Vo Thuy Thien Ngan, Chang Yi-Wei, Su Chun-Jen, Jeng U-Ser, Cheng Chih-Chia, Sun Ya-Sen, Chuang Wei-Tsung
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.
J Appl Crystallogr. 2025 Apr 25;58(Pt 3):909-918. doi: 10.1107/S1600576725002808. eCollection 2025 Jun 1.
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.
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。
