Immobilization of Methyl Orange and Methylene Blue within the Matrix of Charge-Imbalanced Amphoteric Nanogels and Study of Dye Release Kinetics as a Function of Temperature and Ionic Strength

Aigerim Ayazbayeva, S. Nauryzova, V. Aseyev, A. Shakhvorostov
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Abstract

Cross-linked polyampholyte nanogels consisting of neutral N-isopropylacrylamide (NIPAM), negatively charged sodium salt of 2-acrylamido-2-methylpropanesulfonate (AMPS), and positively charged (3-acryl-amidopropyltrimethylammonium chloride (APTAC) monomers were synthesized via conventional redox ini-tiated free radical copolymerization using N,N-methylenebis(acrylamide) (MBAA) as a crosslinking agent. The resulting nanogels were characterized by means of FTIR and 1H NMR spectroscopy, dynamic light scat-tering (DLS) and zeta-potential measurements. Surface morphology was analyzed using scanning electron microscopy. Due to the presence of thermally responsive NIPAM units and varying molar ratios of anionic (AMPS) and cationic (APTAC) units, the resulting nanogels were responsive to multiple stimuli in aqueous media and can be used for controlled delivery of dyes. Thus, the NIPAM90-APTAC7.5-AMPS2.5 nanogel with an excess of the cationic units was chosen for immobilization of the anionic dye, methyl orange (MO), whereas the NIPAM90-APTAC2.5-AMPS7.5 nanogel with an excess of the anionic units was chosen for immo-bilization of the cationic dye, methylene blue (MB). The release kinetics of the dyes from the nanogel was studied depending on the phase transition temperature and the salt content. Mechanism of the dye release from the nanogel matrix was determined using the Ritger-Peppas equation. Disappearance of the ionic con-tacts between the charged groups of the nanogels and the ionic dyes was suggested to be the main reason for the diffusion of the dyes through the dialysis membrane into external solution.
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甲基橙和亚甲基蓝在电荷不平衡两性纳米凝胶基质内的固定化及染料释放动力学与温度和离子强度的关系研究
以N,N-亚甲基双丙烯酰胺(MBAA)为交联剂,采用常规氧化还原自由基共聚法制备了中性N-异丙基丙烯酰胺(NIPAM)、带负电荷的2-丙烯酰胺-2-甲基丙磺酸钠盐(AMPS)和带正电荷的3-丙烯-酰胺丙基三甲基氯化铵(APTAC)单体的交联聚两性聚合物纳米凝胶。通过FTIR和1H NMR、动态光散射(DLS)和ζ电位测量对所得纳米凝胶进行了表征。用扫描电镜分析表面形貌。由于热响应NIPAM单元的存在以及阴离子(AMPS)和阳离子(APTAC)单元的不同摩尔比,所得到的纳米凝胶对水介质中的多种刺激有响应,可用于染料的控制递送。因此,选择含有过量阳离子单元的NIPAM90-APTAC7.5-AMPS2.5纳米凝胶固定阴离子染料甲基橙(MO),而选择含有过量阴离子单元的NIPAM90-APTAC2.5-AMPS7.5纳米凝胶固定阳离子染料亚甲基蓝(MB)。研究了染料在纳米凝胶中的释放动力学随相变温度和盐含量的变化。利用Ritger-Peppas方程确定了染料从纳米凝胶基质中释放的机理。纳米凝胶中带电基团与离子染料之间离子接触的消失是染料通过透析膜向外溶液扩散的主要原因。
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