Publications

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This is the final report for the Presidential Early Career Award for Science and Engineering - PECASE (LDRD projects 93369 and 118841) awarded to Professor Yunfeng Lu (Tulane University and University of California-Los Angeles). During the last decade, mesoporous materials with tunable periodic pores have been synthesized using surfactant liquid crystalline as templates, opening a new avenue for a wide spectrum of applications. However, the applications are somewhat limited by the unfavorabe pore orientation of these materials. Although substantial effort has been devoted to align the pore channels, fabrication of mesoporous materials with perpendicular pore channels remains challenging. This project focused on fabrication of mesoporous materials with perpendicularly aligned pore channels. We demonstrated structures for use in water purification, separation, sensors, templated synthesis, microelectronics, optics, controlled release, and highly selective catalysts.

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Controlled assembly in soft-particle colloidal suspensions is a technology poised to advance manufacturing methods for nano-scale templating, coating, and bio-conjugate devices. Applications for soft-particle colloids include photovoltaics, nanoelectronics, functionalized thin-film coatings, and a wide range of bio-conjugate devices such as sensors, assays, and bio-fuel cells. This presentation covers the topics of modeling and simulation of soft-particle colloidal systems over dewetting, evaporation, and irradiation gradients, including deposition of particles to surfaces. By tuning particle/solvent and environmental parameters, we transition from the regime of self-assembly to that of controlled assembly, and enable finer resolution of features at both the nano-scale and meso-scale. We report models of interparticle potentials and order parametrization techniques including results from simulations of colloids utilizing soft-particle field potentials. Using LAMMPS (Large-Scale Atomic/Molecular Massively Parallel Simulator), we demonstrate effects of volume fraction, shear and drag profiles, adsorbed and bulk polymer parameters, solvent chi parameter, and deposition profiles. Results are compared to theoretical models and correlation to TEM images from soft-particle irradiation experiments.

Affordable clean water is both a global and a national security issue as lack of it can cause death, disease, and international tension. Furthermore, efficient water filtration reduces the demand for energy, another national issue. The best current solution to clean water lies in reverse osmosis (RO) membranes that remove salts from water with applied pressure, but widely used polymeric membrane technology is energy intensive and produces water depleted in useful electrolytes. Furthermore incremental improvements, based on engineering solutions rather than new materials, have yielded only modest gains in performance over the last 25 years. We have pursued a creative and innovative new approach to membrane design and development for cheap desalination membranes by approaching the problem at the molecular level of pore design. Our inspiration comes from natural biological channels, which permit faster water transport than current reverse osmosis membranes and selectively pass healthy ions. Aiming for an order-of-magnitude improvement over mature polymer technology carries significant inherent risks. The success of our fundamental research effort lies in our exploiting, extending, and integrating recent advances by our team in theory, modeling, nano-fabrication and platform development. A combined theoretical and experimental platform has been developed to understand the interplay between water flux and ion rejection in precisely-defined nano-channels. Our innovative functionalization of solid state nanoporous membranes with organic protein-mimetic polymers achieves 3-fold improvement in water flux over commercial RO membranes and has yielded a pending patent and industrial interest. Our success has generated useful contributions to energy storage, nanoscience, and membrane technology research and development important for national health and prosperity.

Heightened interest in micro-scale and nano-scale patterning by imprinting, embossing, and nano-particulate suspension coating stems from a recent surge in development of higher-throughput manufacturing methods for integrated devices. Energy-applications addressing alternative, renewable energy sources offer many examples of the need for improved manufacturing technology for micro and nano-structured films. In this presentation we address one approach to micro- and nano-pattering coating using film deposition and differential wetting of nanoparticles suspensions. Rather than print nanoparticle or colloidal inks in discontinuous patches, which typically employs ink jet printing technology, patterns can be formed with controlled dewetting of a continuously coated film. Here we report the dynamics of a volatile organic solvent laden with nanoparticles dispensed on the surfaces of water droplets, whose contact angles (surface energy) and perimeters are defined by lithographic patterning of initially (super)hydrophobic surfaces.. The lubrication flow equation together with averaged particle transport equation are employed to predict the film thickness and particle average concentration profiles during subsequent drying of the organic and water solvents. The predictions are validated by contact angle measurements, in situ grazing incidence small angle x-ray scattering experiments, and TEM images of the final nanoparticle assemblies.

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Lack of robust manufacturing capabilities have limited our ability to make tailored materials with useful optical and thermal properties. For example, traditional methods such as spontaneous self-assembly of spheres cannot generate the complex structures required to produce a full bandgap photonic crystals. The goal of this work was to develop and demonstrate novel methods of directed self-assembly of nanomaterials using optical and electric fields. To achieve this aim, our work employed laser tweezers, a technology that enables non-invasive optical manipulation of particles, from glass microspheres to gold nanoparticles. Laser tweezers were used to create ordered materials with either complex crystal structures or using aspherical building blocks.

We have designed and built electrostatically actuated microvalves compatible with integration into a PDMS based microfluidic system. The key innovation for electrostatic actuation was the incorporation of carbon nanotubes into the PDMS valve membrane, allowing for electrostatic charging of the PDMS layer and subsequent discharging, while still allowing for significant distention of the valveseat for low voltage control of the system. Nanoparticles were applied to semi-cured PDMS using a stamp transfer method, and then cured fully to make the valve seats. DC actuation in air of these valves yielded operational voltages as low as 15V, by using a supporting structure above the valve seat that allowed sufficient restoring forces to be applied while not enhancing actuation forces to raise the valve actuation potential. Both actuate to open and actuate to close valves have been demonstrated, and integrated into a microfluidic platform, and demonstrated fluidic control using electrostatic valves.

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Pure, amine-derivatized and nickel-doped sol-gel silica membranes have been developed on tubular Membralox-type commercial ceramic supports for the purpose of carbon dioxide separation from nitrogen under coal-fired power plant flue gas conditions. An extensive synthetic and permeation test study was carried out in order to optimize membrane CO{sub 2} permeance, CO{sub 2}:N{sub 2} separation factor and resistance against densification. Pure silica membranes prepared under optimized conditions exhibited an attractive combination of CO{sub 2} permeance of 2.0 MPU (1 MPU = 1 cm{sup 3}(STP) {center_dot} cm{sup -2} min{sup -1} atm{sup -1}) and CO{sub 2}:N{sub 2} separation factor of 80 with a dry 10:90 (v/v) CO{sub 2}:N{sub 2} feed at 25 C. However, these membranes exhibited flux decline phenomena under prolonged exposure to humidified feeds, especially in the presence of trace SO{sub 2} gas in the feed. Doping the membranes with nickel (II) nitrate salt was effective in retarding densification, as manifested by combined higher permeance and higher separation factor of the doped membrane compared to the pure (undoped) silica membrane after 168 hours exposure to simulated flue gas conditions.

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A molecular-scale interpretation of interfacial processes is often downplayed in the analysis of traditional water treatment methods. However, such an approach is critical for the development of enhanced performance in traditional desalination and water treatments. Water confined between surfaces, within channels, or in pores is ubiquitous in technology and nature. Its physical and chemical properties in such environments are unpredictably different from bulk water. As a result, advances in water desalination and purification methods may be accomplished through an improved analysis of water behavior in these challenging environments using state-of-the-art microscopy, spectroscopy, experimental, and computational methods.

Laser tweezers optical trapping provides a unique noninvasive capability to trap and manipulate particles in solution at the focal point of a laser beam passed through a microscope objective. Additionally, combined with image analysis, interaction forces between colloidal particles can be quantitatively measured. By looking at the displacement of particles within the laser trap due to the presence of a neighboring particle or looking at the relative diffusion of two particles held near each other by optical traps, interparticle interaction forces ranging from pico- to femto-Newtons can be measured. Understanding interaction forces is critical for predicting the behavior of particle dispersions including dispersion stability and flow rheology. Using a new analysis method proposed by Sainis, Germain, and Dufresne, we can simultaneously calculate the interparticle velocity and particle diffusivity which allows direct calculation of the interparticle potential for the particles. By applying this versatile tool, we measure difference in interactions between various phospholipid bilayers that have been coated onto silica spheres as a new type of solid supported liposome. We measure bilayer interactions of several cell membrane lipids under various environmental conditions such as pH and ionic strength and compare the results with those obtained for empty liposomes. These results provide insight into the role of bilayer fluctuations in liposome fusion, which is of fundamental interest to liposome based drug delivery schemes.

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A gecko's extraordinary ability to suspend itself from walls and ceilings of varied surface roughness has interested humans for hundreds of years. Many theories and possible explanations describing this phenomenon have been proposed including sticky secretions, microsuckers, and electrostatic forces; however, today it is widely accepted that van der Waals forces play the most important role in this type of dry adhesion. Inarguably, the vital feature that allows a gecko's suspension is the presence of billions 3 of tiny hairs on the pad of its foot called spatula. These features are small enough to reach within van der Waals distances of any surface (spatula radius %7E100 nm); thus, the combined effect of billions of van der Waals interactions is more than sufficient to hold a gecko's weight to surfaces such as smooth ceilings or wet glass. Two lithographic approaches were used to make hierarchal structures with dimensions similar to the gecko foot dimensions noted above. One approach combined photo-lithography with soft lithography (micro-molding). In this fabrication scheme the fiber feature size, defined by the alumina micromold was 0.2 um in diameter and 60 um in height. The second approach followed more conventional photolithography-based patterning. Patterned features with dimensions %7E0.3 mm in diameter by 0.5 mm tall were produced. We used interfacial force microscopy employing a parabolic diamond tip with a diameter of 200 nm to measure the surface adhesion of these structures. The measured adhesive forces ranged from 0.3 uN - 0.6 uN, yielding an average bonding stress between 50 N/cm2 to 100 N/cm2. By comparison the reported literature value for the average stress of a Tokay gecko foot is 10 N/cm2. Acknowledgements This work was funded by Sandia National Laboratory's Laboratory Directed Research & Development program (LDRD). All coating processes were conducted in the cleanroom facility located at the University of New Mexico's Center for High Technology Materials (CHTM). SEM images were performed at UNM's Center for Micro-Engineering on equipment funded by a NSF New Mexico EPSCoR grant. 4

Low solid interfacial energy and fractally rough surface topography confer to Lotus plants superhydrophobic (SH) properties like high contact angles, rolling and bouncing of liquid droplets, and self-cleaning of particle contaminants. This project exploits the porous fractal structure of a novel, synthetic SH surface for aerosol collection, its self-cleaning properties for particle concentration, and its slippery nature 3 to enhance the performance of fluidic and MEMS devices. We propose to understand fundamentally the conditions needed to cause liquid droplets to roll rather than flow/slide on a surface and how this %22rolling transition%22 influences the boundary condition describing fluid flow in a pipe or micro-channel. Rolling of droplets is important for aerosol collection strategies because it allows trapped particles to be concentrated and transported in liquid droplets with no need for a pre-defined/micromachined fluidic architecture. The fluid/solid boundary condition is important because it governs flow resistance and rheology and establishes the fluid velocity profile. Although many research groups are exploring SH surfaces, our team is the first to unambiguously determine their effects on fluid flow and rheology. SH surfaces could impact all future SNL designs of collectors, fluidic devices, MEMS, and NEMS. Interfaced with inertial focusing aerosol collectors, SH surfaces would allow size-specific particle populations to be collected, concentrated, and transported to a fluidic interface without loss. In microfluidic systems, we expect to reduce the energy/power required to pump fluids and actuate MEMS. Plug-like (rather than parabolic) velocity profiles can greatly improve resolution of chip-based separations and enable unprecedented control of concentration profiles and residence times in fluidic-based micro-reactors. Patterned SH/hydrophilic channels could induce mixing in microchannels and enable development of microflow control elements. Acknowledgements This work was funded by Sandia National Laboratory's Laboratory Directed Research & Development program (LDRD). Some coating processes were conducted in the cleanroom facility located at the University of New Mexico's Center for High Technology Materials (CHTM). SEM images were performed at UNM's Center for Micro-Engineering on equipment funded by a NSF New Mexico EPSCoR grant. 4

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Our discovery that the introduction of living cells (Saccharomyces cerevisiae) alters dramatically the evaporation driven self-assembly of lipid-silica nanostructures suggested the formation of novel bio/nano interfaces useful for cellular interrogation at the nanoscale. This one year ''out of the box'' LDRD focused on the localization of metallic and semi-conducting nanocrystals at the fluid, lipid-rich interface between S. cerevisiae and the surrounding phospholipid-templated silica nanostructure with the primary goal of creating Surface Enhanced Raman Spectroscopy (SERS)-active nanostructures and platforms for cellular integration into electrode arrays. Such structures are of interest for probing cellular responses to the onset of disease, understanding of cell-cell communication, and the development of cell-based bio-sensors. As SERS is known to be sensitive to the size and shape of metallic (principally gold and silver) nanocrystals, various sizes and shapes of nanocrystals were synthesized, functionalized and localized at the cellular surface by our ''cell-directed assembly'' approach. Laser scanning confocal microscopy, SEM, and in situ grazing incidence small angle x-ray scattering (GISAXS) experiments were performed to study metallic nanocrystal localization. Preliminary Raman spectroscopy studies were conducted to test for SERS activity. Interferometric lithography was used to construct high aspect ratio cylindrical holes on patterned gold substrates and electro-deposition experiments were performed in a preliminary attempt to create electrode arrays. A new printing procedure was also developed for cellular integration into nanostructured platforms that avoids solvent exposure and may mitigate osmotic stress. Using a different approach, substrates comprised of self-assembled nanoparticles in a phospholipid templated silica film were also developed. When printed on top of these substrates, the cells integrate themselves into the mesoporous silica film and direct organization of the nanoparticles to the cell surface for integration into the cell.

The ability of semiconductor nanocrystals (NCs) to display multiple (size-specific) colors simultaneously during a single, long term excitation holds great promise for their use in fluorescent bio-imaging. The main challenges of using nanocrystals as biolabels are achieving biocompatibility, low non-specific adsorption, and no aggregation. In addition, functional groups that can be used to further couple and conjugate with biospecies (proteins, DNAs, antibodies, etc.) are required. In this project, we invented a new route to the synthesis of water-soluble and biocompatible NCs. Our approach is to encapsulate as-synthesized, monosized, hydrophobic NCs within the hydrophobic cores of micelles composed of a mixture of surfactants and phospholipids containing head groups functionalized with polyethylene glycol (-PEG), -COOH, and NH{sub 2} groups. PEG provided biocompatibility and the other groups were used for further biofunctionalization. The resulting water-soluble metal and semiconductor NC-micelles preserve the optical properties of the original hydrophobic NCs. Semiconductor NCs emit the same color; they exhibit equal photoluminescence (PL) intensity under long-time laser irradiation (one week) ; and they exhibit the same PL lifetime (30-ns). The results from transmission electron microscopy and confocal fluorescent imaging indicate that water-soluble semiconductor NC-micelles are biocompatible and exhibit no aggregation in cells. We have extended the surfactant/lipid encapsulation techniques to synthesize water-soluble magnetic NC-micelles. Transmission electron microscopy results suggest that water-soluble magnetic NC-micelles exhibit no aggregation. The resulting NC-micelles preserve the magnetic properties of the original hydrophobic magnetic NCs. Viability studies conducted using yeast cells suggest that the magnetic nanocrystal-micelles are biocompatible. We have demonstrated, for the first time, that using external oscillating magnetic fields to manipulate the magnetic micelles, we can kill live cells, presenting a new magnetodynamic therapy without side effects.