Joel C. Keay

Incorporation of single-walled carbon nanotubes into ferrocene-modified linear polyethylenimine redox polymer films.

In this study, we describe the effects of incorporating single-walled carbon nanotubes (SWNTs) into redox polymer-enzyme hydrogels. The hydrogels were constructed by combining the enzyme glucose oxidase with a redox polymer (Fc-C(6)-LPEI) in which ferrocene was attached to linear poly(ethylenimine) by a six-carbon spacer. Incorporation of SWNTs into these films changed their morphology and resulted in a significant increase in the enzymatic response at saturating glucose concentrations (3 mA/cm(2)) as compared to films without SWNTs (0.6 mA/cm(2)). Likewise, the sensitivity at 5 mM glucose was significantly increased in the presence of SWNTs (74 μA/cm(2)·mM) as compared to control films (26 μA/cm(2)·mM). We demonstrate that the increase in the electrochemical and enzymatic response of these films depends on the amount of SWNTs incorporated and the method of SWNT incorporation. Furthermore, we report that the presence of SWNTs in thick films allows for more of the ferrocene redox centers to become accessible. The high current densities of the hydrogels should allow for the construction of miniature biosensors and enzymatic biofuel cells.

Fabrication of protein dot arrays via particle lithography.

The ability to pattern a surface with proteins on both the nanometer and the micrometer scale has attracted considerable interest due to its applications in the fields of biomaterials, biosensors, and cell adhesion. Here, we describe a simple particle lithography technique to fabricate substrates with hexagonally patterned dots of protein surrounded by a protein-repellent layer of poly(ethylene glycol). Using this bottom-up approach, dot arrays of three different proteins (fibrinogen, P-selectin, and human serum albumin) were fabricated. The size of the protein dots (450 nm to 1.1 microm) was independent of the protein immobilized but could be varied by changing the size of the latex spheres (diameter=2-10 microm) utilized in assembling the lithographic bead monolayer. These results suggest that this technique can be extended to other biomolecules and will be useful in applications where arrays of protein dots are desired.

Anisotropic structural and electronic properties of InSb/ AlxIn1-xSb quantum wells grown on GaAs (001) substrates

InSb quantum wells (QWs) with remotely doped Al/sub x/In/sub 1-x/Sb barriers are candidates for several novel device structures that rely on a long electron mean free path. Mesoscopic magnetoresistors that take advantage of the high electron mobility in InSb QWs at room temperature are currently being developed for read-head applications. The promise of InSb QWs for spin-transistor applications has been shown recently by experiments that demonstrate a large zero-field spin splitting and ballistic transport at temperatures as high as 185 K. Since a semi-insulating substrate is required for electronic applications, the InSb/Al/sub x/In/sub 1-x/Sb structures are grown on GaAs [001] substrates. The /spl sim/14% lattice mismatch between the epilayers and the substrate results in a high defect density that partially limits the electron mean free path. We will present a detailed characterization of these defects and elucidate their role in limiting electron mobility.

Bandgap energies and refractive indices of Pb1-xSrxSe

Optical transmission measurements were carried out on Pb1−xSrxSe samples, grown by molecular beam epitaxy, with different Sr compositions (x) ranging from 0 to 1. Refractive indices were calculated for all the samples at room temperature and at 77 K by fitting the transmittance data. Bandgap energies of all compositions were calculated by fitting the absorption coefficients to theoretical models of direct and indirect transitions. A distinct bandgap inversion from the direct to the indirect was observed at a Sr composition of approximately x=0.20. The direct and indirect bandgaps of SrSe calculated from the experimental results were found to be 3.81 and 1.82 eV, respectively.

Effect of Surfactant Type and Redox Polymer Type on Single-Walled Carbon Nanotube Modified Electrodes

Electrodes modified with single-walled carbon nanotubes (SWNTs) offer a number of attractive properties for developing novel electrochemical sensors. A common method to immobilize SWNTs onto the electrode surface is by placing a droplet of a SWNT suspension onto the electrode surface and allowing the solvent to evaporate. In order to maximize the properties of individual SWNTs, surfactants are normally present in these suspensions to provide stable and homogeneous SWNT dispersions. In this study we investigated the effect of different surfactants on the electrochemical and enzymatic performance of SWNT modified glassy carbon electrodes (GCEs). Amperometic biosensors for glucose were fabricated by a two-step procedure. In the first step, SWNT films were deposited onto GCEs by solution casting suspensions of SWNTs in water, Triton X-100, Tween 20, sodium cholate or sodium dodecylbenzenesulfonate (NaDDBS). In the second step, hydrogels containing a redox polymer and the enzyme, glucose oxidase (GOX), were deposited and cross-linked onto the SWNT-modified GCE. Three different redox polymers were tested: 3-ferrocenylpropyl-modified LPEI, (Fc-C3-LPEI), 6-ferrocenylhexyl-modified LPEI, (Fc-C6-LPEI), and poly[(vinylpyridine)Os(bipyridyl)2Cl](2+/3+)(PVP-Os). Biosensors constructed with SWNT films from suspensions of Triton X-100 or Tween 20 generally produced the highest electrochemical and enzymatic responses, with Triton X-100 films producing current densities of ~1.7-2.1 mA/cm(2) for the three different redox polymers. In contrast, biosensors constructed with SWNT films from sodium cholate suspensions resulted in significant decreases in the electrochemical and enzymatic response and in some cases showed no enzymatic activity. The results with SWNT films from NaDDBS suspensions were dependent upon the specific redox polymer used, but in general gave reduced enzymatic responses (~0.05-0.4 mA/cm(2)). These results demonstrate the importance of surfactant type in fabricating SWNT-modified electrode films.

Independently controlling protein dot size and spacing in particle lithography

Particle lithography is a relatively simple, inexpensive technique used to pattern inorganics, metals, polymers, and biological molecules on the micro- and nanometer scales. Previously, we used particle lithography to create hexagonal patterns of protein dots in a protein resistant background of methoxy-poly(ethylene glycol)-silane (mPEG-sil). In this work, we describe a simple heating procedure to overcome a potential limitation of particle lithography: the simultaneous change in feature size and center-to-center spacing as the diameter of the spheres used in the lithographic mask is changed. Uniform heating was used to make single-diameter protein patterns with dot sizes of approximately 2-4 or 2-8 μm, depending on the diameter of the spheres used in the lithographic mask, while differential heating was used to make a continuous gradient of dot sizes of approximately 1-9 μm on a single surface. We demonstrate the applicability of these substrates by observing the differences in neutrophil spreading on patterned and unpatterned protein coated surfaces.

MBE growth optimization of InAs (001) homoepitaxy

The optimal conditions for growth of homoepitaxial InAs layers by molecular beam epitaxy were investigated over a wide range of substrate temperatures and As2/In flux ratios at a growth rate of 0.66 monolayer/s. Material quality was investigated using a variety of techniques: differential interference contrast microscopy, scanning electron microscopy, and atomic force microscopy. The results indicated that the InAs layer grown at a temperature between 430 and 450 °C with an As2/In flux ratio of about 15:1 yielded the highest quality, with a defect density of 2 × 104 cm−2 and a root mean square roughness of 0.19 nm. The quality can be further improved by growth at a lower growth rate of 0.22 monolayer/s. The morphology of large oval hillock defects on the InAs layers suggested that these defects originated at the substrate surface.

Band offsets between amorphous LaAlO3 and In0.53Ga0.47As

The band offsets between an amorphous LaAlO3 dielectric prepared by molecular-beam deposition and a n-type In0.53Ga0.47As (001) layer have been measured using synchrotron radiation photoemission spectroscopy. The valence and conduction band offsets at the postdeposition annealed LaAlO3∕InGaAs interface are 3.1±0.1 and 2.35±0.2eV, respectively. The band gap of LaAlO3, as determined by Al 2p and O 1s core level energy loss spectra, is 6.2±0.1eV. Within the resolution of the medium energy ion scattering technique, no interfacial oxide layer is seen between the InGaAs and the 3.6nm thick amorphous LaAlO3.

Mobility anisotropy in InSb/AlxIn1−xSb single quantum wells

Three types of defects at the surface of InSb quantum well samples are identified: hillocks, square mounds, and oriented abrupt steps. The electron mobility in the quantum well correlates to the density of abrupt features, such that samples with a high density of anisotropic defects show anisotropy in the mobility. We propose that the dominant scattering mechanism associated with these abrupt features is a fluctuation in the quantum well morphology.

The role of fibrinogen spacing and patch size on platelet adhesion under flow

Platelet adhesion to the vessel wall during vascular injury is mediated by platelet glycoproteins binding to their respective ligands on the vascular wall. In this study we investigated the roles that ligand patch spacing and size play in regulating platelet interactions with fibrinogen under hemodynamic flow conditions. To regulate the size and distance between patches of fibrinogen we developed a photolithography-based technique to fabricate patterns of proteins surrounded by a protein-repellant layer of poly(ethylene glycol). We demonstrate that when mepacrine labeled whole blood is perfused at a shear rate of 100 s ⁻¹ over substrates patterned with micron-sized wide lines of fibrinogen, platelets selectively adhere to the areas of patterned fibrinogen. Using fluorescent and scanning electron microscopy we demonstrate that the degree of platelet coverage (3-35%) and the ability of platelet aggregates to grow laterally are dependent upon the distance (6-30 μm) between parallel lines of fibrinogen. We also report on the effects of fibrinogen patch size on platelet adhesion by varying the size of the protein patch (2-20 μm) available for adhesion, demonstrating that the downstream length of the ligand patch is a critical parameter in platelet adhesion under flow. We expect that these results and protein patterning surfaces will be useful in understanding the spatial and temporal dynamics of platelet adhesion under physiologic flow, and in the development of novel platelet adhesion assays.