Materials Chemistry Commons^™

The Development And Application Of Instrumental Methods For The Identification Of Materials And Processes Used In The Manufacture Of Orotone, Hand-Colored Orotone, And Silvertone Photographs, Ivanny Jeannette Jácome-Valladares

Dissertations and Theses

Orotone photographs are positive photographic images on glass with a gold-colored metallic coating or backing. Although the materials and process used in the production of orotones have been previously documented, there is limited published scientific research on the subject. This study focused on expanding those published works by analyzing a greater number of photographs, including eleven orotones, four hand-colored orotones, two silvertones, and one uncoated orotone. The photographs, dating from the early to mid-20^th century, were from the University of Washington (UW) Libraries' collection, except for one orotone that was from the Portland Art Museum.

X-ray Fluorescence (XRF) spectroscopy, …

Soft Lithographic Replication Of High Length-Scale Micropillars From Laser-Ablated Fused-Silica Templates, Jason Pitts

University Honors Theses

Soft lithography is a well-established route to wafer-scale reproduction of micro- and nanoscale features in a wide variety of materials. Nevertheless, micron length scales have yet to be explored, despite the potential utility of such structures. Here, polymer micropillars of 6-12 μm length, approximately 0.5-1.5 μm wide at 10 μm spacing are reproduced from a polydimethylsiloxane (PDMS) mold made from patterned cellulose acetate (CA). The patterned CA was cast from a rigid fused silica template machined by a pulsed femtosecond laser. Pore topographic features were successfully reproduced in Norland Optical Adhesive (NOA), polycaprolactone (PCL), Nafion, acrylonitrile butadiene styrene (ABS), and …

A Simple Predictive Model For Estimating Relative E-Cigarette Toxic Carbonyl Levels, Shawna Vreeke, Xijing Zhu, Robert Strongin

Chemistry Faculty Publications and Presentations

E-cigarette devices are wide ranging, leading to significant differences in levels of toxic carbonyls in their respective aerosols. Power can be a useful method in predicting relative toxin concentrations within the same device, but does not correlate well to inter-device levels. Herein, we have developed a simple mathematical model utilizing parameters of an e-cigarette’s coil and wick in order to predict relative levels of e-liquid solvent degradation. Model 1, which is coil length/(wick surface area*wraps), performed in the moderate-to-substantial range as a predictive tool (R² = 0.69). Twelve devices, spanning a range of coil and wick styles, were analyzed. …

Dft Analysis Into The Intermediates Of Nickel Pyridenthiolate Catalysed Proton Reduction, Carolyn N. Virca, Theresa M. Mccormick

Chemistry Faculty Publications and Presentations

Nickel pyridine 2-thiolate (Ni(PyS)₃ −) has shown good stability and activity as a H₂ generation catalyst for use in solar energy storage. The experimentally proposed catalytic pathway is explored using DFT calculations. Free energy changes along the reaction coordinate, spin states, localization of charge and geometry of the intermediates were explored. Calculations were performed using Gaussian 09 with a B3P86/ 6-31+G(d) basis set and a CPCM water solvation model. Of particular interest were our findings that the first reduction occurs at the nickel rather than through non-innocent ligands and that water coordination is not favourable although protonation of …

Phthalimide-Based Π-Conjugated Small Molecules With Tailored Electronic Energy Levels For Use As Acceptors In Organic Solar Cells, Arthur D. Hendsbee, Seth M. Mcafee, Jon-Paul Sun, Theresa M. Mccormick, Ian G. Hill, Gregory C. Welch

Chemistry Faculty Publications and Presentations

The design, synthesis, and characterization of seven phthalimide-based organic π-conjugated small molecules are reported. The new materials are based on a phthalimide–thiophene–CORE–thiophene–phthalimide architecture. The CORE units utilized were phthalimide (M2), diketopyrrolopyrrole (M3), isoindigo (M4), naphthalene diimide (M5), perylene diimide (M6), and difluorobenzothiadiazole (M7); they were specifically selected to progressively increase the electron affinity of the resulting compound. A small molecule with no core (M1) was synthesized for comparison. Each material was synthesized through optimized direct heteroarylation cross-coupling procedures using bench top solvents in air. Combinations of …

Reducing The Effects Of Shot Noise Using Nanoparticles, Moshood K. Morakinyo, Shankar B. Rananavare

Chemistry Faculty Publications and Presentations

We present a hybrid nano-lithographic approach to minimizes the effects of line edge roughness and shot noise in nano-hole patterning by reflowing photoresist polymers around the nanoparticles deposited using self-assembly and simple etch chemistries. The method extends the transistor contact holes patterning limits to below 20 nm.

A Facile Route To Tailoring Peptide-Stabilized Gold Nanoparticles Using Glutathione As A Synthon, Rosina Ho Wu, Tan P. Nguyen, Grant W. Marquart, Thomas J. Miesen, Theresa Mau, Marilyn R. Mackiewicz

Chemistry Faculty Publications and Presentations

The preparation of gold nanoparticles (AuNPs) of high purity and stability remains a major challenge for biological applications. This paper reports a simple synthetic strategy to prepare water-soluble peptide-stabilized AuNPs. Reduced glutathione, a natural tripeptide, was used as a synthon for the growth of two peptide chains directly on the AuNP surface. Both nonpolar (tryptophan and methionine) and polar basic (histidine and dansylated arginine) amino acids were conjugated to the GSH-capped AuNPs. Ultracentrifugation concentrators with polyethersulfone (PES) membranes were used to purify precursor materials in each stage of the multi-step synthesis to minimize side reactions. Thin layer chromatography, transmission electron …

The Impact Of Surface Ligands And Synthesis Method On The Toxicity Of Glutathione-Coated Gold Nanoparticles, Bryan Harper, Federico Sinche, Meenambika Gowrishankar, Grant Marquart, Marilyn R. Mackiewicz, Stacey L. Harper

Chemistry Faculty Publications and Presentations

Gold nanoparticles (AuNPs) are increasingly used in biomedical applications, hence understanding the processes that affect their biocompatibility and stability are of significant interest. In this study, we assessed the stability of peptide-capped AuNPs and used the embryonic zebrafish (Danio rerio) as a vertebrate system to investigate the impact of synthesis method and purity on their biocompatibility. Using glutathione (GSH) as a stabilizer, Au-GSH nanoparticles with identical core sizes were terminally modified with Tryptophan (Trp), Histidine (His) or Methionine (Met) amino acids and purified by either dialysis or ultracentrifugation. Au-GSH-(Trp)2 purified by dialysis elicited significant morbidity and mortality at …

Photocatalytic Hydrogen Production From A Noble Metal Free System Based On A Water Soluble Porphyrin Derivative And A Cobaloxime Catalyst, Theodore Lazarides, Milan Delor, Igor V. Sazanovich, Theresa M. Mccormick, Irene Georgakaki, Georgios Charalambidis, Julia A. Weinstein, Athanassios G. Coutsolelos

Chemistry Faculty Publications and Presentations

A combination of noble-metal free components, a water soluble porphyrin photosensitizer zincmeso-tetrakis(1-methylpyridinium-4-yl)porphyrin chloride [ZnTMPyP⁴⁺]Cl₄ (1) with cobaloxime complex [Co^III(dmgH)₂(py)Cl] (2) as a catalyst, creates an efficient system for photochemical hydrogen production acting under visible light with 280 TONs. This is the first example of a water soluble porphyrin acting as a photosensitizer for cobaloxime catalysed H₂ production.

Robust Visible Light Photoswitching With Ortho-Thiol Substituted Azobenzenes, Subhas Samanta, Theresa M. Mccormick, Simone K. Schmidt, Dwight S. Seferos, G. Andrew Woolley

Chemistry Faculty Publications and Presentations

Introduction of S-ethyl groups in all four ortho positions of azobenzene prevents reduction of the azo group by intracellular glutathione, while enhancing the absorptivity to ∼10000 M⁻¹ cm⁻¹ in the blue and green regions of the visible spectrum. cis-to-trans isomerization occurs thermally on the minutes timescale. Further, this substitution pattern permits switching with red light, a color that is more penetrating through biological tissues than other parts of the visible spectrum.

Surfactant-Free Hybridization Of Transition Metal Oxide Nanoparticles With Conductive Graphene For High-Performance Supercapacitor, Wen Qian, Zhiqiang Chen, Steven Cottingham, William Alexander Merrill, Natasja A. Swartz, Andrea Goforth, Tami Lasseter Clare, Jun Jiao

Chemistry Faculty Publications and Presentations

In order to improve specific capacitance and limit electrical resistance, high-quality exfoliatedgraphene decorated with transition metal (Fe, Mn, Co) oxide nanoparticles (NPs) has been successfully synthesized without the use of surfactant via a simple, general, environmentally-friendly chemical process. The specific capacitance of as-prepared graphene/Mn₃O₄ composite reach 239.6 F/g, when employed as the anode material in neutral NaCl electrolyte solutions (cf. 98.2 F/g for pristine graphene and 141.4 F/g for pure Mn₃O₄ NPs), which indicate the synergetic effects from both graphene and attached Mn₃O₄ NPs. Moreover, the high conductivity of …

Microscopic Formulation Of The Zimm-Bragg Model For The Helix-Coil Transition, A. V. Badasyan, A. Giacometti, Y. S. Mamasakhlisov, V. F. Morozov, Albert S. Benight

Chemistry Faculty Publications and Presentations

A microscopic spin model is proposed for the phenomenological Zimm-Bragg model for the helix-coil transition in biopolymers. This model is shown to provide the same thermophysical properties of the original Zimm-Bragg model and it allows a very convenient framework to compute statistical quantities. Physical origins of this spin model are made transparent by an exact mapping into a one-dimensional Ising model with an external field. However, the dependence on temperature of the reduced external field turns out to differ from the standard one-dimensional Ising model and hence it gives rise to different thermophysical properties, despite the exact mapping connecting them. …

A Photochemically Initiated Chemistry For Coupling Underivatized Carbohydrates To Gold Nanoparticles, Xin Wang, Olof Ramström, Mingdi Yan

Chemistry Faculty Publications and Presentations

The sensitive optoelectronic properties of metal nanoparticles make nanoparticle-based materials a powerful tool to study fundamental biorecognition processes. Here we present a new and versatile method for coupling underivatized carbohydrates to gold nanoparticles (Au NPs) via the photochemically induced reaction of perfluorophenylazide (PFPA). A one-pot procedure was developed where Au NPs were synthesized and functionalized with PFPA by a ligand-exchange reaction. Carbohydrates were subsequently immobilized on the NPs by a fast light activation. The coupling reaction was efficient, resulting in high coupling yield as well as high ligand surface coverage. A colorimetric system based on the carbohydrate-modified Au NPs was …

Enhanced Magnetic Quantum Oscillations In The Mixed State Of A Two-Dimensional Organic Superconductor, J. Wosnitza, J. Hagel, P. J. Meeson, D. Bintley, J. A. Schlueter, Javid Mohtasham, Rolf Walter Winter, Gary L. Gard

Chemistry Faculty Publications and Presentations

We report on de Haas–van Alphen (dHvA) oscillations observed in the mixed state of the organic superconductor β″–(BEDT-TTF)₂SF₅CH₂CF₂SO₃ (BEDT-TTF stands for bisethylenedithio-tetrathiafulvalene) utilizing the field-modulation technique and torque magnetometry. At low temperatures (30 mK), the dHvA signal persists down to 1.4 T well below the upper critical field Bc2≈3.6T. Contrary to most theoretical predictions and previous experimental findings, no additional damping of the dHvA-oscillation amplitude, but a reduced damping of the dHvA signal is found. This highly unusual effect might indicate a reduced quasiparticle scattering rate or an additional oscillatory contribution in the superconducting state.

Orientational Phase Transition In Na_{X}C_{60} (1, T. Yildirim, J. E. Fischer, A. B. Harris, Peter W. Stephens, Dengfa Liu, Laurent Brard, Robert M. Strongin, Amos B. Smith Iii

Chemistry Faculty Publications and Presentations

X-ray diffraction and calorimetry data on cubic Na_xC₆₀(1<x60, e.g., T_m(x=1.3)=325 K. The ordered phases are the same as in pure C₆₀: simple cubic, space group Pa3¯, but the orientations in the disordered phase are more restricted. We explain how Na stabilizes the ordered phase to rather high T, while K and Rb do not, in terms of Coulomb interactions between C₆₀ molecules and and Na ions which we calculate from the local charge density of C₆₀.

Kinetics Of The Cope Rearrangement Of 3,4-Diphenylhexa-1,5-Diene, Harlan Albert Jerome Berg

Dissertations and Theses

Kinetics investigations of the thermal Cope rearrangement of meso-and d1-3,4-diphenylhexa-1,5-dienes were undertaken in order to gain information about the transition states for these reactions by determining the appropriate enthalpies and entropies of activation. Of particular interest were the activation parameters for the meso compounds' rearrangement as it represents the only known example in which both four-and six-centered transition states are of comparable energy.

Kinetics of the dl isomers' rearrangement in the temperature range 90-110⁰were determined using 5 X 10¯⁵M solutions of the olefin in heptane contained within sealed Pyrex ampules. Extents of reaction were determined from UV absorbance measurements at …

On The Mechanism Of The Diels-Alder Reaction--Dimerization Of Trans-Phenylbutadiene, Michael Ward Mcnicholas

Dissertations and Theses

The Diels-Alder dimerization of trans-1-substituted butadienes is expected to yield a cyclohexene adduct with the substituents in the 3 and 4 positions cis to one another. This prediction is based on past observations of other Diels-Alder additions. The cis-isomer is the only one consistent with a two-stage mechanism proposed by Woodward and Katz.

In the case of trans-phenylbutadiene, the expected adduct is cis-3-phenyl 1-4-(trans-styry1) cyclohexene. Alder, Haydn and Vogt, however, reported that the corresponding trans-isomer is the dimerization product. There is reason to believe that the observation of the trans-isomer may have been the result of product isomerization during purification. …

Evidence For The Existence Of Two Stable Sites For Cobalt Impurity Atoms In Aluminum, Arun Venkatachar

Dissertations and Theses

Using Fe⁵⁷Mössbauer spectroscopy, two alternative sites occupied by cobalt (10^-4 at. % ) impurity atoms in aluminum have been isolated. The substitutional site A is the stable position after annealing the sample above 840 K, followed by a rapid quench. The impurity atoms in site A are characterized by a single line Mössbauer spectrum (indicative of a cubic environment), a room-temperature f = 0.502 (r. m. s. displ. 0.071 A) and an I. S. (reI. to Fe) = -0.421 mm/sec. For anneals below 770 K the cobalt atoms migrate to site B, which is characterized by a …

Investigation Of The Alpha-Sub-Gamma Phase In Alnico 6, Cortez Samuel

Dissertations and Theses

The purpose of this research project was to study the αᵧ phase in Alnico 6. Other phases were studies for comparison. Also the effect of an applied magnetic field on the formation of the αᵧ phase was investigated.

Three single crystals of Alnico 6 were heat treated for one hour—one at 1250°C, one at 1000°C, and one at 800°C—and water-quenched. The microstructure of each sample was observed with the optical microscope, and X-ray diffraction patterns were taken to determine the crystal structure of the phases present.

Several single crystal samples of Alnico 6 were heat treated at 1000°C and furnace-cooled. …