目的 为了从分子层面揭示紫外光响应型微胶囊的控释机理,通过分子动力学模拟,系统探讨芯材分子在微胶囊体系中的扩散行为以及控释机理。方法 以4-羟基-7-甲氧基香豆素改性β-环糊精为壁材,对甲氧基苯甲醛为芯材,构建两相模型,从均方位移、扩散系数角度研究不同光照下芯材的扩散行为,从相互作用能、自由体积、运动轨迹角度探索紫外光控释机理。结果 对甲氧基苯甲醛分子在未经过、经过365 nm和经过256 nm紫外光照的微胶囊体系中的最大均方位移分别为1.65×10-1、2.0×10-2、3.5×10-2 nm2;扩散系数分别为6.21×10-8、1.58×10-9、1.09×10-8 cm2/s;相互作用能分别为-1 052.57、-1 114.95、-1 195.37 kJ/mol;自由体积分别为10.81%、10.95%、9.59%;运动轨迹均存在明显的轨迹重叠与团簇现象。结论 光照后对甲氧基苯甲醛的最大均方位移与扩散系数均呈现下降趋势,且365 nm紫外光对体系的影响更显著。分子间相互作用和自由体积的变化规律表明扩散行为是由多种因素共同作用的结果,其扩散方式表现为蠕动扩散。本研究证实分子动力学模拟是揭示光响应控释机理的有效手段,可为光响应控释载体的结构设计提供理论指导。
Abstract
To reveal the controlled-release mechanism of UV-responsive microcapsules at the molecular level, the work aims to systematically investigate the diffusion behavior and controlled-release mechanism of core material molecules within the microcapsule system through molecular dynamics simulation. With 4-hydroxy-7-methoxycoumarin-modified β-cyclodextrin (4H7MC-ECH-g-β-CD) as the shell material, and p-methoxybenzaldehyde as the core material, a two-phase model was established. The diffusion behavior of core materials under different light irradiation conditions was studied from the perspectives of mean square displacement and diffusion coefficient, and the UV-triggered controlled-release mechanism was explored based on interaction energy, free volume and molecular trajectories. The maximum mean square displacement of p-methoxybenzaldehyde in the microcapsule systems without ultraviolet light exposure and after 365 nm and 256 nm ultraviolet light exposure was 1.65×10-1, 2.0×10-2 and 3.5×10-2 nm2, respectively. The diffusion coefficient was 6.21×10-8, 1.58×10-9 and 1.09×10-8 cm2/s respectively. The interaction energy was -1 052.57, -1 114.95 and -1 195.37 kJ/mol, respectively. The free volume was 10.81%, 10.95% and 9.59%, respectively. Obvious trajectory overlap and clustering phenomena existed in all motion trajectories. After light exposure, the maximum mean square displacement and diffusion coefficient of p-methoxybenzaldehyde both have a downward trend, and the effect of 365 nm ultraviolet light on the system is more significant. The variation laws of intermolecular interaction and free volume are inconsistent with the above parameters, indicating that the diffusion behavior is the result of the combined action of multiple factors, and its diffusion mode is manifested as peristaltic diffusion. This work confirms that molecular dynamics simulation is an effective means to reveal the mechanism of light-responsive controlled-release and can provide theoretical guidance for the structural design of light-responsive controlled-release carriers.
关键词
对甲氧基苯甲醛 /
紫外光响应控释微胶囊 /
扩散机理 /
分子动力学模拟
Key words
p-methoxybenzaldehyde /
UV-responsive controlled-release microcapsules /
diffusion mechanism /
molecular dynamics simulation
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基金
“十三五”国家重点研发计划项目（2016YFD0400700）;江南大学博士后基金
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