Person:

Zarzar, Lauren

Arrays of high-aspect-ratio (HAR) nano- and microstructures are of great interest for designing surfaces for applications in optics, bio−nano interfaces, microelectromechanical systems, and microfluidics, but the difficulty of systematically and conveniently varying the geometries of these structures significantly limits their design and optimization for a specific function. This paper demonstrates a low-cost, high-throughput benchtop method that enables a HAR array to be reshaped with nanoscale precision by electrodeposition of conductive polymers. The method—named STEPS (structural transformation by electrodeposition on patterned substrates)—makes it possible to create patterns with proportionally increasing size of original features, to convert isolated HAR features into a closed-cell substrate with a continuous HAR wall, and to transform a simple parent two-dimensional HAR array into new three-dimensional patterned structures with tapered, tilted, anisotropic, or overhanging geometries by controlling the deposition conditions. We demonstrate the fabrication of substrates with continuous or discrete gradients of nanostructure features, as well as libraries of various patterns, starting from a single master structure. By providing exemplary applications in plasmonics, bacterial patterning, and formation of mechanically reinforced structures, we show that STEPS enables a wide range of studies of the effect of substrate topography on surface properties leading to optimization of the structures for a specific application. This research identifies solution-based deposition of conductive polymers as a new tool in nanofabrication and allows access to 3D architectures that were previously difficult to fabricate.

Dynamic materials which can sense changes in their surroundings and subsequently respond or adapt by autonomously altering their functionality, surface chemistry, transparency, color, wetting behavior, adhesiveness, shape, etc. are primed to be integral components of future "smart" technologies. However, such systems can be quite complex and often require intricate coordination between both chemical and mechanical inputs/outputs as well as the combination of multiple materials working cooperatively to achieve the proper functionality. It is critical to not only understand the fundamental behaviors of existing dynamic chemo-mechanical systems, but also to apply that knowledge and explore new avenues for design of novel materials platforms which could provide a basis for future adaptive technologies. Part 1 explores the use of environmentally-sensitive hydrogels, either alone or within arrays of high-aspect-ratio nano/microstructures, as chemo-mechanical actuators. Chapters 1 through 7 describe a bio-inspired approach to the design of hybrid actuating surfaces in which the volume-changing hydrogel acts as the “muscle” that reversibly actuates the microstructured "bone". In particular, the different actuation mechanisms arising from variations in how the hydrogel is integrated into the structure array, how chemical signals can be used to manipulate actuation parameters, and finally how such a system may be used for applications ranging from adaptive optics to manipulation of chemical reactions are described. Chapter 8 discusses the use of responsive hydrogel scaffolds as a means to mechanically compress cells and direct differentiation. Part II explores dynamic microsystems involving the integration of catalytic sites within intricately structured 3D microenvironments. Specifically, we explore a generalizable and straightforward route to fabricate microscale patterns of nanocrystalline platinum and palladium using multiphoton lithography. The catalytic, electrical, and electrochemical properties are characterized, and we demonstrate high resolution integration of catalysts within 3D-defined microenvironments to generate directed particle and fluid transport.

The ability to manipulate the movement of surface microstructures is essential for the development of dynamic, responsive materials. We demonstrate that in addition to bulk actuation upon drying, a unique type of highly localized, directional actuation can be achieved when microstructures embedded in pH responsive gel are exposed to pH gradients. Theory and modelling elucidates the underlying mechanism behind this novel approach to inducing responsive actuation.

Mechanical forces in the cell’s natural environment have a crucial impact on growth, differentiation and behavior. Few areas of biology can be understood without taking into account how both individual cells and cell networks sense and transduce physical stresses. However, the field is currently held back by the limitations of the available methods to apply physiologically relevant stress profiles on cells, particularly with sub-cellular resolution, in controlled in vitro experiments. Here we report a new type of active cell culture material that allows highly localized, directional, and reversible deformation of the cell growth substrate, with control at scales ranging from the entire surface to the subcellular, and response times on the order of seconds. These capabilities are not matched by any other method, and this versatile material has the potential to bridge the performance gap between the existing single cell micro-manipulation and 2D cell sheet mechanical stimulation techniques.

Dynamic materials that can sense changes in their surroundings and functionally respond by altering many of their physical characteristics are primed to be integral components of future “smart” technologies. A fundamental reason for the adaptability of biological organisms is their innate ability to convert environmental or chemical cues into mechanical motion and reconfiguration on both the molecular and macroscale. However, design and engineering of robust chemomechanical behavior in artificial materials has proven a challenge. Such systems can be quite complex and often require intricate coordination between both chemical and mechanical inputs and outputs, as well as the combination of multiple materials working cooperatively to achieve the proper functionality. It is critical to not only understand the fundamental behaviors of existing dynamic chemomechanical systems but also apply that knowledge and explore new avenues for design of novel materials platforms that could provide a basis for future adaptive technologies. In this Account, we explore the chemomechanical behavior, properties, and applications of hybrid-material surfaces consisting of environmentally sensitive hydrogels integrated within arrays of high-aspect-ratio nano- or microstructures. This bio-inspired approach, in which the volume-changing hydrogel acts as the “muscle” that reversibly actuates the microstructured “bones”, is highly tunable and customizable. Although straightforward in concept, the combination of just these two materials (structures and hydrogel) has given rise to a far more complex set of actuation mechanisms and behaviors. Variations in how the hydrogel is physically integrated within the structure array provide the basis for three fundamental mechanisms of actuation, each with its own set of responsive properties and chemomechanical behavior. Further control over how the chemical stimulus is applied to the surface, such as with microfluidics, allows for generation of more precise and varied patterns of actuation. We also discuss the possible applications of these hybrid surfaces for chemomechanical manipulation of reactions, including the generation of chemomechanical feedback loops. Comparing and contrasting these many approaches and techniques, we aim to put into perspective their highly tunable and diverse capabilities but also their future challenges and impacts.