Selected Publications

BYU Authors: Nitesh Madaan, Aaron Terry, John Harb, Robert C. Davis, and Matthew R. Linford, published in J. Phys. Chem. C
Self-assembly of organic thiols is the most common S H way to introduce functional groups onto gold surfaces. Although the gold-sulfur (Au-S) bond is moderately strong (similar to 45 kcal/mol), it is also prone to oxidation, which substantially weakens the Au-S interaction. In this work, we describe the creation of more robust molecular assemblies on gold. As a first step, a thiolated monolayer is prepared on gold with an a,alpha,omega-dithiol. Experiments are also reported for a mercaptosilane monolayer on silicon dioxide. An oligomer of polybutadiene (PBd) was then tethered to these surfaces using thiol-ene chemistry. Residual groups on the PBd are then reacted with thiols, including octadecanethiol (ODT), 1H,1H,2H,2H-perfluoroalkanethiol, and a thiol-terminated 25-mer of DNA. Little nonspecific adsorption of a non-thiolated DNA oligomer was observed. Surface characterization was performed with X-ray photoelectron spectroscopy (XPS), contact angle goniometry, time-of-flight secondary ion mass spectrometry (ToF-SIMS), and spectroscopic ellipsometry. A thiol-gold monolayer and an analogous assembly of the same thiol tethered to gold through PBd on a dithiol monolayer were both exposed to air and light for 2 weeks and then rinsed with water. The monolayer on gold was removed in this process, while the thiol in the assembly appeared unaffected.
BYU Authors: David S. Jensen, Vipul Gupta, Rebecca E. Olsen, Alex T. Miller, Robert C. Davis, Daniel H. Ess, and Matthew R. Linford, published in J. Chromatogr. A
Porous graphitic carbon (PGC) particles were functionalized/passivated in situ in packed beds at elevated temperature with neat di-tert-amylperoxide (DTAP) in a column oven. The performance of these particles for high performance liquid chromatography (HPLC) was assayed before and after this chemistry with the following analytes: benzene, toluene, ethyl benzene, n-propyl benzene, n-butyl benzene, p-xylene, phenol, 4-methylphenol, phenetole, 3,5-xylenol, and anisole. After the first functionalization/passivation, the retention factors, k, of these compounds decreased by about 5% and the number of theoretical plates (N) increased by ca. 15%. These values of k then remained roughly constant after a second functionalization/passivation but a further increase in N was noticed. In addition, after each of the reactions, the peak asymmetries decreased by ca. 15%, for a total of ca. 30%. The columns were then subjected twice to methanol at 100 C for 5 h at 1 mL/min. After these stability tests, the values of k remained roughly constant, the number of plates increased, which is favorable, and the asymmetries rose and then declined, where they remained below the initial values for the unfunctionalized columns. Functionalized and unfunctionalized particles were characterized by scanning electron microscopy and BET measurements, which showed no difference between the functionalized and unfunctionalized materials, and X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS), where ToF-SIMS suggested some chemical differences between the functionalized and unfunctionalized materials. In particular ToF-SIMS suggested that the expected five-carbon fragments from DTAP exist at higher concentrations on DTAP-functionalized PGC. First principle calculations on model graphitic surfaces suggest that the first addition of a DTAP radical to the surface proceeds in an approximately isothermal or slightly favorable fashion, but that subsequent DTAP additions are then increasingly thermodynamically favorable. Thus, this analysis suggests that the direct functionalization/passivation of PGC with DTAP is plausible. Chemometric analyses of the chromatographic and ToF-SIMS data are also presented. (C) 2011 Elsevier B.V. All rights reserved.
BYU Authors: Walter C. Fazio, Jason M. Lund, Taylor S. Wood, Brian D. Jensen, Robert C. Davis, and Richard R. Vanfleet, published in ASME 2011 International Mechanical Engineering Congress and Exposition, (November 2011, Denver, CO)
Carbon nanotubes can be grown vertically from a substrate to form dense forests hundreds of microns tall. The space between the nanotubes can then be filled with carbon using chemical vapor deposition to create solid structures. These infiltrated structures can be detached from the substrate and operated as single-piece MEMS. To facilitate the design of compliant microdevices using this process, we explored the influence of two fabrication parameters—iron layer thickness and infiltration time—on the material’s mechanical properties, using the fracture strain to judge suitability for compliance. We prepared samples of a simple meso-scale cantilever beam pattern at various levels of these parameters, applied vertical loads to the tips of the beams, and recorded the forces and deflections at brittle failure. These data were then used in conjunction with a nonlinear FEA model of the beams to determine Young’s modulus and fracture stress for each experimental setting. From these data the fracture strains were obtained. The highest fracture strain observed was 2.48%, which is approximately 3.5 times that of polycrystalline silicon. This was obtained using an iron layer thickness of 10 nm and an infiltration time of 30 minutes. We used a test device—a compliant gripper mechanism for holding mammalian egg cells—to demonstrate the use of this material in compliant MEMS design.
BYU Authors: Lei Pei, Jonathan Abbott, Kyle Zufelt, Andrew Davis, Richard Vanfleet, Matthew R. Linford, and Robert Davis, published in Nanosci. Nanotechnol. Lett.
Here we report a straightforward method for fabricating freely suspended, thin, carbon nanotube (CNT) membranes infiltrated with polymers. A CNT film was made by compressing (rolling) vertically aligned carbon nanotubes (VACNTs) on a silicon substrate. A nanotube-polymer composite film was then fabricated by spin casting a polymer layer on top of the flattened CNT film. The composite film was subsequently released from the silicon substrate by dipping in HF solution, resulting in thin, smooth, suspended membranes. To aid in releasing intact, quality films, a mesh frame was adhered to the films prior to release. Characterization of the film and membrane was performed via scanning electron microscopy (SEM) and atomic force microscopy (AFM). This process is a new approach for making thin, reinforced, smooth films or membranes with high concentrations of CNTs, which may lead to higher performance materials.
BYU Authors: Landon A. Wiest, David S. Jensen, Chuan-Hsi Hung, Rebecca E. Olsen, Robert C. Davis, and Matthew R. Linford, published in Anal. Chem.
A new stationary phase for reversed-phase high performance liquid chromatography (RP HPLC) was created by coating spherical 3 mu m carbon core particles in a layer-by-layer (LbL) fashion with poly(allylamine) (PAAm) and nano-diamond. Unfunctionalized core carbon particles were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and Raman spectroscopy. After LbL of PAAm and nanodiamond, which yields ca. 4 mu m core-shell particles, the particles were simultaneously functionalized and cross-linked using a mixture of 1,2-epoxyoctadecane and 1,2,7,8-diepoxyoctane to obtain a mechanically stable C-18/C-8 bonded outer layer. Core-shell particles were characterized by SEM, and their surface area, pore diameter, and volume were determined using the Brunauer-Emmett-Teller (BET) method. Short stainless steel columns (30 x 4.6 mm i.d.) were packed and the corresponding van Deemter plots obtained. The Supporting information Contains a MATLAB program used to fit the van Deemter data. The retentions of a suite of analytes were investigated on a conventional HPLC at various organic solvent compositions, pH values of mobile phases, including extreme pH values, and column temperatures. At 60 degrees C, a chromatogram of 2,6-diisopropylphenol showed 71 500 plates/m (N/m). Chromatograms obtained under acidic conditions (pH 2.7) of a mixture of acetaminophen, diazepam, and 2,6-diisopropylphenol and a mixture of phenol, 4-methylphenol, 2-chlorophenol, 4-chlorophenol, 4-bromophenol, and 1-tert-butyl-4-methylphenol are presented. Retention of amitriptyline, cholesterol, and diazinon at temperatures ranging from 35 to 80 degrees C and at pH 11.3 is reported. A series of five basic drugs was also separated at this pH. The stationary phase exhibits considerable hydrolytic stability at high pH (11.3) and even pH 13 over extended periods of time. An analysis run on a UHPLC with a "sandwich" injection appeared to reduce extra column band broadening and gave best efficiencies of 110 000 120 000 N/m.
BYU Authors: Anthony C. Pearson, Elisabeth Pound, Adam T. Woolley, Matthew R. Linford, John N. Harb, and Robert C. Davis, published in Nano Lett.
We have used block copolymer patterned arrays of 5 nm gold nanopartides (AuNPs) for chemically aligned surface attachment of DNA origami. Addition of single-stranded DNA-thiol to AuNPs allowed a base paired attachment of sticky end modified DNA origami. Results indicate a stable, selective attachment between the DNA origami and ssDNA modified AuNPs. Yield data showed 74% of AuNP binding sites forming an attachment with a DNA origami rectangle, and control surfaces showed less than 0.5% nonspecific adsorption.