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Frontiers of Materials Science

ISSN 2095-025X

ISSN 2095-0268(Online)

CN 11-5985/TB

Postal Subscription Code 80-974

2018 Impact Factor: 1.701

Front. Mater. Sci.    2019, Vol. 13 Issue (3) : 296-304    https://doi.org/10.1007/s11706-019-0469-9
RESEARCH ARTICLE
Facile preparation of acid/CO2 stimuli-responsive sheddable nanoparticles based on carboxymethylated chitosan
Weiwei FAN(), Jilu WANG, Jiajun FENG, Yong WANG
Hubei Collaborative Innovation Center of Targeted Antitumor Drug, College of Chemical Engineering and Pharmacy, Jingchu University of Technology, Jingmen 448000, China
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Abstract

The present study describes the facile preparation of acid/CO2 stimuli-responsive sheddable nanoparticles based on carboxymethylated chitosan (CMCS). Commercially available CMCS was grafted with monomethoxy polyethylene glycol (mPEG) chains via an acid/CO2 responsive linker, i.e., benzoic-imine, and then was used for the cross-linking with CaCl2. With a high CMCS concentration up to 7 mg/mL, stable nanoparticles were successfully prepared. The particle size grew slightly with increasing the molecular weight of mPEG. When the concentration of CaCl2 and the feed ratio of CMCS to mPEG increased, the particle size decreased at first and then increased after reaching a minimum size. When the particles were stimulated by CO2 or acid, benzoic-imine cleaved quickly, and mPEG fell off the nanoparticles simultaneously, and then flocculation and precipitation occurred. These sheddable nanoparticles might have potential application in the biomedical field including the intelligent drug delivery system.

Keywords carboxymethylated chitosan      nanoparticles      benzoic-imine      ionic cross-linking      acid-sensitivity     
Corresponding Author(s): Weiwei FAN   
Online First Date: 01 August 2019    Issue Date: 29 September 2019
 Cite this article:   
Weiwei FAN,Jilu WANG,Jiajun FENG, et al. Facile preparation of acid/CO2 stimuli-responsive sheddable nanoparticles based on carboxymethylated chitosan[J]. Front. Mater. Sci., 2019, 13(3): 296-304.
 URL:  
https://academic.hep.com.cn/foms/EN/10.1007/s11706-019-0469-9
https://academic.hep.com.cn/foms/EN/Y2019/V13/I3/296
Entry CMCS-g-mPEG Z-average size a)/nm PDI
1 CMCS-g-mPEG1k 282±2.2 0.188
2 CMCS-g-mPEG2k 314±4.0 0.154
3 CMCS-g-mPEG4k 332±2.5 0.196
Tab.1  The size and the size distribution of nanoparticles (measured by DLS)
Fig.1  Scheme 1 Preparation of mPEG-CHO, CMCS-g-mPEG and nanoparticles.
Fig.2  1H NMR spectra of mPEG2k-CHO (a), CMCS (b) and mPEG2k-g-CMCS (c) with D2O as the solvent.
Fig.3  DLS plots of CS nanoparticles: CMCS-g-mPEG1k (a); CMCS-g-mPEG2k (b); CMCS-g-mPEG4k (c).
Fig.4  Particle size with different molecular weights of mPEG. Error bars were calculated from 3 independent measurements.
Fig.5  TEM images of nanoparticles based on CMCS-g-mPEG1k of (a) 5 mg/mL and (b) 1.67 mg/mL, CMCS-g-mPEG2k of (c)(d) 5 mg/mL and (e) 1.67 mg/mL, and CMCS-g-mPEG2k of (f) 5 mg/mL and (g) 1.67 mg/mL.
Fig.6  Sizes and distributions of nanoparticles (Mn(mPEG) = 2000, m(CMCS):m(mPEG) = 2:1): (a) plots of Z-average size; size distribution with the concentration of CMCS at (b) 3 mg/mL, (c) 5 mg/mL and (d) 7 mg/mL. Error bars were calculated from 3 independent measurements.
Fig.7  Dependence of the particle size on the feed ratio of CMCS to mPEG (Mn(mPEG) = 2000, c(CaCl2) = 1.7 mg/mL, c(CMCS) = 5 mg/mL). Error bars were calculated from 3 independent measurements.
Fig.8  (a) The nanoparticle dispersion (Sample 2 in Table 1) and (b) the state after bubbling with CO2 for 10 min.
Fig.9  1H NMR spectra of CMCS-g-mPEG2k: in D2O (a); in D2O and after bubbling with CO2 for 10 min (b).
Fig.10  TEM images of the nanoparticle dispersion (c(CMCS-g-mPEG2k) = 5 mg/mL) after bubbling with CO2: (a) turbid state before precipitating; (b) turbid state after precipitating.
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