Synthesis and pH‐responsive assembly of methoxy poly(ethylene glycol)‐b‐poly(ε‐caprolactone) with pendant carboxyl groups

Abstract

pH‐responsive methoxy poly(ethylene glycol)‐b‐poly(ε‐caprolactone) bearing pendant carboxyl groups mPEG‐b‐P(2‐CCL‐co‐6‐CCL) was synthesized based on our newly monomer benzyloxycarbonylmethly functionalized ε‐caprolactone. Their structure was confirmed by 1H NMR, 13C NMR, and Fourier transform infrared spectrum spectra. In addition, SEC results indicated that the copolymers had a relatively narrow polydispersity. WXRD and DSC demonstrated that the introduction of carboxymethyl groups had significant effect on the crystallinity of the copolymers. Furthermore, the solution behavior of mPEG‐b‐P(2‐CCL‐co‐6‐CCL) has been studied by various methods. The results indicated that mPEG‐b‐P(2‐CCL‐co‐6‐CCL) had a rich pH‐responsive behavior and the micelles could be formed by pH induction, and the mPEG‐b‐P(2‐CCL‐co‐6‐CCL) could existed as unimers, micelles or large aggregates in different pH range accordingly. The mechanism of which was supposed to depend on the counteraction between the hydrophobic interaction from PCL and the ionization of the carboxyl groups along the polymer chain. Moreover, the mPEG‐b‐P(2‐CCL‐co‐6‐CCL) copolymers displayed good biocompatibility according to the preliminary cytotoxicity study. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 188–199

Pendant small functional groups on poly(ϵ-caprolactone) substrate modulate adhesion, proliferation and differentiation of human mesenchymal stem cells

“…[30], PCL bearing COOH was prepared as reported in Refs. [31,32] and PCL bearing OH and C O were prepared as in Ref. [33].…”

Synthesis of well-defined carboxyl poly(ε-caprolactone) by fine-tuning the protection group

“…Each substitution ended up with the mixture of isomers containing 2-BCL and 6-BCL, which were confirmed by 1 H NMR and 13 C NMR spectroscopy (Fig. 25 Furthermore, an electron donating group (CH 3 ) in para position of the substitution promoted the regioselectivity in generating maximum proportion of 6-BCL, indicating that BV oxidation was also affected by electronic effects. According to HPLC analysis in Table S1, the isomer ratio of 6-BCL to 2-BCL with CH 3 , NO 2 and H groups were 7:1, 6:1 and 5:1, respectively.…”

“…19,20 The substitution routinely occurs on the α-, γ-or ε-position of ε-caprolactone ring, i.e., 2-CL, 4-CL and 6-CL, among which the asymmetry degree of chiral carbon appears higher in 2-CL and 6-CL than in 4-CL. [22][23][24][25] For example, Marc A. Hillmyer and colleagues have tried to separate 2-(CH 3 )CL from 6-(CH 3 )CL by fractional distillation, 24 but the concentration of 2-(CH 3 )BCL did not change upon purification. Since they were very alike in physical and chemical properties, the purification of 2-CL and 6-CL isomers was kept extremely challenging.…”

Synthesis and Properties of the Poly(ε-caprolactone)-paclitaxel Prodrug

“…由于聚己内酯不含有侧基官 能团, 基于聚己内酯-紫杉醇的前药系统的研究鲜有报 道. 本研究利用侧链带有羧基的两亲性官能化聚己内酯 嵌段共聚物 Pluronic-b-P(CL-co-CCL) (FC)为底物 [13] [14,15] . 根据文献报道 [8] , [16,17] .…”