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基于剪切诱导导电胶束网络的电响应水凝胶用于按需药物释放的流变小角X射线散射研究

Rheo-SAXS study on electrically responsive hydro-gels with shear-induced conductive micellar networks for on-demand drug release.

作者信息

Vo Thuy Thien Ngan, Chang Yi-Wei, Su Chun-Jen, Jeng U-Ser, Cheng Chih-Chia, Sun Ya-Sen, Chuang Wei-Tsung

机构信息

Graduate Institute of Applied Science and Technology National Taiwan University of Science and Technology Taipei106335 Taiwan.

Department of Chemical and Materials Engineering National Central University Taoyuan32001 Taiwan.

出版信息

J Appl Crystallogr. 2025 Apr 25;58(Pt 3):909-918. doi: 10.1107/S1600576725002808. eCollection 2025 Jun 1.

Abstract

This study presents a novel approach to creating electrically responsive hydro-gels utilizing a poly(ethyl-ene oxide)-poly(propyl-ene oxide)-poly(ethyl-ene oxide) (PEO-PPO-PEO) triblock copolymer, functionalized with benzene-sulfonate end groups to form sF127. This functionalization allows the incorporation of sF127 into F127 micelles, resulting in tailored micelles designated as FSP when combined with poly(3,4-ethyl-ene-dioxy-thio-phene):poly(benzene-sulfonate) (PEDOT:PSS). For comparison, a control system using non-functionalized PEDOT:PSS/F127 micelles, designated FSP, was also developed. Using piroxicam as a model hydro-phobic drug, we evaluated the hydro-gel's drug encapsulation efficiency and electrical responsiveness. The functionalized FSP hydro-gel demonstrated superior performance of electrically stimulated drug release, especially when prepared with a blade-coating process. rheological small-angle X-ray scattering (rheo-SAXS) measurements under large amplitude oscillatory shear revealed that function-alization facilitates crystal plane sliding, leading to the formation of a randomly hexagonal close-packed (rHCP) sliding layer structure. This behavior contrasts with the face-centered cubic to rHCP phase transition observed in the unfunctionalized hydro-gel. SAXS analysis under applied electric fields (E-SAXS) further confirmed the electroresponsive micellar deformation. By integrating the rheo-SAXS and E-SAXS findings with blade-coating processing insights, we identify a clear structure-function relationship that governs the performance of these hydro-gels. The enhanced drug delivery of the function-al-ized FSP hydro-gel is attributed to the electrostatic attraction between the positively charged PEDOT and the negatively charged benzene-sulfonate-functionalized micelles. This interaction creates conductive nanonetworks within the hydro-gel, significantly improving its ability to release drugs in response to electrical stimulation. This work highlights the potential of electrically responsive hydro-gels for precise, localized drug delivery applications.

摘要

本研究提出了一种利用聚(环氧乙烷)-聚(环氧丙烷)-聚(环氧乙烷)(PEO-PPO-PEO)三嵌段共聚物制备电响应水凝胶的新方法,该共聚物用苯磺酸盐端基官能化形成sF127。这种官能化使得sF127能够掺入F127胶束中,当与聚(3,4-乙撑二氧噻吩):聚(苯磺酸盐)(PEDOT:PSS)结合时,形成定制的胶束,称为FSP。为了进行比较,还开发了一种使用未官能化的PEDOT:PSS/F127胶束的对照体系,称为FSP。使用吡罗昔康作为模型疏水药物,我们评估了水凝胶的药物包封效率和电响应性。官能化的FSP水凝胶在电刺激药物释放方面表现出优异的性能,特别是采用刮涂工艺制备时。在大振幅振荡剪切下的流变小角X射线散射(rheo-SAXS)测量表明,官能化促进了晶面滑动,导致形成随机六方密堆积(rHCP)滑动层结构。这种行为与未官能化水凝胶中观察到的面心立方到rHCP的相变形成对比。施加电场下的SAXS分析(E-SAXS)进一步证实了电响应性胶束变形。通过将rheo-SAXS和E-SAXS的结果与刮涂工艺的见解相结合,我们确定了一种明确的结构-功能关系,该关系决定了这些水凝胶的性能。官能化的FSP水凝胶增强的药物递送归因于带正电的PEDOT与带负电的苯磺酸盐官能化胶束之间的静电吸引。这种相互作用在水凝胶内形成导电纳米网络,显著提高了其在电刺激下释放药物的能力。这项工作突出了电响应水凝胶在精确、局部药物递送应用中的潜力。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e469/12135972/cf86d3f48f05/j-58-00909-fig1.jpg

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