Shirman, Tanya

Phillips KR, Shirman T, Shirman E, Shneidman AV, Kay TM, Aizenberg J. Nanocrystalline Precursors for the Co-Assembly of Crack-Free Metal Oxide Inverse Opals. Adv. Mater. [Internet]. 2018;30 :1706329. Publisher's VersionAbstract

Inorganic microstructured materials are ubiquitous in nature. However, their formation in artificial self-assembly systems is challenging as it involves a complex interplay of competing forces during and after assembly. For example, colloidal assembly requires fine-tuning of factors such as the size and surface charge of the particles and electrolyte strength of the solvent to enable successful self-assembly and minimize crack formation. Co-assembly of templating colloidal particles together with a sol–gel matrix precursor material helps to release stresses that accumulate during drying and solidification, as previously shown for the formation of high-quality inverse opal (IO) films out of amorphous silica. Expanding this methodology to crystalline materials would result in microscale architectures with enhanced photonic, electronic, and catalytic properties. This work describes tailoring the crystallinity of metal oxide precursors that enable the formation of highly ordered, large-area (mm2) crack-free titania, zirconia, and alumina IO films. The same bioinspired approach can be applied to other crystalline materials as well as structures beyond IOs.

Shirman T, Lattimer J, Luneau M, Shirman E, Reece C, Aizenberg M, Madix RJ, Aizenberg J, Friend CM. New Architectures for Designed Catalysts: Selective Oxidation using AgAu Nanoparticles on Colloid-Templated Silica. Chem. Eur. J. [Internet]. 2018;24 :1833 –1837 . Publisher's VersionAbstract

A highly modular synthesis of designed catalysts with controlled bimetallic nanoparticle size and composition and a well-defined structural hierarchy is demonstrated. Exemplary catalysts—bimetallic dilute Ag-in-Au nanoparticles partially embedded in a porous SiO2 matrix (SiO2–AgxAuy)— were synthesized by the decoration of polymeric colloids with the bimetallic nanoparticles followed by assembly into a colloidal crystal backfilled with the matrix precursor and subsequent removal of the polymeric template. This work reports that these new catalyst architectures are significantly better than nanoporous dilute AgAu alloy catalysts (nanoporous Ag3Au97) while retaining a clear predictive relationship between their surface reactivity with that of single-crystal Au surfaces. This paves the way for broadening the range of new catalyst architectures required for translating the designed principles developed under controlled conditions to designed catalysts under operating conditions for highly selective coupling of alcohols to form esters. Excellent catalytic performance of the porous SiO2–AgxAuy structure for selective oxidation of both methanol and ethanol to produce esters with high conversion efficiency, selectivity, and stability was demonstrated, illustrating the ability to translate design principles developed for support-free materials to the colloid-templated structures. The synthetic methodology reported is customizable for the design of a wide range of robust catalytic systems inspired by design principles derived from model studies. Fine control over the composition, morphology, size, distribution, and availability of the supported nanoparticles was demonstrated.

Shirman E, Shirman T, Shneidman AV, Grinthal A, Phillips KR, Whelan H, Bulger E, Abramovitch M, Patil J, Nevarez R, et al. Modular Design of Advanced Catalytic Materials Using Hybrid Organic–Inorganic Raspberry Particles. Adv. Func. Mater. [Internet]. 2017 :1704559. Publisher's VersionAbstract

Catalysis is one of the most sophisticated areas of materials research that encompasses a diverse set of materials and phenomena occurring on multiple length and time scales. Designing catalysts that can be broadly applied toward global energy and environmental challenges requires the development of universal frameworks for complex catalytic systems through rational and independent (or quasi-independent) optimization of multiple structural and compositional features. Toward addressing this goal, a modular platform is presented in which sacrificial organic colloids bearing catalytic nanoparticles on their surfaces self-assemble with matrix precursors, simultaneously structuring the resulting porous networks and fine-tuning the locations of catalyst particles. This strategy allows combinatorial variations of the material building blocks and their organization, in turn providing numerous degrees of freedom for optimizing the material’s functional properties, from the nanoscale to the macroscale. The platform enables systematic studies and rational design of efficient and robust systems for a wide range of catalytic and photocatalytic reactions, as well as their integration into industrial and other real-life environments.

Sutton A, Shirman T, Timonen JVI, England GT, Kim P, Kolle M, Ferrante T, Zarzar LD, Strong E, Aizenberg J. Photothermally triggered actuation of hybrid materials as a new platform for in vitro cell manipulation. Nat. Commun. [Internet]. 2017;8 :14700. Full TextAbstract

Mechanical forces in the cell’s natural environment have a crucial impact on growth,
differentiation and behaviour. 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.

Phillips KR, England GT, Sunny S, Shirman E, Shirman T, Vogel N, Aizenberg J. A colloidoscope of colloid-based porous materials and their uses. Chem. Soc. Rev. [Internet]. 2016;45 (2) :281-322. Full TextAbstract
Nature evolved a variety of hierarchical structures that produce sophisticated functions. Inspired by these natural materials, colloidal self-assembly provides a convenient way to produce structures from simple building blocks with a variety of complex functions beyond those found in nature. In particular, colloid-based porous materials (CBPM) can be made from a wide variety of materials. The internal structure of CBPM also has several key attributes, namely porosity on a sub-micrometer length scale, interconnectivity of these pores, and a controllable degree of order. The combination of structure and composition allow CBPM to attain properties important for modern applications such as photonic inks, colorimetric sensors, self-cleaning surfaces, water purification systems, or batteries. This review summarizes recent developments in the field of CBPM, including principles for their design, fabrication, and applications, with a particular focus on structural features and materials' properties that enable these applications. We begin with a short introduction to the wide variety of patterns that can be generated by colloidal self-assembly and templating processes. We then discuss different applications of such structures, focusing on optics, wetting, sensing, catalysis, and electrodes. Different fields of applications require different properties, yet the modularity of the assembly process of CBPM provides a high degree of tunability and tailorability in composition and structure. We examine the significance of properties such as structure, composition, and degree of order on the materials' functions and use, as well as trends in and future directions for the development of CBPM.
Vogel N, Utech S, England GT, Shirman T, Phillips KR, Koay N, Burgess IB, Kolle M, Weitz DA, Aizenberg J. Color from hierarchy: Diverse optical properties of micron-sized spherical colloidal assemblies. Proc. Nat. Acad. Sci. [Internet]. 2015;112 (35) :10845-10850. Publisher's VersionAbstract
Materials in nature are characterized by structural order over multiple length scales have evolved for maximum performance and multifunctionality, and are often produced by self-assembly processes. A striking example of this design principle is structural coloration, where interference, diffraction, and absorption effects result in vivid colors. Mimicking this emergence of complex effects from simple building blocks is a key challenge for man-made materials. Here, we show that a simple confined self-assembly process leads to a complex hierarchical geometry that displays a variety of optical effects. Colloidal crystallization in an emulsion droplet creates micron-sized superstructures, termed photonic balls. The curvature imposed by the emulsion droplet leads to frustrated crystallization. We observe spherical colloidal crystals with ordered, crystalline layers and a disordered core. This geometry produces multiple optical effects. The ordered layers give rise to structural color from Bragg diffraction with limited angular dependence and unusual transmission due to the curved nature of the individual crystals. The disordered core contributes nonresonant scattering that induces a macroscopically whitish appearance, which we mitigate by incorporating absorbing gold nanoparticles that suppress scattering and macroscopically purify the color. With increasing size of the constituent colloidal particles, grating diffraction effects dominate, which result from order along the crystal’s curved surface and induce a vivid polychromatic appearance. The control of multiple optical effects induced by the hierarchical morphology in photonic balls paves the way to use them as building blocks for complex optical assemblies—potentially as more efficient mimics of structural color as it occurs in nature.
Koay N, Burgess I, Kay T, Nerger B, Miles-Rossouw M, Shirman T, Vu T, England G, Phillips K, Utech S, et al. Hierarchical structural control of visual properties in self-assembled photonic-plasmonic pigments. Opt. Express [Internet]. 2014;22 (23) :27750-27768. Publisher's VersionAbstract

We present a simple one-pot co-assembly method for the synthesis of hierarchically structured pigment particles consisting of silica inverse-opal bricks that are doped with plasmonic absorbers. We study the interplay between the plasmonic and photonic resonances and their effect on the visual appearance of macroscopic collections of photonic bricks that are distributed in randomized orientations. Manipulating the pore geometry tunes the wavelength- and angle-dependence of the scattering profile, which can be engineered to produce angle-dependent Bragg resonances that can either enhance or contrast with the color produced by the plasmonic absorber. By controlling the overall dimensions of the photonic bricks and their aspect ratios, their preferential alignment can either be encouraged or suppressed. This causes the Bragg resonance to appear either as uniform color travel in the former case or as sparse iridescent sparkle in the latter case. By manipulating the surface chemistry of these photonic bricks, which introduces a fourth length-scale (molecular) of independent tuning into our design, we can further engineer interactions between liquids and the pores. This allows the structural color to be maintained in oil-based formulations, and enables the creation of dynamic liquid-responsive images from the pigment.