Chen
刊名	MACROMOLECULAR RAPID COMMUNICATIONS
	2017
关键词	aliphatic polycarbonates eight-membered cyclic carbonates intramolecular cyclization oxidative degradation phenylboronic esters RING-OPENING POLYMERIZATION INTRAMOLECULAR CYCLIZATION BIOMEDICAL APPLICATIONS POLY(ESTER AMIDE)S GENE DELIVERY POLYMERS MONOMERS ACID COPOLYMERS BEHAVIOR
DOI	10.1002/marc.201700400
英文摘要	Oxidation-responsive aliphatic polycarbonates represent a promising branch of functional biodegradable polymers. This paper reports the synthesis and ring-opening polymerization (ROP) of an eight-membered cyclic carbonate possessing phenylboronic pinacol ester (C3) and the H2O2-triggered degradation of its polymer (PC3). C3 is prepared from the inexpensive and readily available diethanolamine with a moderate yield and undergoes the well-controlled anionic ROP with a living character under catalysis of 1,8-diazabicyclo[5.4.0] undec-7-ene. It can also be copolymerized with l-lactide, trimethylene carbonate, and 5-ter-butyloxycarbonylamino trimethylene carbonate, affording the copolymers with a varied distribution of the repeating units. To clearly demonstrate the oxidative degradation mechanism of PC3, this paper first investigates the H2O2-induced decomposition of small-molecule model compounds by proton nuclear magnetic resonance (H-1 NMR). It is found that the adduct products formed by the in-situ-generated secondary amines and p-quinone methide (QM) are thermodynamically unstable and can decompose slowly back to QM and the amines. On this basis, this paper further studies the H2O2-accelerated degradation of PC3 nanoparticles that are prepared by the o/w emulsion method. A sequential process of oxidation of the phenylboronic ester, 1,6-elimination of the in-situ-generated phenol, releasing CO2 and intramolecular cyclization or isomerization is proposed as the degradation mechanism of PC3.; National Natural Science Foundation of China [21474001, 21225416]; National Key Research and Development Program of China [2016YFA0201400]; SCI(E); ARTICLE; 20; 38
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/484798]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Qiu, Fang-Yi,Yu, Li,Du, Fu-Sheng,et al. Oxidation-Responsive Aliphatic Polycarbonates from N-Substituted Eight-Membered Cyclic Carbonate: Synthesis and Degradation Study[J]. MACROMOLECULAR RAPID COMMUNICATIONS,2017.
APA	Qiu, Fang-Yi,Yu, Li,Du, Fu-Sheng,&Li, Zi-Chen.(2017).Oxidation-Responsive Aliphatic Polycarbonates from N-Substituted Eight-Membered Cyclic Carbonate: Synthesis and Degradation Study.MACROMOLECULAR RAPID COMMUNICATIONS.
MLA	Qiu, Fang-Yi,et al."Oxidation-Responsive Aliphatic Polycarbonates from N-Substituted Eight-Membered Cyclic Carbonate: Synthesis and Degradation Study".MACROMOLECULAR RAPID COMMUNICATIONS (2017).