Chemistry Commons^™

Annealing Temperature And Initial Iron Valence Ratio Effects On The Structural Characteristics Of Nanoscale Nickel Zinc Ferrite, S. Calvin, M. D. Schultz, L. Glowzenski, E. E. Carpenter

Chemistry Publications

Nickelzincferrite (NZFO) nanoparticles were synthesized via a reverse micelle method with a nonionic surfactant. Three different initial Fe3+/Fe2+ ratios were employed along with three different firing temperatures (200, 500, 1000 °C) to investigate the effects on the NZFO system. Extended x-rayabsorption fine structure (EXAFS) results reveal zinc loss at high annealing temperatures; at 1000 °C, the loss is nearly total for Fe3+/Fe2+ ratios other than 10:90. Annealing at 500 °C, however, appears necessary for fully incorporating the zinc and nickel into the spinel phase. The best nanoferrite was thus obtained using an initial Fe3+/Fe2+ ratio of 10:90 and a moderate …

Dual Mode Nanoparticles: Cds Coated Iron Nanoparticles, F. N. Radwan, K. J. Carroll, E. E. Carpenter

Chemistry Publications

Reverse micelles can be used in a sequential fashion to make core-shell nanoparticles. Using this technique it is possible to make a magnetic quantum dot, by coating an iron core with a cadmium sulfide shell. Transmission electron microscopy indicated core-shell morphology and narrow size distribution of the obtained particles. Collectively, x-ray powder diffraction and x-ray photoelectron spectroscopy verified the presence of cadmium sulfide on the surface of the nanoparticles. Optical properties of the coated particles were demonstrated using fluorescence spectroscopy. A vibrating sample magnetometer was used to determine magnetic properties. Dual mode cadmium sulfide coatediron core-shell nanoparticles make unique candidates …

High Magnetization Aqueous Ferrofluid: A Simple One-Pot Synthesis, Kyler J. Carroll, Michael D. Schultz, Panos P. Fatouros, Everett E. Carpenter

Chemistry Publications

A one-step polyol method was utilized to prepare a stable aqueous iron/iron oxide ferrofluid. The dried powders were characterized by x-ray diffraction, electron microscopy, x-ray absorption spectroscopy, and vibrating sample magnetometry for the determination of phase, morphology, and magnetic properties. To show its potential for imaging applications, the ferrofluid was also investigated as a magnetic resonance imaging contrast agent.

Localized Surface Plasmon Resonance Enhanced Magneto-Optical Activity In Core-Shell Fe-Ag Nanoparticles, L. Wang, K. Yang, C. Clavero, A. J. Nelson, K. J. Carroll, E. E. Carpenter, R. A. Lukaszew

Chemistry Publications

Metallic nanoparticles (NPs) are suitable platforms for miniaturized biosensing based on their optical and magneto-opticalproperties. It is possible to enhance the sensitivity of specific kinds of NPs by exploiting their optical and magneto-opticalproperties under suitable external magnetic field modulation. Here, the magneto-opticalproperties of Fe–Ag core-shell ferromagnet-noble metal NPs have been investigated as a function of the incident light frequency. For Fe–Ag NPs with a concentration ratio around 25:75, an optical absorption band centered at 3 eV due to localized surface plasmon resonance (LSPR) excitation is observed. A strong enhancement of the Faraday rotation is also observed, greatly exceeding the value …

Spectrally Tunable Magnetic Nanoparticles Designed For Distribution/Recollection Applications, Nicholas B. Mcdowall, James R. Wilkins, Kyler J. Carroll, Jarrod D. Edwards, Jean D. Nelson, Everett E. Carpenter, Garry P. Glaspell

Chemistry Publications

The comprehensive goal of this research is the synthesis and characterization of nanomaterials that are spectrally tunable in terms of their electromagnetic signal, are robust, magnetic (allowing their piloted movement), and have the potential to be functionalized for the detection of CBRNE threats. Various chemical methods were utilized for synthesis of magnetic (iron) and luminescent rare earth (RE) components, and their mixtures. Effects of integrating an iron core into RE luminescent lattices (excited by UV, emit in the VIS) were investigated. The determination of the optimum balances between magnetic and luminescent components such that the magnetism was maximized while maintaining …

Annealing Of Amorphous Fexco100-X Nanoparticles Synthesized By A Modified Aqueous Reduction Using Nabh4, Kyler J. Carroll, Daniel M. Hudgins, L. W. Brown Iii, S. D. Yoon, D. Heiman, V. G. Harris, Everett E. Carpenter

Chemistry Publications

FexCo100−x nanoparticles were synthesized by aqueous reduction in iron (II) sulfate and cobalt (II) sulfate using sodium borohydride and sodium citrate. The initial concentrations of iron and cobalt were varied while maintaining an overall metal concentration of 4.60 mM. Increasing the cobalt content from 0 to 100 at. % decreased the magnetization saturation from 152 to 48 emu/g, as determined by room temperature vibrating sample magnetometry. Annealing the samples at 450 and 600 °C showed an increase in crystallite size. Powder x-ray diffraction and transmission electron microscopy was performed to determine the phases and morphology of the materials.

Nonclassical Crystallization Of Amorphous Iron Nanoparticles By Radio Frequency Methods, Kyler J. Carroll, J. A. Pitts, Kai Zhang, A. K. Pradhan, E. E. Carpenter

Chemistry Publications

Amorphousironnanoparticles were synthesized using an aqueous reduction in iron(II) sulfate with sodium borohydride and sodium citrate. Various radio frequency (rf) exposure times were investigated in order to determine trends in nonclassical crystallization. RF times from 15 to 300 s revealed an increase in crystallite size from 5 to 60 nm, as determined by powde rx-ray diffraction. Also, solvent optimization revealed that ethanol produced the largest trends for increasing crystallite size without total oxidation of the samples. Magnetic characterization by room temperature vibrating sample magnetometry and high resolution transmission microscopy was performed to verify magnetic properties and particle morphology.

Contact Angle Of A Nano-Drop On A Heterogeneous Surface, John Ritchie

Theses and Dissertations

CONTACT ANGLE OF A NANO-DROP ON A HETEROGENEOUS SURFACE By John Andre Ritchie, Master of Science A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science at Virginia Commonwealth University Virginia Commonwealth University, 2010 Major Director: Dr. Alenka Luzar, Professor of Chemistry

We examine the relation between contact angle of a nanodrop of water and the location of surface-water interaction energy at the perimeter and beneath the drop. Young’s equations gives the relationship between surface tension, at the three phase solid liquid vapor interface, and contact angle on a homogeneous surface. Cassie and Baxter …

Modeling Hydrophobic Effects At Different Lengthscales, Jihang Wang

Theses and Dissertations

Understanding hydrophobic effects at different length scales is relevant to many complex and poorly understood everyday phenomena in materials science and biology. In this thesis, a variety of theory/computational methods in statistical physics and statistical mechanics are used to address three separated, but interconnected problems: (1) How solvation free energy scales with a partical size that is charged? This problem has never been attempted to solve before despite its immense importance in colloidal and protein solutions (J. Wang, D. Bratko, K. Leung and A. Luzar, Hydrophobic hydration at different length-scales: manipulating the crossover by charges, to be submitted to J. …

Multidimensional Methods: Applications In Drug-Enzyme Intrinsic Clearance Determination And Comprehensive Two-Dimensional Liquid Chromatography Peak Volume Determination, Dennis Thekkudan

Theses and Dissertations

The goal of the first project was to evaluate strategies for determining the in vitro intrinsic clearance (CLint) of dextrorphan (DR) as metabolized by the UGT2B7 enzyme to obtain dextrorphan glucuronide (DR-G). A direct injection liquid chromatography-mass spectrometry (LC-MS) method was used to monitor products using the pseudo-first-order (PFO) model. Standard enzymatic incubations were also quantified using LC-MS. These data were fit utilizing both PFO and Michaelis-Menten (MM) models to determine estimates of kinetic parameters. The CLint was determined to be 0.28 (± 0.08) µL/min/mg protein for a baculovirus insect cell-expressed UGT2B7 enzyme. This is the first confirmation that dextrorphan …

Preparation And Characterization Of Stable Macroporous Titania Nano-Wells, Hema Santhi Aluri

Theses and Dissertations

Silica based sol-gel thin films have been extensively studied because of their advantages that include optical transparency, high biodegradability and low intrinsic fluorescence. However, one concern with silica based sol-gel derived materials is their long term stability in aqueous solutions. Another concern is their limited porosity. These two concerns limit the application of these materials in catalysis and separations. The main objective of this study is to prepare porous, thin films using titanium alkoxides as precursors and evaluate their long term stability in aqueous solutions. Colloidal crystal templating will be used to introduce macrosized pores into the titania network. The …

Spectroscopic Characterizations Of The Compound Ii Intermediate Of Soybean Peroxidase From Soybean Seed Coatings, Andoh-Baidoo Rosemarie Agyepong

Theses and Dissertations

Spectroscopic characterization of ferric soybean peroxidase with peroxides were studied to determine the ligand coordination and to characterize the structure of the heme active site and its intermediates (ferryl species). The lifetime, chemical reactivity and distinctive colors of the ferryl species (FeIV) formed during the oxidation of peroxidase (FeIII) by peroxides enabled structure, dynamics and reaction mechanisms to be studied. Resonance Raman spectroscopy was used as a means of characterizing the structure of the soybean peroxidase and its intermediates. Excitation in the Soret absorption band at 406.7nm with 2-5mW laser power was used for this study. Resonance Raman spectra in …

Poly(Styrene-Co-Vinylbenzylchloride-Co-Divinylbenzene) Coated Iron Oxide: Synthesis And Effects On Size And Morphology, M. D. Shultz, J. R. Marin, S. H. Naik, J. Wilkins, J. M. Laza, J. L. Vilas, M. Rodriguez, N. Perez, E. E. Carpenter

Chemistry Publications

Iron oxide nanoparticles were coated with a polymer synthesized from the monomers of styrene, divinylbenzene, and vinylbenzylchloride. The resultant polymer microspheres from synthesis without nanoparticle loading are primarily monodispersed with a diameter of 3.45 μm as measured by scanning electron microscopy. The addition of 1% nanoparticles by mass appears to decrease the size of the microspheres down to 2.04 μm as well as increase the polydispersity. This trend is also seen to continue as you add more nanoparticles to the system going from 3.45 μm with 0% nanoparticles down to below 1 μm for 5% nanoparticles. This indicates that the …

One Parameter Control Of The Size Of Iron Oxide Nanoparticles Synthesized In Reverse Micelles, M. D. Shultz, W. Braxton, C. Taylor, E. E. Carpenter

Chemistry Publications

Iron oxide nanoparticles were synthesized via reverse micelle methods. The initial iron concentration was varied, while maintaining all other parameters constant, in order to investigate the effect of the iron concentration on the resultant iron oxide nanoparticle size. Increasing the iron concentration from 0.125M to 0.5M yielded an increase in average nanoparticle diameter from 4.71 to 7.95 nm, as measured by transmission electron microscopy. Three other concentrations between 0.125M and 0.5M showed corresponding size variations, all with statistical significance. Magnetic characterization by vibrating sample magnetometry and powder x-ray diffraction was performed to verify proper phase and material. Further insight into …

Microscopic Dynamics Of The Orientation Of A Hydrated Nanoparticle In An Electric Field, C. D. Daub, D. Bratko, A. Towshif, A. Luzar

Chemistry Publications

We use atomistic simulations to study the orientational dynamics of a nonpolar nanoparticle suspended in water and subject to an electric field. Due to molecular-level effects we describe, the torque exerted on the nanoparticle exceeds continuum-electrostatics based estimates by about a factor of two. The reorientation time of a 16.2×16.2×3.35 ̊A3 nanoparticle in a field E > 0.015V/ ̊A is an order of magnitude less than the field-free orientational time (∼ 1 ns). Surprisingly, the alignment speed is nearly independent of the nanoparticle size in this regime. These findings are relevant for design of novel nanostructures and sensors and development of …

Noncovalent Interaction Of Platinum Planar Amine Compounds With Tryptophan: A Strategy To Interfere With P53-Mdm2 Interactions And Targeting Retroviral Zn Finger-Dna Interaction (Hiv Ncp7), Aaron Bate

Theses and Dissertations

Non-covalent interactions involving π-π stacking play an essential role in self-assembly and molecular recognition processes such as protein folding and DNA/RNA-protein selective recognition. The knowledge gained from these studies could provide insight into possible site recognition complexes, inhibiting or mimicking protein-protein or protein-DNA interactions. Based on molecular modeling as well as HOMO and LUMO energies, several chromophores were selected with a variety of ∆ε values (∆ε= |εHOMO,NAcTrp – εLUMO,chromophores|), high and low, to establish a correlating trend with the modeling and experimental data. The corresponding Pt(dien) compounds were synthesized and their ability to stack to N-acetyl tryptophan was evaluated by …

Mechanistic Studies On The Electrochemistry Of Glutathione And Homocysteine, Olufemi Oyesanya

Theses and Dissertations

This research work has investigated the electrochemistry of glutathione (GSH)and homocysteine (HCSH) in order to develop sensors for these biological thiols.Ru(bpy)₃³⁺ and IrCl₆²⁻ have been used as mediators for the electrooxidation of GSH andHCSH because direct oxidation of these thiols is slow at most conventional electrodes.The electrochemical detection of GSH and HCSH has been pursued because of their biological roles.

Concerted proton electron transfer (CPET) and stepwise proton electron transfer(PT/ET) pathways have been observed in the electrooxidation of GSH and HCSH.Oxidation of GSH by Ru(bpy)₃³⁺ carried out in deuterated and undeuterated buffered (pH= pD …

Magnetic Properties Of La 0.6 Sr 0.4 Mno 3 Thin Films On Srtio 3 And Buffered Si Substrates With Varying Thickness, A. K. Pradhan, D. Hunter, T. Williams, B. Lasley-Hunter, R. Bah, H. Mustafa, R. Rakhimov, J. Zhang, D. J. Sellmyer, E. E. Carpenter, D. R. Sahu, J. -L. Huang

Chemistry Publications

La0.60Sr0.40MnO3 (LSMO) thin films of varying thickness from 12 to 55 nm were deposited using the pulsed-laser deposition technique onto single-crystalline SrTiO3 (STO) and STO-buffered Si substrates. The Tc of LSMO filmsgrown on STO-buffered Si substrates decreases faster than films directly grown on STO with decreasing film thickness. The LSMO/STO film with thickness of 55 nm shows Tc at about 360 K, which is close to the bulk value, whereas TcLSMO film on STO-buffered Si film of similar thickness is reduced to 320 K. This difference is attributed to the strain and interfacial disorders in LSMO film on STO/Si. The …

Transverse Susceptibility Study Of The Effect Of Varying Dipolar Interactions On Anisotropy Peaks In A Three-Dimensional Assembly Of Soft Ferrite Nanoparticles, Pankaj Poddar, Marienette B. Morales, Natalie A. Frey, Shannon A. Morrison, Everett E. Carpenter, Hariharan Srikanth

Chemistry Publications

Collective magnetization dynamics in nanoparticle assemblies is of current interest as it forms the basis of high density storage media. It is important to understand how interparticle interactions in a three-dimensional (3D) arrangement of superparamagnetic nanoparticles would affect the overall effective magnetic anisotropy of the system. We have studied the influence of varying strengths of dipolar interaction on the static and dynamic magnetic properties of surfactant-coated monodispersed manganese zinc ferrite nanoparticles using reversible transverse susceptibility. We track the evolution of the anisotropy peaks with varying magnetic field, temperature, and interaction strength. The blocking temperature shows an increase from 28 to …

Poly(D,L-Lactide-Co-Glycolide) Microcomposite Containing Magnetic Iron Core Nanoparticles As A Drug Carrier, Sweta Naik, Everett E. Carpenter

Chemistry Publications

Today many potent anticancer drugs like cisplatin are available which carry a number of side effects. A promising way of reducing the side effects is to target the drug to tissue sites by coating it with biocompatible materials like Poly (dl-lactide-co-glycolide) (PLGA) polymer where controlled drug release is achieved during the biodegradation of the polymer. Also the efficacy of anticancer drugs like cisplatin increases at elevated temperatures, so if local heating can be achieved where the drug is targeted. Local heating can be achieved by introducing iron core nanoparticles in the composites along with the drug, which can be heated …

Magnetic Nanoparticles Based On Iron: Synthesis, Characterization, Design, And Application, Michael David Shultz

Theses and Dissertations

Magnetic nanoparticles are of great interest for a wide range of applications. This work has focused on three primary forms of iron based nanoparticles and combinations thereof: α-iron, iron oxide, and iron carbide or cementite. The synthesis of several core-shell particles including cementite-iron oxide, α-iron-cementite, and α-iron-iron oxide was accomplished through reverse micelle routes and high temperature decomposition of iron pentacarbonyl in various media. Structural analysis to confirm the structures was performed using extended x-ray absorption fine structure (EXAFS) techniques. A rapid characterization technique was developed utilizing a correlation between Fourier transform infrared spectroscopy and EXAFS to determine the full …

Characterization Of Microorganisms Of Interest To Homeland Security And Public Health Utilizing Liquid Chromatography/Mass Spectrometry, Robert A. Everley

Theses and Dissertations

Liquid chromatography/quadrupole time of flight mass spectrometry (LC/QTOF MS) utilizing electrospray ionization was employed to monitor protein expression in Escherichia coli and Shigella organisms. Automated charge state deconvolution, spectral subtraction and spectral mirroring were used to reveal subtle differences in the LC/MS data. Reproducible intact protein biomarkers were discovered based on their unique mass, retention time and relative intensity. These markers were implemented to differentiate closely related strain types, (e.g. two distinct isolates of E. coli O157:H7) and to correctly identify unknown pathogens. Notable, was the distinction of multiple serotypes of enterohaemorrhagic E. coli which cannot be distinguished by clinical …

Control Of The Cation Occupancies Of Mnzn Ferrite Synthesized Via Reverse Micelles, M. D. Shultz, M. J. Allsbrook, E. E. Carpenter

Chemistry Publications

Variations in cation occupancy in mixed metal ferrite systems can affect their electronic and magnetic properties. It is known that different synthesis parameters can lead to various cation distributions and the ability to tune these distributions is of great interest. This study uses the extended x-ray-absorption fine structure–IR relationship to investigate the effect of various Fe2+/Fe3+ ratios in initial synthesis conditions on cation distribution for manganesezincferrite (MZFO). Differences in the precipitated material before firing could lead to differences in the final material if fired under similar conditions. This work uses several different ratios of Fe3+/Fe2+, which will affect the initial …

Vapor Phase Nucleation On Neutral And Charged Nanoparticles: Condensation Of Supersaturated Trifluoroethanol On Mg Nanoparticles, Victor Abdelsayed, M. Samy El-Shall

Chemistry Publications

A new technique is described to study the condensation of supersaturated vapors on nanoparticles under well-defined conditions of vapor supersaturation, temperature, and carrier gas pressure. The method is applied to the condensation of supersaturated trifluoroethanol (TFE) vapor on Mg nanoparticles. The nanoparticles can be activated to act as condensation nuclei at supersaturations significantly lower than those required for homogeneous nucleation. The number of activated nanoparticles increases with increasing the vapor supersaturation. The small difference observed in the number of droplets formed on positively and negatively charged nanoparticles is attributed to the difference in the mobilities of these nanoparticles. Therefore, no …

Investigations On The Structure Of Dimethyl Sulfoxide And Acetone In Aqueous Solution, Sylvia E. Mclain, Alan K. Soper, Alenka Luzar

Chemistry Publications

Aqueous solutions of dimethyl sulfoxide (DMSO) and acetone have been investigated using neutron diffraction augmented with isotopic substitution and empirical potential structure refinement computer simulations. Each solute has been measured at two concentrations—1:20 and 1:2 solute:water mole ratios. At both concentrations for each solute, the tetrahedral hydrogen bonding network of water is largely unperturbed, though the total water molecule coordination number is reduced in the higher 1:2 concentrations. With higher concentrations of acetone, water tends to segregate into clusters, while in higher concentrations of DMSO the present study reconfirms that the structure of the liquid is dominated by DMSO-water interactions. …

Size Dependent Magnetic Properties And Cation Inversion In Chemically Synthesized Mnfe2o4 Nanoparticles, C. N. Chinnasamy, Aria Yang, S. D. Yoon, Kailin Hsu, M. D. Shultz, E. E. Carpenter, S. Mukerjee, C. Vittoria, V. G. Harris

Chemistry Publications

MnFe2O4nanoparticles with diameters ranging from about 4to50nm were synthesized using a modified coprecipitation method. X-ray diffractograms revealed a pure phase spinel ferrite structure for all samples. Transmission electron microscopy showed that the particles consist of a mixture of both spherical (smaller) and cubic (larger) particles dictated by the reaction kinetics. The Néel temperatures (TN) of MnFe2O4 for various particle sizes were determined by using high temperature magnetometry. The ∼4nm MnFe2O4 particles showed a TN of about 320°C whereas the ∼50nm particles had a TN of about 400°C. The high Néel temperature, compared with the bulk MnFe2O4 TN of 300°C, is …

Effect Of Field Direction On Electrowetting In A Nanopore, D. Bratko, Christopher D. Daub, Kevin Leung, Alenka Luzar

Chemistry Publications

We manifest a significant influence of field direction and polarity on surface wetting, when the latter is tuned by application of an external electric field. Thermodynamics of field-induced filling of hydrocarbon-like nanopores with water is studied by open ensemble molecular simulation. Increased field strength consistently results in water-filling and electrostriction in hydrophobic nanopores. A threshold field commensurate with surface charge density of about one elementary charge per 10 nm2 suffices to render prototypical paraffin surfaces hydrophilic. When a field is applied in the direction perpendicular to the confining walls, the competition between orientational polarization and angle preferences of interfacial water …

Electrowetting At The Nanoscale, C. D. Daub, D. Bratko, K. Leung, A. Luzar

Chemistry Publications

Using molecular simulations of nano-sized aqueous droplets on a model graphite surface we demonstrate remarkable sensitivity of water contact angles to the applied electric field polarity and direction relative to the liquid/solid interface. The effect is explained by analyzing the influence of the field on interfacial hydrogen bonding in the nanodrop, which in turn affects the interfacial tensions. The observed anisotropy in droplet wetting is a new nanoscale phenomenon that has so far been elusive as, in current experimental setups, surface molecules represent a very low fraction of the total number affected by the field. Our findings may have important …

Drift Tube Ion Mobility Measurements For Thermochemistry, Kinetics And Polymerization Of Cluster Ions, Ridha Ben Mohsen Mabrouki

Theses and Dissertations

In this work, the Drift Tube Ion Mobility technique is used to study the hydrophobic hydration and solvation of organic ions and measure the thermochemistry and kinetics of ion-molecule reactions. Furthermore, an exploratory study of the intracluster polymerization of isoprene will be presented and discussed. The ion hydration study is focused on the C3H3+ cation1 and Pyridine▪+ radical cation.2 The chemistry of the cyclic C3H3+ cation1 has received considerable attention and continues to be an active area of research.3-7 The binding energies of the first 5 H2O molecules to c-C3H3+ were determined by equilibrium measurements. The measured binding energies of …

Hydration Studies Of Electrospray Ions From Amino Acids And Small Peptides, Chuong Quoc Nguyen

Theses and Dissertations

This project was undertaken to gain a better understanding of the hydration behaviors of gas phase ions from solutions containing amino acids and peptides. In order to characterize their hydration behavior, the molecules of interest in solutions were first converted into gas phase ions by electrospray ionization (ESI). The completely desolvated ions were then deliberately dispersed into an inert bath gas, usually nitrogen, containing accurately known concentrations of solvent vapor. The resulting mixtures of ions and bath gas were subsequently passed into a vacuum chamber by way of an adiabatic supersonic free jet expansion. The cooling during that expansion caused …