Publications by Year: 2006

2006
Chun, J. ; Li, J. L. ; Car, R. ; Aksay, I. A. ; Saville, D. A. Anisotropic adsorption of molecular assemblies on crystalline surfaces. Journal of Physical Chemistry B 2006, 110, 16624-16632.Abstract
Orientational order of surfactant micelles and proteins on crystalline templates has been observed but, given that the template unit cell is significantly smaller than the characteristic size of the adsorbate, this order cannot be attributed to lattice epitaxy. We interpret the template-directed orientation of rodlike molecular assemblies as arising from anisotropic van der Waals interactions between the assembly and crystalline surfaces where the anisotropic van der Waals interaction is calculated using the Lifshitz methodology. Provided the assembly is sufficiently large, substrate anisotropy provides a torque that overcomes rotational Brownian motion near the surface. The probability of a particular orientation is computed by solving a Smoluchowski equation that describes the balance between van der Waals and Brownian torques. Torque aligns both micelles and protein fibrils; the interaction energy is minimized when the assembly lies perpendicular to a symmetry axis of a crystalline substrate. Theoretical predictions agree with experiments for both hemi-cylindrical micelles and protein fibrils adsorbed on graphite.
Chen, C. H. ; Saville, D. A. ; Aksay, I. A. Electrohydrodynamic "drop-and-place" particle deployment. Applied Physics Letters 2006, 88.Abstract
The "drop-and-place" paradigm aims at delivering and positioning liquid drops using a pulsed electrohydrodynamic jet. On-demand drops much smaller than the diameter of the delivery nozzle may also contain particles. We report proof-of-concept experiments on the delivery of single 2 mu m diameter particles using a 50 mu m nozzle and identify the control parameters for dosing and positioning accuracies. A positioning accuracy at the micrometer level is achieved by eliminating contact line pinning on a hydrophobic surface and minimizing impingement-induced motion. The dosing statistics follow the random Poisson distribution, indicating that single-particle accuracy can be achieved using a gating mechanism. (c) 2006 American Institute of Physics.
Bhansali, S. H. ; Jarvis, J. M. ; Aksay, I. A. ; Carbeck, J. D. Enhanced resonator sensitivity with nanostructured porous silica coatings. Langmuir 2006, 22, 6676-6682.Abstract
We present a strategy to increase the sensitivity of resonators to the presence of specific molecules in the gas phase, measured by the change in resonant frequency as the partial pressure of the molecule changes. We used quartz crystals as the resonators and coated them with three different thin films (< 1 mu m thick) of porous silica: silica xerogel, silica templated by an ordered hexagonal phase of surfactant micelles, and silica templated by an isotropic L-3 phase surfactant micellar system. We compared the sensitivity of coated resonators to the presence of water vapor. The crystals coated with hexagonal phase-templated silica displayed a sensitivity enhancement up to 100-fold compared to an uncoated quartz crystal in the low-pressure regime where adsorption played a dominant role. L-3 phase-templated silica displayed the highest sensitivity (up to a 4000-fold increase) in the high partial pressure regimes where capillary condensation was the main accumulation mechanism. Three parameters differentiate the contributions of these coatings to the sensitivity of the underlying resonator: (i) specific surface area per unit mass of the coating, (ii) accessibility of the surfaces to a target molecule, and (iii) distribution in the characteristic radii of curvature of internal surfaces, as measured by capillary condensation.
Schniepp, H. C. ; Li, J. L. ; McAllister, M. J. ; Sai, H. ; Herrera-Alonso, M. ; Adamson, D. H. ; Prud'homme, R. K. ; Car, R. ; Saville, D. A. ; Aksay, I. A. Functionalized single graphene sheets derived from splitting graphite oxide. Journal of Physical Chemistry B 2006, 110, 8535-8539.Abstract
A process is described to produce single sheets of functionalized graphene through thermal exfoliation of graphite oxide. The process yields a wrinkled sheet structure resulting from reaction sites involved in oxidation and reduction processes. The topological features of single sheets, as measured by atomic force microscopy, closely match predictions of first-principles atomistic modeling. Although graphite oxide is an insulator, functionalized graphene produced by this method is electrically conducting.
Saville, D. A. ; Chun, J. ; Li, J. L. ; Schniepp, H. C. ; Car, R. ; Aksay, I. A. Orientational order of molecular assemblies on inorganic crystals. Physical Review Letters 2006, 96.Abstract
Surfactant micelles form oriented arrays on crystalline substrates although registration is unexpected since the template unit cell is small compared to the size of a rodlike micelle. Interaction energy calculations based on molecular simulations reveal that orientational energy differences on a molecular scale are too small to explain matters. With atomic force microscopy, we show that orientational ordering is a dynamic, multimolecule process. Treating the cooperative processes as a balance between van der Waals torque on a large, rodlike micellar assembly and Brownian motion shows that orientation is favored.
Li, J. L. ; Kudin, K. N. ; McAllister, M. J. ; Prud'homme, R. K. ; Aksay, I. A. ; Car, R. Oxygen-driven unzipping of graphitic materials. Physical Review Letters 2006, 96.Abstract
Optical microscope images of graphite oxide (GO) reveal the occurrence of fault lines resulting from the oxidative processes. The fault lines and cracks of GO are also responsible for their much smaller size compared with the starting graphite materials. We propose an unzipping mechanism to explain the formation of cracks on GO and cutting of carbon nanotubes in an oxidizing acid. GO unzipping is initiated by the strain generated by the cooperative alignment of epoxy groups on a carbon lattice. We employ two small GO platelets to show that through the binding of a new epoxy group or the hopping of a nearby existing epoxy group, the unzipping process can be continued during the oxidative process of graphite. The same epoxy group binding pattern is also likely to be present in an oxidized carbon nanotube and cause its breakup.
Chen, C. H. ; Saville, D. A. ; Aksay, I. A. Scaling laws for pulsed electrohydrodynamic drop formation. Applied Physics Letters 2006, 89.Abstract
A pulsed electrohydrodynamic jet can produce on-demand drops much smaller than the delivery nozzle. This letter describes an experimentally validated model for electrically pulsed jets. Viscous drag in a thin nozzle limits the flow rate and leads to intrinsic pulsations of the cone jet. A scale analysis for intrinsic cone-jet pulsations is derived to establish the operating regime for drop deployment. The scaling laws are applicable to similar electrohydrodynamic processes in miniaturized electrospraying systems. (c) 2006 American Institute of Physics.
Schniepp, H. C. ; Saville, D. A. ; Aksay, I. A. Self-healing of surfactant surface micelles on millisecond time scales. Journal of the American Chemical Society 2006, 128, 12378-12379.
Malik, A. S. ; Dabbs, D. M. ; Katz, H. E. ; Aksay, I. A. Silica monoliths templated on L-3 liquid crystal. Langmuir 2006, 22, 325-331.Abstract
Dimensionally stable, optically clear, highly porous (similar to 65% of the apparent volume), and high surface area (up to 1400 m(2)/g) silica monoliths were fabricated as thick disks (0.5 cm) by templating the isotropic liquid crystalline L-3 phase with silica through the hydrolysis and condensation of a silicon alkoxide and then removing the organic constituents by supercritical ethanol extraction. The L3 liquid crystal is a stable phase formed by the cosurfactants cetylpyridinium chloride monohydrate and hexanol in HCl(aq) solvent. Extracted 0.5 cm thick disks exhibited a low ratio of scattered to transmitted visible light (1.5 x 10(-6) at 22 from the surface normal). The degree of silica condensation in the monoliths was high, as determined by Si-29 NMR measurements of Q(3) and Q(4) peak intensities (0.53 and 0.47, respectively). As a result, the extracted and dried monoliths were mechanically robust and did not fracture when infiltrated by organic solvents. Photoactive liquid monomers were infiltrated into extracted silica monoliths and polymerized in situ, demonstrating the possible application of templated silica to optical storage technology.
Dabbs, D. M. ; Mulders, N. ; Aksay, I. A. Solvothermal removal of the organic template from L-3 ("sponge") templated silica monoliths. Journal of Nanoparticle Research 2006, 8 603-614.Abstract
We compare the methods of continuous solvent (Soxhlet) and supercritical solvent extractions for the removal of the organic template from nanostructured silica monoliths. Our monoliths are formed by templating the L-3 liquid crystal phase of cetylpyridinium chloride in aqueous solutions with tetramethoxy silane. The monoliths that result from both Soxhlet and supercritical extraction methods are mechanically robust, optically clear, and free of cracks. The Soxhlet method compares favorably with supercritical solvent extraction in that equivalent L-3-templated silica can be synthesized without the use of specialized reactor hardware or higher temperatures and high pressures, while avoiding noxious byproducts. The comparative effectiveness of various solvents in the Soxhlet process is related to the Hildebrand solubility parameter, determined by the effective surface area of the extracted silica.
Bhansali, S. H. ; Malik, A. S. ; Jarvis, J. M. ; Akartuna, I. ; Dabbs, D. M. ; Carbeck, J. D. ; Aksay, I. A. The stability of L-3 sponge phase in acidic solutions. Langmuir 2006, 22, 4060-4064.Abstract
In the synthesis of the disordered lyotropic liquid crystalline L-3 sponge phase prepared with the cosurfactants cetylpyridinium chloride and hexanol, aqueous NaCl solution is used as the solvent. When this sponge phase is used as the template for L3 silica-phase processing, we replace NaCl with HCl to facilitate the acid catalysis of tetramethoxysilane in forming a templated silica gel, assuming that changing the solvent from NaCl(aq) to HCl(aq) of equivalent ionic strength does not affect the stability range of the L3 phase. In this work, we confirm that changing the pH of the solvent from neutral to acidic (with HQ has negligible effect on the L3 phase region. Equivalent ionic strength is provided by either NaCl(aq) or HCl(aq) solvent; therefore, a similar phase behavior is observed regardless of which aqueous solvent is used.