Preparation and Recognization Property of Chiral Thermo-sensitive P(NIPAM-co-NALL) Hydrogels†

doi:10.7503/cjcu20130743

Abstract

Abstract:

A series of novel thermo-sensitive hydrogels based on N-isopropylacrylamide(NIPAM) containing L-leucine groups was designed and synthesized for chiral recognition. L-Leucine used as chiral pool, the chiral monomer N-acryloyl-L-leucine methyl ester(NALL) was obtained by sterifization with methanol to protect carboxyl group and then condensation with acryloyl chloride in the presence of trirthylamine in N,N-dimethylfo-mamid(DMF)and gave the chiral monomers N-acryloyl-L-leucine methyl ester(NALL), whose structure was characterized by infrared(IR) and proton nuclear magnetic resonance(¹H NMR). Then the subsequent copolymerization was carried on between NALL as chiral recognition units, NIPAM and N,N'-methylenebisacry-lamide(MBAA) as linkage agent in the presence of azobisisobutyronitrile(AIBN) in ethanol with different mass ratios. The P(NIPAM-co-NALL) hydrogels were identified by IR. The swelling behavior, deswelling and reswelling kinetics of the chiral hydrogels were studied, and the results showed that all the P(NIPAM-co-NALL) hydrogels exhibited evident temperature-sensitivity. Due to the hydrophobicity of NALL incorporated into the structure of the chiral gels, the thermo-sensitivity of the chiral gels was lower than that of PNIPAM gel. The chiral selective adsorption and chiral recognition performance were also investigated by D, L-phenylalanine(D, L-Phe) as model drugs. The results indicated that compared with PNIPAM gel, the chiral gels performed higher adsorption rate and larger adsorption quantities for D-Phe enantiomers. Increasing the contents of chiral monomer or the controlling temperature would improve the chiral recognizable capacity and efficiency of resolution. Furthermore, P(NIPAM-co-NALL) hydrogels could be reused, which remained the chiral recognition property after three-times reuse although the absorption capacity decreased to 27.6% of the original.

Key words: Thermo-sensitive hydrogel, N-Isopropylacrylamide, L-Leucine, Chiral recognization

CLC Number:

O632
O647

TrendMD:

CHEN Jiaojiao, HOU Lintong, JIANG Yi, ZHANG Xia. Preparation and Recognization Property of Chiral Thermo-sensitive P(NIPAM-co-NALL) Hydrogels^†[J]. Chem. J. Chinese Universities, 2014, 35(3): 645.

Figures/Tables 12

Scheme 1 Synthetic routes of P(NIPAM-co-NALL) hydrogels

Table 1 Feed composition of P(NIPAM-co-NALL) hydrogels

r	m(NIPAM)/mg	m(NALL)/mg	m(MBAA)/mg	m(AIBN)/mg
0	339.5	0	23.1	5
0.05	326.7	16.3	23.1	5
0.1	314.9	31.5	23.1	5

Fig.1 FTIR spectra of PNIPAM and P(NIPAM-co-NALL) hydrogels with various NALL contents r: a. 0; b. 0.05; c. 0.1.

Fig.2 Relationship between SR and temperature(A) and DSC curves(B) of PNIPAM and P(NIPAM-co-NALL) hydrogels r: a. 0; b. 0.05; c. 0.1.

Fig.3 Deswelling kinetics of PNIPAM and P(NIPAM- co-NALL) hydrogels at 45 ℃ r: a. 0; b. 0.05; c. 0.1.

Fig.4 Reswelling kinetics of PNIPAM and P(NIPAM- co-NALL) hydrogels at 25 ℃ r: a. 0; b. 0.05; c. 0.1.

Fig.5 Equilibrium absorption capacity of PNIPAM and P(NIPAM-co-NALL) hydrogels(r=0.1) at 40 ℃

Fig.6 Absorption kinetics of P(NIPAM-co-NALL) hydrogels(r=0.1) at 25 ℃(a) and 40 ℃(b)

Fig.7 Variation of absorption kinetics of PNIPAM and P(NIPAM-co-NALL) hydrogels with various NALL contents at 40 ℃ r: a. 0; b. 0.05; c. 0.1.

Fig.8 Equilibrium absorption capacity of P(NIPAM-co-NALL) hydrogels(r=0.1) at 40 ℃ in multiple absorption-release test

Fig.9 Optical rotation([α]) with adsorbing time of PNIPAM and P(NIPAM-co-NALL) hydrogelsInitial total concentration of rac-phenlyalanine solution, 50 mmol/L. r: a. 0; b. 0.05; c. 0.1.

Fig.10 Optical rotation([α]) with adsorbing time of P(NIPAM-co-NALL) hydrogels(r=0.1) at 25 ℃(a) and 40 ℃(b)

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