Perro, A. ; Manoharan, V. N. Bulk Synthesis of Polymer-Inorganic Colloidal Clusters . Langmuir 2010, 26, 18669-18675. Publisher's VersionAbstract

We describe a procedure to synthesize colloidal clusters with polyhedral morphologies in high yield (liter quantities at up to 70% purity) using a combination of emulsion polymerization and inorganic surface chemistry. We show that the synthesis initially used for silica-polystyrene hybrid clusters can be generalized to create clusters from other inorganic and polymer particles. We also show that high yields of particular morphologies can be obtained by precise control of the inorganic seed particle size, a finding that can be explained using a hard-sphere packing model. These clusters can be further chemically modified for a variety of applications. Introducing a cross-linker leads to colloidal clusters that can be index matched in an appropriate solvent, allowing them to be used for particle tracking or optical studies of colloidal self-assembly. Also, depositing a thin silica layer on these colloids allows the surface properties to be controlled using silane chemistry.

McGorty, R. ; Fung, J. ; Kaz, D. ; Manoharan, V. N. Colloidal self-assembly at an interface. Materials Today 2010, 13, 34-42. Publisher's VersionAbstract

Mix a drop of water into a vial of oil. With some surfactant and a vigorous shake, that one droplet has become thousands, and the total interfacial area has increased by an order of magnitude or more. Like the folded membranes in our mitochondria, the alveoli in our lungs, and the catalytic converters in our cars, oil-water emulsions contain a vast reservoir of interfacial area that can be used to control and transform the things that encounter it. The oil-water interface is especially well-suited to directing the assembly of colloidal particles, which bind to it rapidly and often irreversibly.

Fan, J. A. ; Bao, K. ; Wu, C. ; Bao, J. ; Bardhan, R. ; Halas, N. J. ; Manoharan, V. N. ; Shvets, G. ; Nordlander, P. ; Capasso, F. Fano-like Interference in Self-Assembled Plasmonic Quadrumer Clusters . Nano Letters 2010, 10, 4680-4685. Publisher's VersionAbstract

Assemblies of strongly interacting metallic nanoparticles are the basis for plasmonic nanostructure engineering. We demonstrate that clusters of four identical spherical particles self-assembled into a close-packed asymmetric quadrumer support strong Fano-like interference. This feature is highly sensitive to the polarization of the incident electric field due to orientation-dependent coupling between particles in the cluster. This structure demonstrates how careful design of self-assembled colloidal systems can lead to the creation of new plasmonic modes and the enabling of interference effects in plasmonic systems.

Fan, J. A. ; Wu, C. ; Bao, K. ; Bao, J. ; Bardhan, R. ; Halas, N. J. ; Manoharan, V. N. ; Nordlander, P. ; Shvets, G. ; Capasso, F. Self-Assembled Plasmonic Nanoparticle Clusters. Science 2010, 328, 1135-1138. Publisher's VersionAbstract

The self-assembly of colloids is an alternative to top-down processing that enables the fabrication of nanostructures. We show that self-assembled clusters of metal-dielectric spheres are the basis for nanophotonic structures. By tailoring the number and position of spheres in close-packed clusters, plasmon modes exhibiting strong magnetic and Fano-like resonances emerge. The use of identical spheres simplifies cluster assembly and facilitates the fabrication of highly symmetric structures. Dielectric spacers are used to tailor the interparticle spacing in these clusters to be approximately 2 nanometers. These types of chemically synthesized nanoparticle clusters can be generalized to other two- and three-dimensional structures and can serve as building blocks for new metamaterials.

Dimiduk, T. G. ; Kosheleva, E. A. ; Kaz, D. ; McGorty, R. ; Gardel, E. J. ; Manoharan, V. N. A Simple, Inexpensive Holographic Microscope. In Digital Holography and Three-Dimensional Imaging 2010 (OSA Topical Meeting); Optical Society of America: Miami, FL, 2010; pp. Paper JMA38. Publisher's VersionAbstract

We have built a simple holographic microscope completely out of consumer components. We obtain at least 2.8 μm resolution and depth of field greater than 200 μm from an instrument costing less than $1000.

Manoharan, V. N. Digital Holographic Microscopy for 3D Imaging of Complex Fluids and Biological Systems. Frontiers of Engineering: Reports on Leading-edge Engineering from the 2009 Symposium, 2010, 5-12. Full Text
Meng, G. ; Arkus, N. ; Brenner, M. P. ; Manoharan, V. N. The Free-Energy Landscape of Clusters of Attractive Hard Spheres. Science 2010, 327, 560-563. Publisher's VersionAbstract

The study of clusters has provided a tangible link between local geometry and bulk condensed matter, but experiments have not yet systematically explored the thermodynamics of the smallest clusters. Here we present experimental measurements of the structures and free energies of colloidal clusters in which the particles act as hard spheres with short-range attractions. We found that highly symmetric clusters are strongly suppressed by rotational entropy, whereas the most stable clusters have anharmonic vibrational modes or extra bonds. Many of these clusters are subsets of close-packed lattices. As the number of particles increases from 6 to 10, we observe the emergence of a complex free-energy landscape with a small number of ground states and many local minima.

Perro, A. ; Meng, G. ; Fung, J. ; Manoharan, V. N. Design and Synthesis of Model Transparent Aqueous Colloids with Optimal Scattering Properties. Langmuir 2009, 25, 11295-11298. Publisher's VersionAbstract

We demonstrate the synthesis and self-assembly of colloidal particles with independently controlled diameter and scattering cross section. We show that it is possible to prepare bulk colloidal suspensions that are nearly transparent in water, while the particles themselves can be individually resolved using optical microscopy. These particles may be ideal model colloids for real-space studies of self-assembly in aqueous media. Moreover, they illustrate the degree to which the optical properties of colloids can be engineered through straightforward chemistry.

Arkus, N. ; Manoharan, V. N. ; Brenner, M. P. Minimal Energy Clusters of Hard Spheres with Short Range Attractions. Physical Review Letters 2009, 103, 118303-4. Publisher's VersionAbstract

We calculate the ground states of hard-sphere clusters, in which n identical hard spherical particles bind by isotropic short-ranged attraction. Combining graph theoretic enumeration with basic geometry, we analytically solve for clusters of n<=10 particles satisfying minimal rigidity constraints. For n<=9 the ground state degeneracy increases exponentially with n, but for n>9 the degeneracy decreases due to the formation of structures with >3n-6 contacts. Interestingly, for n=10 and possibly at n=11 and n=12, the ground states of this system are subsets of hexagonal close-packed crystals. The ground states are not icosahedra at n=12 and n=13. We relate our results to the structure and thermodynamics of suspensions of colloidal particles with short-ranged attractions.

Arkus et al. - 2009 - Minimal Energy Clusters of Hard Spheres.pdf
Ali, N. ; Manoharan, V. N. RNA folding and hydrolysis terms explain ATP-independence of RNA interference in human systems. Oligonucleotides 2009, 19, 341-346. Publisher's VersionAbstract

Although RNA interference (RNAi) has emerged as an important tool for studying the effects of gene knockdown, it is still difficult to predict the success of RNAi effectors in human systems. By examining the basic thermodynamic equations for RNA interactions in RNAi, we demonstrate how the free energies of RNA folding and phosphoester bond hydrolysis can drive RNAi without ATP. Our calculations of RNAi efficiency are close to actual values obtained from in vitro experimental data from 2 previous studies, for both silencing complex formation (2.50 vs. 2.40 for relative efficiency of RISC formation) and mRNA cleavage (0.50 vs. 0.56 for proportion cleaved). Our calculations are also in agreement with previous observations that duplex unwinding and target site folding are major energy barriers to RNAi.

Ali and Manoharan - 2009 - RNA folding and hydrolysis terms explain ATP-independence.pdf
Perro, A. ; Duguet, E. ; Ravaine, S. ; Manoharan, V. N. Self-Assembly of Polyhedral Hybrid Colloidal Particles. MRS Proceedings, 2009, 1135, 1135-CC06-08. Publisher's VersionAbstract

We have developed a new method to produce hybrid particles with polyhedral shapes in very high yield (liter quantities at up to 70% purity) using a combination of emulsion polymerization and inorganic surface chemistry. The procedure has been generalized to create complex geometries, including hybrid line segments, triangles, tetrahedra, octahedra, and more. The optical properties of these particles are tailored for studying their dynamics and self-assembly. For example, we produce systems that consist of index-matched spheres allowing us to define the position of each elementary particle in three-dimensional space. We present some preliminary studies on the self-assembly of these complex shaped systems based on electron and optical microscopy.

Perro et al. - 2009 - Self-Assembly of Polyhedral Hybrid Colloidal Particles.pdf
McGorty, R. ; Fung, J. ; Kaz, D. ; Ahn, S. ; Manoharan, V. N. Measuring Dynamics and Interactions of Colloidal Particles with Digital Holographic Microscopy. In Digital Holography and Three-Dimensional Imaging Proceedings; Optical Society of America Technical Digest (CD): St. Petersburg, Florida, 2008; Vol. paper DTuB1. Publisher's VersionAbstract

Micrometer-sized colloidal particles are a model system for understanding self-assembly in condensed matter. Here I present the results of digital holographic microscopy experiments that probe the 3D structure and dynamics of these systems.

McGorty et al. - 2008 - Measuring Dynamics and Interactions of Colloidal P.pdf
Yu, H. K. ; Yi, G. - R. ; Kang, J. - H. ; Cho, Y. - S. ; Manoharan, V. N. ; Pine, D. J. ; Yang, S. - M. Surfactant-Assisted Synthesis of Uniform Titania Microspheres and Their Clusters. Chemistry of Materials 2008, 20, 2704-2710. Publisher's VersionAbstract

In this study, we demonstrate the surfactant-assisted synthesis of uniform-sized titania microspheres and their clusters for highly responsive optical materials. Monodisperse titanium glycolate microspheres were produced by controlled hydrolysis of glycolated titanium butoxide in acetone using surfactant as a stabilizer. The diameter of as-prepared particles ranged from 230 to 650 nm and was finely controlled by changing the concentrations of titanium butoxide and surfactant. In particular, the tunable range of the particle size was at a few tens of nanometers scale by the surfactant concentration, which was much finer than that by the concentration of titanium butoxide. Then, as-prepared titanium glycolate microspheres were transformed into monodisperse titania microspheres of anatase phase by heat treatment. Pure clusters of titania microspheres with an identical configuration were obtained by encapsulating a certain number of microspheres in emulsion droplets and subsequently evaporating the emulsion phase to induce self-assembly. Dynamic and static light scattering experiments show that the pure clusters with an identical configuration were well dispersed, and the refractive index of anatase phase titania microspheres was about 2.2. In addition, monodisperse Eu-doped titanium glycolate microspheres were prepared for phosphorescence sources by adding both a soluble precursor Eu(NO3)3-5H2O and glycolated titanium butoxide in acetone. Finally, photoluminescence properties of Eu-doped titania microspheres were examined after annealing.

Manoharan, V. N. Colloidal spheres confined by liquid droplets: Geometry, physics, and physical chemistry. Solid State Communications 2006, 139, 557-561. Publisher's VersionAbstract

I discuss how colloidal particles organize when they are confined by emulsion droplets. In these systems, the interplay between surface tension and interparticle repulsion drives the formation of complex, non-crystalline 3D arrangements. These can be classified into three groups: colloidosomes, or Pickering emulsions, structures that form when particles are bound to the interface of a spherical droplet; colloidal clusters, small polyhedral configurations of colloids formed by capillary forces generated in an evaporating emulsion droplet; and supraparticles, hall-shaped crystallites formed in the interior of emulsion droplets. I discuss the preparation, properties, and structure of each of these systems, using relevant results from geometry to describe how the particles organize.

Manoharan - 2006 - Colloidal spheres confined by liquid droplets.pdf
Cho, Y. - S. ; Yi, G. - R. ; Lim, J. - M. ; Kim, S. - H. ; Manoharan, V. N. ; Pine, D. J. ; Yang, S. - M. Self-organization of bidisperse colloids in water droplets. Journal of the American Chemical Society 2005, 127, 15968-15975. Publisher's VersionAbstract

Most of the colloidal clusters have been produced from oil-in-water emulsions with identical microspheres dispersed in oil droplets. Here, we present new types of binary colloidal clusters from phase-inverted water-in-oil emulsions using various combinations of two different colloids with several size ratios: monodisperse silica or polystyrene microspheres for larger particles and silica or titania nanoparticles for smaller particles. Obviously, a better understanding of how finite groups of different colloids self-organize in a confined geometry may help us control the structure of matter at multiple length scales. In addition, since aqueous dispersions have much better phase stability, we could produce much more diverse colloidal materials from water-in-oil emulsions rather than from oil-in-water emulsions. Interestingly, the configurations of the large microspheres were not changed by the presence of the small particles. However, the arrangement of the smaller particles was strongly dependent on the nature of the interparticle interactions. The experimentally observed structural evolutions were consistent with the numerical simulations calculated using Surface Evolver. These clusters with nonisotropic structures can be used as building blocks for novel colloidal structures with unusual properties or by themselves as light scatterers, diffusers, and complex adaptive matter exhibiting emergent behavior.