Synthesis and Characterization of Poly(E,K) and Poly(E,R)†

doi:10.7503/cjcu20160190

Abstract

Abstract:

A series of random copolymers Poly(E,K) and Poly(E,R) was synthesized by the ring-opening polymerization of amino acid-N-carboxyanhydride(amino acid-NCA), along with changing the feed ratio of glutamin acid-N-carboxyanhydride(BLG-NCA) and lysine(benzyloxycarbonyl)-N-carboxyanhydride[Lys(Z)-NCA] as well as BLG-NCA and ornithine(benzyloxycarbonyl)-N-carboxyanhydride[Orn(Z)-NCA] and by the subsequent deprotection and guanidination. These random copolymers were confirmed by nuclear magnetic resonance(¹H NMR and ¹³C NMR), and the molar ratios of different amino acids in the copolymers were close to the feed ratios of corresponding NCA in the ring-opening polymerization. Dynamic light scattering(DLS) test showed that the random copolymers assemble to uniform micelles with less than 200 nm diameter at pH of 7.4. The zeta potential of the random copolymers could change with the pH of solution, suggesting that the copolymers are pH-sensitive.

Key words: Ring-opening polymerization, Random copolymer, pH-Sensitive

CLC Number:

O631

TrendMD:

WANG Huijie, YU Haiyang, ZHANG Dawei, TANG Zhaohui, CAO Qi. Synthesis and Characterization of Poly(E,K) and Poly(E,R)^†[J]. Chem. J. Chinese Universities, 2017, 38(1): 165.

Figures/Tables 10

Scheme 1 Synthesis routes of Poly(E,K)

Fig.1 1H NMR spectra of Poly[E(Bn),K(Cbz)](A) and Poly(E,K)(B) in TFA-d (A) a. Poly[E(Bn),K(Cbz)]1; b. Poly[E(Bn),K(Cbz)]2; c. Poly[E(Bn),K(Cbz)]3. (B) a. Poly(E,K)1; b. Poly(E,K)2; c. Poly(E,K)3.

Fig.2 Quantitative 13C NMR spectra of Poly(E,K) in TFA-da. Poly(E,K)1; b. Poly(E,K)2; c. Poly(E,K)3.

Scheme 2 Synthesis routes of Poly(E,R)

Fig.3 1H NMR spectra of Poly[E(Bn),O(Cbz)](A), Poly(E,O)(B) and Poly(E,R)(C) in TFA-d (A) a. Poly[E(Bn),O(Cbz)]1; b. Poly[E(Bn),O(Cbz)]2; c. Poly[E(Bn),O(Cbz)]3. (B) a. Poly(E,O)1; b. Poly(E,O)2; c. Poly(E,O)3. (C) a. Poly(E,R)1; b. Poly(E,R)2; c. Poly(E,R)3.

Fig.4 Quantitative 13C NMR spectra of Poly(E,O)(A) and Poly(E,R)(B) in D2O/NaOD (A) a. Poly(E,O)1; b. Poly(E,O)2; c. Poly(E,O)3. (B) a. Poly(E,R)1; b. Poly(E,R)2; c. Poly(E,R)3.

Fig.5 GPC curves of Poly[E(Bn),K(Cbz)](A), Poly[E(Bn),O(Cbz)](B), Poly(E,K)(C), Poly(E,O)(D) and Poly(E,R)(E) (A) a. Poly[E(Bn),K(Cbz)]1; b. Poly[E(Bn),K(Cbz)]2; c. Poly[E(Bn),K(Cbz)]3. (B) a. Poly[E(Bn),O(Cbz)]1; b. Poly[E(Bn),O(Cbz)]2; c. Poly[E(Bn),O(Cbz)]3. (C) a. Poly(E,K)1; b. Poly(E,K)2. (D) a. Poly(E,O)1; b. Poly(E,O)2. (E) Poly(E,R)1.

Table 1 Characterization of copolymers

Copolymer	Feed molar ratio	Resultant molar ratio	10^-3 $M n h$	PDI^h	Conversion ratio(%)
Poly[E(Bn),K(Cbz)]₁	2:1^a	2.2:1.0^c	20.4	1.30	86
Poly[E(Bn),K(Cbz)]₂	1:1^a	1.1:1.0^c	16.6	1.25	87
Poly[E(Bn),K(Cbz)]₃	1:2^a	1.0:1.8^c	12.9	1.26	81
Poly(E,K)₁	2:1^a	2.2:1.0^d	5.5	1.33	95
Poly(E,K)₂	1:1^a	1.0:1.0^d	6.0	1.38	96
Poly(E,K)₃	1:2^a	1.0:1.8^d			93
Poly[E(Bn),O(Cbz)]₁	2:1^b	2.2:1.0^e	16.2	1.37	84
Poly[E(Bn),O(Cbz)]₂	1:1^b	1.2:1.0^e	11.9	1.28	83
Poly[E(Bn),O(Cbz)]₃	1:2^b	1.0:1.9^e	10.5	1.29	87
Poly(E,O)₁	2:1^b	2.0:1.0^f	7.9	1.41	96
Poly(E,O)₂	1:1^b	1.0:1.0^f	6.1	1.45	94
Poly(E,O)₃	1:2^b	1.0:2.0^f			93
Poly(E,R)₁	2:1^b	2.2:1.0^g	15.9	1.43	95
Poly(E,R)₂	1:1^b	1.2:1.0^g			93
Poly(E,R)₃	1:2^b	1.0:1.9^g			92

Table 1 Characterization of copolymers

Copolymer	Feed molar ratio	Resultant molar ratio	10^-3 $M n h$	PDI^h	Conversion ratio(%)
Poly[E(Bn),K(Cbz)]₁	2:1^a	2.2:1.0^c	20.4	1.30	86
Poly[E(Bn),K(Cbz)]₂	1:1^a	1.1:1.0^c	16.6	1.25	87
Poly[E(Bn),K(Cbz)]₃	1:2^a	1.0:1.8^c	12.9	1.26	81
Poly(E,K)₁	2:1^a	2.2:1.0^d	5.5	1.33	95
Poly(E,K)₂	1:1^a	1.0:1.0^d	6.0	1.38	96
Poly(E,K)₃	1:2^a	1.0:1.8^d			93
Poly[E(Bn),O(Cbz)]₁	2:1^b	2.2:1.0^e	16.2	1.37	84
Poly[E(Bn),O(Cbz)]₂	1:1^b	1.2:1.0^e	11.9	1.28	83
Poly[E(Bn),O(Cbz)]₃	1:2^b	1.0:1.9^e	10.5	1.29	87
Poly(E,O)₁	2:1^b	2.0:1.0^f	7.9	1.41	96
Poly(E,O)₂	1:1^b	1.0:1.0^f	6.1	1.45	94
Poly(E,O)₃	1:2^b	1.0:2.0^f			93
Poly(E,R)₁	2:1^b	2.2:1.0^g	15.9	1.43	95
Poly(E,R)₂	1:1^b	1.2:1.0^g			93
Poly(E,R)₃	1:2^b	1.0:1.9^g			92

Fig.6 Sizes of copolymer micelles determined by DLS(A) Poly(E,K)1; (B) Poly(E,K)2; (C) Poly(E,K)3; (D) Poly(E,R)1; (E) Poly(E,R)2; (F) Poly(E,R)3.

Fig.7 Zeta potentials of Poly(E,K)(A) and Poly(E,R)(B) at different pH(A) a. Poly(E,K)1; b. Poly(E,K)2; c. Poly(E,K)3. (B) a. Poly(E,R)1; b. Poly(E,R)2; c. Poly(E,R)3.

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