CAREER: Photodirected Assembly of Custom-Designed Polyelectrolyte Complexes

Lapitsky，Yakov1150908智力优点：PI提出通过聚电解质的光定向组装来创建刺激响应界面微结构和微器件。 化学产品设计、医药和纳米技术的最新进展已经迎来了一个新的时代。聪明吗？对外部刺激（如pH值、离子强度、温度和机械或电磁扰动的变化）作出反应的材料。 刺激响应性微电子复合物通常用作这些材料的构建块，并找到无数的应用，从生物活性有效载荷的控制释放，到自修复材料和软微机电系统（MEMS），到能源设备和水净化。 这些技术需要定制设计的结构，具有各种明确的形态。 然而，用于微制造纳米复合物的方法仍然限于简单的结构基序（例如，平面的、球形的、圆柱形的和棱柱状的或棱柱状的）。这严重限制了可以由聚电解质制备的超分子结构的范围和复杂性，并且在基于聚电解质的微器件的3-D组装中存在主要障碍。为了解决这个问题，PI的目标是通过对聚合物溶液的三维图案化来指导复杂的聚合物结构的组装，其中一种聚合物物种只有在暴露于光时才会带电。 PI假设在多光子激光的焦点处的照射将诱导快速和局部的自组装成胶体材料，其形状和尺寸将由光束路径引导。该项目有三个目标：（1）研究聚电解质的光定向组装作为制备复杂超分子结构的方法，（2）剖析光定向组装过程，以期开发用于控制材料界面结构和刺激敏感性的稳健准则，以及（3）利用微图案化的双金属络合物的刺激响应性质来制备微米级控释装置，致动器和自毁材料。 这项研究利用PI？的背景下，自组装，并将显着扩大范围和复杂性的聚电解质为基础的材料，可以准备定制的控制释放，传感器和执行器technology.Broader影响：这项工作将推进设计和微制造的智能设备的医疗，环境和家庭应用。 同样，生产新型刺激响应结构的能力有可能加速先进膜、涂层、电子和能源设备的发展。 重要的是，这项研究将与教育推广密切结合。 PI将向高中生介绍托莱多公立学校提供的一天工程师和EXCEL课程中的刺激响应聚电解质。 此外，他将继续参与移民学生教师工程（ETMS）远程学习课程。 ETMS为农村社区的教师提供研究生培训，这些教师教农民工的孩子，目的是开发一套实验，证明数学，科学和工程对日常生活的重要性。 PI最近参与了ETMS，并且已经开发了几个使用家用产品中发现的刺激响应聚合物的演示（例如，藻酸盐、聚（丙烯酸）和甲基纤维素）来加强高中化学中所学的概念。 为了更广泛地传播ETMS材料，将在PI？的网站和YouTube上。 这些推广活动将有助于增加理工科学生的入学人数并使其多样化。 此外，PI？该研究将培训本科生和研究生（包括妇女和代表性不足的少数民族）使用材料表征技术，以及胶体和聚合物科学的基础知识。 这项研究还将产生刺激性的例子和项目主题，PI将把它们纳入他将在托莱多大学教授的胶体和传输现象课程中。

Lapitsky, Yakov1150908 Intellectual Merit: The PI proposes to create stimulus-responsive interfacial microstructures and microdevices through the photodirected assembly of polyelectrolytes. Recent advances in chemical product design, medicine and nanotechnology have ushered in a new age of ?smart? materials that respond to external stimuli such as changes in pH, ionic strength, temperature, and mechanical or electromagnetic perturbations. Stimulus-responsive polyelectrolyte complexes are routinely used as building blocks for these materials and find countless applications, ranging from controlled release of bioactive payloads, to self-healing materials and soft microelectromechanical systems (MEMS), to energy devices and water purification. These technologies require custom-designed structures with an assortment of well-defined morphologies. Yet, methods for the microfabrication of polyelectrolyte complexes remain limited to simplistic structural motifs (e.g., planar, spherical, cylindrical, and prism-like or pyramid-like). This severely limits both the range and intricacy of the supramolecular architectures that can be prepared from polyelectrolytes, and presents a major obstacle in the 3-D assembly of polyelectrolyte-based microdevices. To address this, the PI aims to direct the assembly of intricate polyelectrolyte structures via 3-D photopatterning of polyelectrolyte solutions, where one of the polymer species only becomes charged when exposed to light. The PI hypothesizes that the irradiation at the focal point of the multiphoton laser will induce rapid and localized polyelectrolyte self-assembly into colloidal materials, whose shapes and dimensions will be directed by the beam path. This project has three objectives: (1) investigating photodirected assembly of polyelectrolytes as a method for preparing intricate supramolecular structures, (2) dissecting the photodirected assembly process with the view of developing robust guidelines for controlling materials interfacial structure and stimulus sensitivity, and (3) exploiting the stimulus-responsive properties of photopatterned polyelectrolyte complexes to prepare micron-scale controlled release devices, actuators and materials that self-destruct. This research leverages the PI?s background in polyelectrolyte self-assembly, and will dramatically expand the range and intricacy of polyelectrolyte-based materials that can be prepared for customized controlled release, sensor and actuator technologies.Broader Impacts: This work will advance the design and microfabrication of smart devices for medical, environmental and household applications. Likewise, the ability to produce novel stimulus-responsive structures has the potential to accelerate the development of advanced membranes, coatings, electronics and energy devices. Importantly, this research will be closely integrated with educational outreach. The PI will introduce high school students to stimulus-responsive polyelectrolytes in the Engineer for a Day and EXCEL programs that are offered to Toledo Public Schools. Moreover, he will continue his involvement in the Engineering for Teachers of Migrant Students (ETMS) distance learning course. ETMS provides graduate training for teachers in rural communities who teach children of migrant farm workers, and aims to develop a set of experiments that demonstrate the importance of mathematics, science and engineering to everyday life. The PI has recently become involved with ETMS, and has already developed several demonstrations that use stimulus-responsive polymers found in household products (e.g., alginate, poly(acrylic acid), and methylcellulose) to reinforce concepts that are learned in high school chemistry. To disseminate the ETMS materials more broadly, step-by-step tutorials will be posted on the PI?s website and on YouTube. These outreach activities will help increase and diversify the enrollment of science and engineering students. Furthermore, the PI?s research will train undergraduate and graduate students (including women and underrepresented minorities) in the use of materials characterization techniques, and in the fundamentals of colloid and polymer science. This research will also generate stimulating examples and project topics, which the PI will incorporate into the colloids and transport phenomena courses that he will teach at the University of Toledo.