Manish Kulkarni

Hydrophobic properties of TMOS/TMES-based silica aerogels

Abstract The hydrophobic properties of tetramethoxysilane (TMOS)-based silica aerogels by incorporating trimethylethoxysilane (TMES) as a synthesis component, are described. The molar ratio of TMES/TMOS ( M ) was varied from 0 to 4.0 by keeping the TMOS, methanol (MeOH), water (H 2 O) and ammonium hydroxide (NH 4 OH), molar ratio constant at 1:14:4:3.7×10 −3 . The hydrophobic properties of the aerogels were studied using contact angle measurements, infrared spectroscopy and thermal analysis. The contact angle, θ increased from 100 to 140° for M =0.5 to 4. While the volume shrinkage of the aerogels increased whereas the bulk density decreased with increased M values. The hydrophobic aerogels are thermally stable up to a temperature of 300°C and above this temperature the aerogels become hydrophilic.

Carbon microelectromechanical systems as a substratum for cell growth

The study of the biocompatible properties of carbon microelectromechanical systems (carbon-MEMS) shows that this new microfabrication technique is a promising approach to create novel platforms for the study of cell physiology. Four different types of substrates were tested, namely, carbon-MEMS on silicon and quartz wafers, indium tin oxide (ITO) coated glass and oxygen-plasma-treated carbon thin films. Two cell lines, murine dermal fibroblasts and neuroblastoma spinal cord hybrid cells (NSC-34) were plated onto the substrates. Both cell lines showed preferential adhesion to the selectively plasma-treated regions in carbon films. Atomic force microscopy and Fourier transform infrared spectroscopy analyses demonstrated that the oxygen-plasma treatment modifies the physical and chemical properties of carbon, thereby enhancing the adsorption of extracellular matrix-forming proteins on its surface. This accounts for the differential adhesion of cells on the plasma-treated areas. As compared to the methods reported to date, this technique achieves alignment of the cells on the carbon electrodes without relying on direct patterning of surface molecules. The results will be used in the future design of novel biochemical sensors, drug screening systems and basic cell physiology research devices.

Janus silica film with hydrophobic and hydrophilic surfaces grown at an oil-water interface

We report a new methyltrimethoxysilane (MTMS) based route to growing a Janus silica film at the oil–water interface, which upon drying shows anisotropic wetting by water on its two surfaces. The contact angle of water on the surface grown in contact with the oil-side is found to be ∼150°, but it is much smaller, ∼65°, on the side which grew in contact with the aqueous phase. This large difference in the contact angle is found to be primarily because of two reasons: (i) orientation of hydrophobic methyl groups towards the oil-side of the film as confirmed by micro-Raman spectroscopy, and (ii) microstructural differences in the oil and water-side surfaces of the film. The inherently hydrophobic silica cluster network on the oil-side surface also exhibits larger pores that provide an air cushion for the water droplet and engenders a large contact angle. Effects of oil–water interfacial tension on the film growth and on its wetting and microstructural properties are also investigated by addition of cationic and anionic surfactants in the aqueous subphase. Static and dynamic wetting properties of the oil-side surface indicate that these do not change significantly due to variations in either the microstructure or chemical nature of the surface alone, but is a combined effect of both. Interestingly, the Janus films showing asymmetric surface properties can also be grown directly and thus integrated with a variety of porous surfaces like cotton, paper, hydrogel and ceramic substrates by having these surfaces straddle an oil–water interface.

Microfabrication of carbon structures by pattern miniaturization in resorcinol-formaldehyde gel.

A simple and novel method to fabricate and miniaturize surface and subsurface microstructures and micropatterns in glassy carbon is proposed and demonstrated. An aqueous resorcinol-formaldehyde (RF) sol is employed for micromolding of the master pattern to be replicated, followed by controlled drying and pyrolysis of the gel to reproduce an isotropically shrunk replica in carbon. The miniaturized version of the master pattern thus replicated in carbon is about 1 order of magnitude smaller than original master by repeating three times the above cycle of molding and drying. The microfabrication method proposed will greatly enhance the toolbox for a facile fabrication of a variety of carbon-MEMS and C-microfluidic devices.

Multiscale micro-patterned polymeric and carbon substrates derived from buckled photoresist films: fabrication and cytocompatibility

We report here a novel and simple buckling-based multiscale patterning of negative photoresist films which were subsequently pyrolyzed to yield complex micro-patterned carbon surfaces. Unlike other polymers, the use of a photoresist layer allows the overall pattern definition by photolithography on which the geometry and length scale of the buckling-instability are superimposed. The photoresist film swells anisotropically during developing and buckles after subsequent drying due to the difference in the shrinkage of the hard cross-linked layer on top of a softer native pre-polymer. We studied the conditions for the formation of a wide variety of complex, fractal buckling patterns as well as directionally aligned zigzag patterns over a large area. For example, the buckling diminished for the films below a critical thickness and after a prolonged UV exposure, both of which eliminate the softer under-layer. These patterned carbon substrates are also shown to be biocompatible for the cellular adhesion and viability by using L929 mouse fibroblast cells, thus indicating their potential use in bio-MEMS platforms with a conductive substrate. The buckled carbon patterns were found to be a better choice of a substrate for cell growth and viability as compared to flat and simply periodic patterned carbon surfaces.

Hierarchical Micro/Nano Structures by Combined Self-Organized Dewetting and Photopatterning of Photoresist Thin Films

Photoresists are the materials of choice for micro/nanopatterning and device fabrication but are rarely used as a self-assembly material. We report for the first time a novel interplay of self-assembly and photolithography for fabrication of hierarchical and ordered micro/nano structures. We create self-organized structures by the intensified dewetting of unstable thin (∼10 nm to 1 μm) photoresist films by annealing them in an optimal solvent and nonsolvent liquid mixture that allows spontaneous dewetting to form micro/nano smooth dome-like structures. The density, size (∼100 nm to millimeters), and curvature/contact angle of the dome/droplet structures are controlled by the film thickness, composition of the dewetting liquid, and time of annealing. Ordered dewetted structures are obtained simply by creating spatial variation of viscosity by ultraviolet exposure or by photopatterning before dewetting. Further, the structures thus fabricated are readily photopatterned again on the finer length scales after dewetting. We illustrate the approach by fabricating several three-dimensional structures of varying complexity with secondary and tertiary features.

Diblock copolymer lamellae on sinusoidal and fractal surfaces

A scaling analysis of equilibrium orientation of diblock copolymer molecules on fractal surfaces and a brief comparison with a particular experiment is presented in this paper. This work is motivated by a recent experimental finding that a diblock copolymer film of polystyrene-PMMA, when deposited on a rough substrate, can orient its lamellae from a parallel to a perpendicular configuration depending on the topographical characteristics of the substrate surface. It was found that the RMS height itself is not enough to effect the equilibrium configuration, but the fractal dimension of the surface is also important. In general, the orientation of lamellae is a function of the the power spectral density (PSD) curves of the underlying substrate surface. Assuming the diblock lamellae to behave like an Alexander-deGennes brush, we obtain the free energy expressions for this brush in both parallel and perpendicular orientations in various asymptotic regimes. Comparison of their free energy expressions predicts the equilibrium configuration. By examining the PSD curves and using our scaling results, we are able to qualitatively explain some aspects of the experimental observations regarding the equilibrium orientation of the diblock copolymer lamellae on rough surfaces.

Chitosan-fatty acid interaction mediated growth of Langmuir monolayer and Langmuir-Blodgett films

The interaction of chitosan with bio-membranes, which plays important role in deciding its use in biological applications, is realized by investigating the interaction of chitosan with stearic acid (fatty acid) in Langmuir monolayers (at air-water interface) and Langmuir-Blodgett (LB) films (after transferring it onto solid substrate). It is found from the pressure-area isotherms that the chitosan insertion causes an expansion of chitosan-fatty acid hybrid monolayers, which reduces the elasticity and make the film heterogeneous. It is likely that at low surface pressure chitosan is situated at the interface, interacting with stearic acid molecules via electrostatic and hydrophobic interactions whereas at high pressure chitosan mainly located at subsurface beneath stearic acid molecules. In the latter case the interaction is predominantly electrostatic yielding very small contribution to the surface pressure. The reduction of temperature of the subphase water allows more number of chitosan molecules to reach surface to increase the pressure/interaction. On the other hand, although pure chitosan is found difficult to relocate on the substrate from air-water interface due to its hydrophilic-like nature, it alongside stearic acid (amphiphilic molecules) can be transferred onto substrate using LB technique as evident from infrared spectra. Their out-of-plane and in-plane structures, as extracted from two complementary surface sensitive techniques- X-ray reflectivity and atomic force microscopy, are found strongly dependent on the chitosan mole fraction and the deposition pressure. These analysis of the film-structure will essentially allow one to model the system better and provide better insight into the interaction.