Virginia A. Davis

Strong Antimicrobial Coatings: Single-Walled Carbon Nanotubes Armored with Biopolymers

Large scale biomimetic single-walled carbon nanotube (SWNT) coatings with significant antimicrobial activity, high Youngs Modulus, and controlled morphology were fabricated using layer-by-layer assembly. Thickness was controlled within 1.6 nm and SWNT orientation was controlled using a directed air stream. This unique blend of multifunctionality and vertical and lateral control of a bottom-up assembly process is a significant advancement in developing macroscale assemblies with the combined attributes of SWNTs and natural materials.

Single wall carbon nanotube fibers extruded from super-acid suspensions: Preferred orientation, electrical, and thermal transport

Fibers of single wall carbon nanotubes extruded from super-acid suspensions exhibit preferred orientation along their axes. We characterize the alignment by x-ray fiber diagrams and polarized Raman scattering, using a model which allows for a completely unaligned fraction. This fraction ranges from 0.17 to 0.05±0.02 for three fibers extruded under different conditions, with corresponding Gaussian full widths at half maximum (FWHM) from 64° to 44°±2°. FWHM, aligned fraction, electrical, and thermal transport all improve with decreasing extrusion orifice diameter. Resistivity, thermoelectric power, and resonant-enhanced Raman scattering indicate that the neat fibers are strongly p doped; the lowest observed ρ is 0.25 mΩ cm at 300 K. High temperature annealing increases ρ by more than 1 order of magnitude and restores the Raman resonance associated with low-energy van Hove transitions, without affecting the nanotube alignment.

Enhanced stability of enzyme organophosphate hydrolase interfaced on the carbon nanotubes.

In this paper we demonstrate that SWNTs and a covalent immobilization strategy enable very sensitive sensors with excellent long term stability. Organophosphorus hydrolase (OPH) functionalized single and multi-walled carbon nanotube (CNT) conjugates were exploited for direct amperometric detection of paraoxon, a model organophosphate. The catalytic hydrolysis of paraoxon produces equimoles of p-nitrophenol; oxidation was monitored amperometrically in real time under flow-injection (FIA) mode. OPH covalently immobilized on single-walled carbon nanotubes (SWNTs) demonstrated much higher activity than OPH conjugated to multi-walled carbon nanotubes (MWNTs). The dynamic concentration range for SWNT-OPH was 0.5-8.5 micromolL(-1) with a detection limit of 0.01 micromolL(-1) (S/N=3). In addition to this high sensitivity, the immobilized OPH retained a significant degree of enzymatic activity, and displayed remarkable stability with only 25% signal loss over 7 months. These results suggest that covalent immobilization of OPH on CNTs can be used for specific immobilization with advantages of long term stability, high sensitivity, and simplicity.

Amorphous‐state characterization of efavirenz—polymer hot‐melt extrusion systems for dissolution enhancement

The aim of this study was to improve the dissolution rate of efavirenz (EFV) by formulating a physically stable dispersion in polymers. Hot-melt extrusion (HME) was used to prepare solid solutions of EFV with Eudragit EPO (a low-glass transition polymer) or Plasdone S-630 (a high-glass transition polymer). The drug-polymer blends were characterized for their thermal and rheological properties as a function of drug concentration to understand their miscibility and processability by HME. The solid-state stability of extrudates was characterized by differential scanning calorimetry (DSC), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and dissolution studies. Thermal and rheological studies revealed that the drug is miscible with both polymers, and a decrease in melt viscosity was observed as the drug concentration increased. XRD and DSC studies confirmed the existence of amorphous state of EFV in the extrudates during storage. The dissolution rate of EFV from the extrudates was substantially higher than the crystalline drug. FTIR studies revealed an interaction between the EFV and Plasdone S-630, which reduced the molecular mobility and prevented crystallization upon storage. EFV and Eudragit EPO systems lack specific interactions, but are less susceptible to crystallization due to the antiplasticization effect of the polymer.

Cholesteric and nematic liquid crystalline phase behavior of double-stranded DNA stabilized single-walled carbon nanotube dispersions.

The first lyotropic cholesteric single-walled carbon nanotube (SWNT) liquid crystal phase was obtained by dispersing SWNTs in an aqueous solution of double-stranded DNA (dsDNA). Depending on the dispersion methodology, the polydomain nematic phase previously reported for other lyotropic carbon nanotube dispersions could also be obtained. The phase behavior and dispersion microstructure were affected by the relative concentrations of dsDNA and SWNT and whether small bundles were removed prior to concentrating the dispersions. This readily controlled phase behavior opens new routes for producing SWNT films with controlled morphology.

Renewable nanocomposite layer-by-layer assembled catalytic interfaces for biosensing applications.

A novel, easily renewable nanocomposite interface based on layer-by-layer (LbL) assembled cationic/anionic layers of carbon nanotubes customized with biopolymers is reported. A simple approach is proposed to fabricate a nanoscale structure composed of alternating layers of oxidized multiwalled carbon nanotubes upon which is immobilized either the cationic enzyme organophosphorus hydrolase (OPH; MWNT-OPH) or the anionic DNA (MWNT-DNA). The presence of carbon nanotubes with large surface area, high aspect ratio and excellent conductivity provides reliable immobilization of enzyme at the interface and promotes better electron transfer rates. The oxidized MWNTs were characterized by thermogravimetric analysis and Raman spectroscopy. Fourier transform infrared spectroscopy showed the surface functionalization of the MWNTs and successful immobilization of OPH on the MWNTs. Scanning electron microscopy images revealed that MWNTs were shortened during sonication and that LbL of the MWNT/biopolymer conjugates resulted in a continuous surface with a layered structure. The catalytic activity of the biopolymer layers was characterized using absorption spectroscopy and electrochemical analysis. Experimental results show that this approach yields an easily fabricated catalytic multilayer with well-defined structures and properties for biosensing applications whose interface can be reactivated via a simple procedure. In addition, this approach results in a biosensor with excellent sensitivity, a reliable calibration profile, and stable electrochemical response.

Lyotropic liquid crystalline self-assembly in dispersions of silver nanowires and nanoparticles.

We report demixed nematic lyotropic liquid crystalline phase formation in dispersions of silver nanowires and spherical nanoparticle aggregates in ethylene glycol and water. This phase is observed in samples in spite of the high density, large aspect ratio, and long relaxation times of the nanowires which have an average length of 6.8 microm. Remarkably, in the biphasic region, the nanowire-rich liquid crystalline phase exhibits a strandlike morphology which has only previously been reported for single-walled carbon nanotube liquid crystals. Shearing predominantly liquid crystalline dispersions results in both significant nanowire alignment and nanowire-aggregate demixing. The results of this research suggest that the nanoparticle contaminants common to many synthesis schemes facilitate liquid crystalline phase formation and that these dispersions can be processed into aligned coatings.

Liquid Crystalline Phase Behavior of Silica Nanorods in Dimethyl Sulfoxide and Water

We report lyotropic smectic liquid crystalline phase behavior of silica nanorods dispersed in binary mixtures of dimethyl sulfoxide (DMSO) and water (H2O). The phase behavior is affected by nanorod size polydispersity and DMSO concentration in the binary solvent. The isotropic to biphasic transition is strongly affected by the relative amount of DMSO in the solvent, but the solvent has little effect on the biphasic to liquid crystal transition above 40/60 DMSO/H2O by volume. At less than 40% DMSO, increasing silica nanorod concentration initially results in the formation of liquid crystalline domains, but further increasing silica concentration results in crystal solvate formation. The morphology of the liquid crystalline phase is strongly affected by the size polydispersity, with lower polydispersity leading to a more uniform structure. As in other lyotropic nanocylinder systems, the microstructure of continuous solid films produced from the dispersions was affected by both the initial microstructure and the applied shear.

Development of an Antibody Functionalized Carbon Nanotube Biosensor for Foodborne Bacterial Pathogens

With increasing reports on bioterrorism and other bio-threats, rapid and real time detection methods for various pathogens are warranted. Attempts have been made to improve electrochemical biosensor performance by incorporating Carbon Nanotubes (CNTs). The high surface area of CNTs allows both immobilization of antibodies and electrochemical measurements. Salmonella monoclonal antibodies were covalently attached onto CNTs by using diimide activated imidation coupling. CNTs functionalized with antibodies were immobilized onto a glassy carbon electrode and the presence of pathogen was detected by studying the changes in charge transfer resistance and impedance, before and after the formation of antigen-antibody complex. CNTs behave as molecular wires allowing electrical communication between the underlying electrode and the conjugated antigen-antibody complex. Nyquist plots and cyclic voltammograms were studied and comparisons have been made between glassy carbon electrodes as working-electrode by itself, electrodes immobilized with antibodies and after the formation of antigen-antibody complex. Cyclic voltammeter experiments had a potential scan rate of 100 mVs-1, step height of 1.0 mV and applied potential from -1.0 V to 1.0 V. The electrochemical impedance experiments applied a frequency range of 100 kHz -100 mHz with an AC sine wave amplitude of 10 mV. Amplification in the current density was observed for CNTs immobilized on the electrode surface and decrease in current density and increased impedance was observed after the antigens bound specific antibodies. Enzyme-Linked Immune Sorbent Assay (ELISA) was done to determine the titer of the antibodies and their sensitivity at different dilutions for antigen detection. This technique could be an effective way to sense the formation of antigen-antibody complexes, with the potential to make the detection process rapid as compared to conventional pathogen detection methods.

Effects of liquid crystalline and shear alignment on the optical properties of cellulose nanocrystal films

Rheo-optics, microspectrophotometry, and optical contrast measurements were used to gain new insights into the interrelated effects of liquid crystalline phase behavior, flow alignment, and microstructural relaxation on cellulose nanocrystal (CNC) films’ alignment and optical properties. Optical contrast measurements were found to be an effective and facile way of determining changes in anisotropy directly from cross-polarized microscopy images. This method was used to continuously measure microstructural relaxation after the cessation of shear as well as the anisotropy of dried CNC films. Aqueous liquid crystalline CNC dispersions showed greater alignment after shear than isotropic or biphasic dispersions. However, CNC gels exhibited lower alignment at equivalent shear rates. The combination of greater initial alignment and slower relaxation of sheared liquid crystalline dispersions resulted in the most optically anisotropic films. Depending on their thickness, the CNC films were optically transparent in the visible regime or exhibited tunable interference colors. The results of this work highlight the tunability of CNC dispersion processing for producing color filters and other optical materials with controlled properties.