Physical Sciences and Mathematics Commons^™

Structure Of Native Lens Connexin 46/50 Intercellular Channels By Cryo-Em, Janette B. Myers, Bassam G. Haddad, Susan E. O'Neill, Dror S. Chorev, Craig C. Yashioka, Carol V. Robinson, Daniel M. Zuckerman, Steve L. Reichow

Chemistry Faculty Publications and Presentations

Gap junctions establish direct pathways for cell-to-cell communication through the assembly of twelve connexin subunits that form intercellular channels connecting neighbouring cells. Co-assembly of different connexin isoforms produces channels with unique properties and enables communication across cell types. Here we used single-particle cryo-electron microscopy to investigate the structural basis of connexin co-assembly in native lens gap junction channels composed of connexin 46 and connexin 50 (Cx46/50). We provide the first comparative analysis to connexin 26 (Cx26), which—together with computational studies—elucidates key energetic features governing gap junction permselectivity. Cx46/50 adopts an open-state conformation that is distinct from the Cx26 crystal structure, …

Early Detection Of Corrosion Via Hydrogel-Based Spectroelectrochemical Sensors, Capri Ann Price

Dissertations and Theses

The backbone of the industrialized world is comprised of refined, zerovalent metal, a material which thermodynamically favors an oxidative return to more chemically stable states. There are many methods used to slow or delay this process, such as protective coatings, sacrificial anodes, and alloys, but no method can entirely prevent corrosion. This body of work instead proposes detecting the earliest chemical markers of corrosion: that is, metal ions as they solubilize from a metal surface. Such information would allow maintenance personnel to make informed decisions about the necessity or lack thereof of preventive maintenance, and intervene before advanced damage has …

Thiophene-Based Molecular Sensors Towards The Selective Detection Of Mercury(Ii) And Other Metals, Austin Kazuo Shigemoto

Dissertations and Theses

This work describes several thiophene-based molecular sensors and various modifications aimed to improve and understand the photophysical and supramolecular properties, such as the association constant (K_a) and selectivity, towards the development of a selective mercury(II) sensor. From the first generation of sensors containing pyridine and thiophene groups, it was determined that thiophene can offer good selectivity for mercury(II) against other transition metal ions, and provide a ratiometric absorption and fluorescent response. The projects following this focused on improving the K_a of the first generation of sensors through several different strategies. Substitution of thiophene for dibenzothiophene was …

Moving Beyond Alpha: A Primer On Alternative Sources Of Single-Administration Reliability Evidence For Quantitative Chemistry Education Research, Regis Komperda, Thomas C. Pentecost, Jack Barbera

Chemistry Faculty Publications and Presentations

This methodological paper examines current conceptions of reliability in chemistry education research (CER) and provides recommendations for moving beyond the current reliance on reporting coefficient alpha (α) as reliability evidence without regard to its appropriateness for the research context. To help foster a better understanding of reliability and the assumptions that underlie reliability coefficients, reliability is first described from a conceptual framework, drawing on examples from measurement in the physical sciences; then classical test theory is used to frame a discussion of how reliability evidence for psychometric measurements is commonly examined in CER, primarily in the form of single-administration reliability …

Triacetin Enhances Levels Of Acrolein, Formaldehyde Hemiacetals, And Acetaldehyde In Electronic Cigarette Aerosols, Shawna Vreeke, David H. Peyton, Robert Strongin

Chemistry Faculty Publications and Presentations

The health effects of inhaled electronic cigarette (ecigarette) flavoring compounds are largely unknown. Earlier reports of their chemical reactivity have been conflicting, with some claiming, for example, that the degradation of flavoring chemicals in e-cigarettes to aldehydes is statistically insignificant. It is thus important to understand how these molecules react to afford enhanced aerosol products. The purpose of the current study was to investigate the origin of formaldehyde, acrolein, and acetaldehyde in e-cigarettes that contain the popular additive, triacetin (TA). By using 13C labeling and a combination of 1H NMR and 13C NMR, we were able to identify that ester …

Development Of A Direct Aqueous Synthetic Route For The Production Of Elemental Bismuth Nanoparticles, Colin Jon Hiatt

Dissertations and Theses

Bismuth nanoparticles (Bi NPs) for use as an X-ray contrast material have gained significant traction in recent years due to the high atomic number and generally accepted biological tolerance of bismuth. However, to be considered a viable candidate for use in this application, water solubility is a necessity, which poses a challenge, since bismuth tends to readily oxidize. For this reason, research into the direct aqueous synthesis of Bi NPs is still in its infancy and can be very difficult, as described in Chapter 1. The remaining chapters of the thesis describe the direct aqueous synthesis of Bi NPs starting …

A Study Of Fragmentation And Spontaneous Covalent Self-Assembly Of The Azaorcus Ribozyme From Multiple Small Inactive Rna Fragments, Tharuka Sewwandi Jayathilaka

Dissertations and Theses

The question about the origins of life often appears as a difficult question to answer. A more reliable candidate molecule for the chemical origins of life would be a molecule that is capable of making copies of itself from simple precursors. With the finding of the catalytic activities of RNA molecules by Thomas Cech and Sid Altman in late 1980s, the term ribozyme was introduced to define an RNA molecule with catalytic activity. The RNA World is a conceptual period in the early stages in the development of life because RNA simultaneously possesses evolvability and catalytic function. An RNA molecule …

Analytical And Toxicological Evaluation Of Flavor Chemicals In Electronic Cigarette Refill Fluids, Rachel Z. Behar, Wentai Luo, Kevin J. Mcwhirter, James F. Pankow, Prue Talbot

Chemistry Faculty Publications and Presentations

Thousands of electronic cigarette refill fluids are commercially available. The concentrations of nicotine and the solvents, but not the flavor chemicals, are often disclosed on product labels. The purpose of this study was to identify and quantify flavor chemicals in 39 commercial refill fluids that were previously evaluated for toxicity. Twelve flavor chemicals were identified with concentrations ≥1 mg/ml: cinnamaldehyde, menthol, benzyl alcohol, vanillin, eugenol, p-anisaldehyde, ethyl cinnamate, maltol, ethyl maltol, triacetin, benzaldehyde, and menthone. Transfer of these flavor chemicals into aerosols made at 3V and 5V was efficient (mean transfer = 98%). We produced lab-made refill fluids containing …

Using Quenching To Detect Corrosion On Sculptural Metalwork: A Real-World Application Of Fluorescence Spectroscopy, Cory Hensen, Tami Lasseter Clare, Jack Barbera

Chemistry Faculty Publications and Presentations

Fluorescence spectroscopy experiments are a frequently taught as part of upper-division teaching laboratories. To expose undergraduate students to an applied fluorescence technique, a corrosion detection method, using quenching, was adapted from authentic research for an instrumental analysis laboratory. In the experiment, students acquire fluorescence spectra of sensing molecules in the presence of mock sculpture samples and discuss the condition of the sculptures based on the levels of soluble iron detected. This real-world-based experiment allows students the chance to engage with ongoing research and further understand the challenges with early detection of corrosion. Most students successfully completed the experiment, wrote a …

E-Cigarettes Can Emit Formaldehyde At High Levels Under Conditions That Have Been Reported To Be Non-Averse To Users, James C. Salamanca, Jiries Meehan-Attrash, Shawna Vreeke, Jorge O. Escobedo, David H. Peyton, Robert M. Strongin

Chemistry Faculty Publications and Presentations

E-cigarette aerosol emission studies typically focus on benchmarking toxicant levels versus those of cigarettes. However, such studies do not fully account for the distinct chemical makeup of e-liquids and their unique properties. These approaches often conclude that there are fewer and lower levels of toxins produced by e-cigarettes than by cigarettes. In 2015, we reported the discovery of new hemiacetals derived from the reaction of formaldehyde and the e-liquid solvents. The main finding was that they constituted a significant proportion of potentially undetected formaldehyde. Moreover, unlike gaseous formaldehyde, the hemiacetals reside in the aerosol particulate phase, and thus are capable …

Metallodithiolate Ligands For Reversing Metal Ion Induced Aggregation Of Beta Amyloid, Eleanor K. Adams, Marilyn Rampersad Mackiewicz

Student Research Symposium

Alzheimer’s Disease (AD) is the sixth leading cause of death in the United States with no known methods to cure, reverse or halt disease progression. The “metal hypothesis” states that Fe^II, Cu^II, Zn^II, and Al^II bind to truncated Aβ peptides and form soluble oligomers which deposit as senile plaques. These plaques play a crucial role in AD pathogenesis. For example, metallated-Aβ aggregates are hypothesized to disrupt membranes or generate a reactive oxygen species (ROS) through redox cycling in the presence of Cu^I/II or Fe^III/II and a reducing agent. ROS can lead …

Diagnostic Platform For Current Health Status Monitoring, Albert S. Benight, Megan M. Koslen, Matthew W. Eskew

Student Research Symposium

Our approach is based on physical measurements of blood plasma and exploits the plethora of information contained in the human plasma proteome, as a reporter of human health status. The assay involves collection and analysis ofthermograms of plasma from human blood measured by differential scanning calorimetry (DSC).

Plasma thermograms arise from the temperature-induced denaturation profile of proteins within blood plasma measured by DSC. This insightful measurement thereby provides a snapshot of the current state of the human plasma proteome which directly informs on overall systemic health. Such measurements have been shown to be highly accurate and sensitive indicators of health …

Multivalency Regulates Activity In An Intrinsically Disordered Transcription Factor, Sarah Clark, Janette B. Myers, Ashleigh King, Radovan Fiala, Jiri Novacek, Grant Pearce, Steve L. Reichow, Elisar J. Barbar

Chemistry Faculty Publications and Presentations

The transcription factor ASCIZ (ATMIN, ZNF822) has an unusually high number of recognition motifs for the product of its main target gene, the hub protein LC8 (DYNLL1). Using a combination of biophysical methods, structural analysis by NMR and electron microscopy, and cellular transcription assays, we developed a model that proposes a concerted role of intrinsic disorder and multiple LC8 binding events in regulating LC8 transcription. We demonstrate that the long intrinsically disordered C-terminal domain of ASCIZ binds LC8 to form a dynamic ensemble of complexes with a gradient of transcriptional activity that is inversely proportional to LC8 occupancy. The preference …

Imide Arylation With Aryl(Tmp)Iodonium Tosylates, Souradeep Basu, Alexander H. Sandtorv, David R. Stuart

Chemistry Faculty Publications and Presentations

Herein, we describe the synthesis of N-aryl phthalimides by metal-free coupling of potassium phthalimide with unsymmetrical aryl(TMP)iodonium tosylate salts. The aryl transfer from the iodonium moiety occurs under electronic control with the electronrich trimethoxyphenyl group acting as a competent dummy ligand. The yields of N-aryl phthalimides are moderate to high and the coupling reaction is compatible with electron-deficient and sterically encumbered aryl groups.

Combined Theoretical And Experimental Investigation Of Hydrogen Production Catalysis, Carolyn Noelle Virca

Dissertations and Theses

The widespread use of solar energy has been limited in part by the issue of effective storage. Water splitting is a means of converting solar energy into chemical fuel, in the form of hydrogen gas. It can be performed through both photochemical and electrochemical processes, via the two half reactions of water oxidation and proton reduction. Electrochemically, the catalyst receives electrons from an external circuit, which can be coupled to a renewable source such as a solar cell. Photochemically, a light-absorbing molecule provides an excited electron to a catalyst, which either generates oxygen or hydrogen gas. The work described herein …

The Preparation Of Diaryliodonium Salts For Application In Arylation Chemistry, Thomas Ludwig Seidl

Dissertations and Theses

Diaryliodonium salts offer potential as novel reagents for arylation chemistry. An overall goal and successful outcome of this work has been to further understanding of diaryliodonium salt chemistry by developing practical methods that enable chemists more convenient access to these reagents, for the purpose of reaction development. To this end a robust and convenient preparation method has been developed and resulted in novel commercially available diaryliodonium salts. The remainder of the work described, has focused on understanding the parameters important to diaryliodonium mediated arylation and has resulted in a solid framework that multiple future development efforts can build upon.

A …

Using Spectral Methods To Obtain Particle Size Information From Optical Data: Applications To Measurements From Cares 2010, Dean B. Atkinson

Chemistry Faculty Publications and Presentations

Multi-wavelength in situ aerosol extinction, absorption and scattering measurements made at two ground sites during the 2010 Carbonaceous Aerosols and Radiative Effects Study (CARES) are analyzed using a spectral deconvolution method that allows extraction of particle-sizerelated information, including the fraction of extinction produced by the fine-mode particles and the effective radius of the fine mode. The spectral deconvolution method is typically applied to analysis of remote sensing measurements. Here, its application to in situ measurements allows for comparison with more direct measurement methods and validation of the retrieval approach. Overall, the retrieved finemode fraction and effective radius compare well with …

Crystal Growth And Surface Modification Of Pyrite For Use As A Photovoltaic Material, Eric Rustad Young

Dissertations and Theses

Pyrite (FeS₂) has recently attracted significant interest as a photovoltaic material due to its promising optical properties, high photon to electron conversion yield, and low-cost raw materials. However, hopes have been tempered by recent discoveries that suggest the presence of hard to remove bulk sulfur defects. This research was focused on engineering and implementing the crystallization of pyrite from a sulfur rich solution to counteract the material's natural tendency to form bulk sulfur defects. Homoeptiaxial layers and single-crystal samples have been grown from tellurium sulfur melts with an Fe:S ratio of 1:4 using both natural and synthetic substrates. …

Development Of A Liquid Contacting Method For Investigating Photovoltaic Properties Of Pbs Quantum Dot Solids, Vitalii Alekseevich Dereviankin

Dissertations and Theses

Photovoltaic (PV) devices based on PbS quantum dot (QD) solids demonstrate high photon-to-electron conversion yields. However, record power conversion efficiencies remain limited mainly due to bulk and interfacial defects in the light absorbing material (QD solids). Interfacial defects can be formed when a semiconductor, such as QD solid, is contacted by another material and may predetermine the semiconductor/metal or semiconductor/metal-oxide junction properties. The objective of the work described in this dissertation was set to explore whether electrochemical contacting using liquid electrolytes can provide sufficient means of contacting the QD solids to investigate their PV performance without introducing the unwanted interfacial …

Flavour Chemicals In A Sample Of Non-Cigarette Tobacco Products Without Explicit Flavour Names Sold In New York City In 2015, Shannon M. Farley, Kevin R.J. Schroth, Victoria Grimshaw, Wentai Luo, Julia Lynn Degagne, Peyton A. Tierney, Kilsun Kim, James F. Pankow

Chemistry Faculty Publications and Presentations

Background Youth who experiment with tobacco often start with flavoured products. In New York City (NYC), local law restricts sales of all tobacco products with ‘characterising flavours’ except for ‘tobacco, menthol, mint and wintergreen’. Enforcement is based on packaging: explicit use of a flavour name (eg, ‘strawberry’) or image depicting a flavour (eg, a fruit) is presumptive evidence that a product is flavoured and therefore prohibited. However, a tobacco product may contain significant levels of added flavour chemicals even when the label does not explicitly use a flavour name.

Methods Sixteen tobacco products were purchased within NYC in 2015 that …

E‑Cigarette Airflow Rate Modulates Toxicant Profiles And Can Lead To Concerning Levels Of Solvent Consumption, Tetiana Korzun, Maryana Lazurko, Tetiana Korzun, Ian Munhenzva, Kelley Barsanti, Yilin Huang, R. Paul Jensen, Jorge O. Escobedo, Wentai Luo, David H. Peyton, Robert M. Strongin

Chemistry Faculty Publications and Presentations

Electronic cigarettes enabling enhanced airflow have grown in popularity in recent years. The objective of this study is to show that flow rates modulate the levels of specific aerosol toxicants produced in electronic cigarettes. Flow rates used in various laboratory investigations involving e-cigarettes have varied widely to date, and can thus promote interlaboratory variability in aerosol product profiles. The thermal decomposition of hydroxyacetone and glycolaldehyde is less favorable at lower temperatures, supporting the observations of these products at higher flow rates/lower heating coil temperatures. Higher temperatures promote the formation of acetaldehyde from hydroxyacetone and formaldehyde from both hydroxyacetone and glycolaldehyde. …

Connecting Chemistry To Community With Deliberative Democracy, Regis Komperda, Jack Barbera, Erin Shortlidge, Gwen Shusterman, Stem Education And Equity Institute, Portland State University

Biology Faculty Publications and Presentations

Science education communities have called for rethinking curricula to improve student understanding of the nature of science and the role of science in addressing controversial modern issues such as climate change, energy policy, and pollution levels. One approach to meeting this call is integrating these topics into class activities that require students to use discussion and scientific approaches to solve problems and deliberate potential policy solutions. Deliberative democracy (DD) is one such active learning approach in which students work in peer groups to reach a consensus on a scientific topic relevant to both real-world issues and course content. During DD …

Structure And Mechanism Of A Bacterial T6a Biosynthesis System, Amit Luthra, William Swinehart, Susan Bayooz, Phuc Phan, Boguslaw Stec, Dirk Iwata-Reuyl, Manal A. Swairjo

Chemistry Faculty Publications and Presentations

The universal N(6)-threonylcarbamoyladenosine (t⁶A) modification at position 37 of ANN-decoding tRNAs is central to translational fidelity. In bacteria, t⁶A biosynthesis is catalyzed by the proteins TsaB, TsaC/TsaC2, TsaD and TsaE. Despite intense research, the molecular mechanisms underlying t⁶A biosynthesis are poorly understood. Here, we report biochemical and biophysical studies of the t⁶A biosynthesis system from Thermotoga maritima. Small angle X-ray scattering analysis reveals a symmetric 2:2 stoichiometric complex of TsaB and TsaD (TsaB₂D₂), as well as 2:2:2 complex (TsaB₂D₂E₂), in …

Evaluation Of The Influence Of Wording Changes And Course Type On Motivation Instrument Functioning In Chemistry, Regis Komperda, Kathryn N. Hosbein, Jack Barbera

Chemistry Faculty Publications and Presentations

Increased understanding of the importance of the affective domain in chemistry education research has led to the development and adaptation of instruments to measure chemistry-specific affective traits, including motivation. Many of these instruments are adapted from other fields by using the word ‘chemistry’ in place of other disciplines or more general ‘science’ wording. Psychometric evidence is then provided for the functioning of the new adapted instrument. When an instrument is adapted from general language to specific (e.g. replacing ‘science’ with ‘chemistry’), an opportunity exists to compare the functioning of the original instrument in the same context as the adapted instrument. …

Paracest Agents Encapsulated In Reverse Nano-Assembled Capsules (Racs): How Slow Molecular Tumbling Can Quench Cest Contrast, Annah Farashishiko, Jacqueline R. Slack, Mauro Botta, Mark Woods

Chemistry Faculty Publications and Presentations

Although paraCEST is a method with immense scope for generating image contrast in MRI, it suffers from the serious drawback of high detection limits. For a typical discrete paraCEST agent the detection limit is roughly an order of magnitude higher than that of a clinically used relaxation agent. One solution to this problem may be the incorporation of a large payload of paraCEST agents into a single macromolecular agent. Here we report a new synthetic method for accomplishing this goal: incorporating a large payload of the paraCEST agent DyDOTAM3+ into a Reverse Assembled nano-Capsule. An aggregate can be generated between …

Varied Length Stokes Shift Bodipy-Based Fluorophores For Multicolor Microscopy, Amy M. Bittel, Ashley M. Davis, Lei Wang, Michel A. Nederlof, Jorge O. Escobedo, Robert Strongin, Summer L. Gibbs

Chemistry Faculty Publications and Presentations

Multicolor microscopy tools necessary to localize and visualize the complexity of subcellular systems are limited by current fluorophore technology. While commercial fluorophores cover spectral space from the ultraviolet to the near infrared region and are optimized for conventional bandpass based fluorescence microscopy, they are not ideal for highly multiplexed fluorescence microscopy as they tend to have short Stokes shifts, restricting the number of fluorophores that can be detected in a single sample to four to five. Herein, we synthesized a library of 95 novel boron-dipyrromethene (BODIPY)- based fluorophores and screened their photophysical, optical and spectral properties for their utility in …

Free-Base Nicotine Determination In Electronic Cigarette Liquids By 1H Nmr Spectroscopy, Anna K. Duell, James F. Pankow, David H. Peyton

Chemistry Faculty Publications and Presentations

E-liquids usually contain significant nicotine, which will exist primarily in two forms, monoprotonated and free-base, the proportions of which are alterable through the effective pH of the medium. The fraction of nicotine in the free-base form is α_fb, with 0 ≤ α_fb ≤ 1. When dosed via aerosol, the two nicotine forms have different mechanisms and kinetics of delivery, as well as differing implications for harshness of the inhaled aerosol, so α_fb is relevant regarding abuse liability. Previous attempts to determine α_fb in electronic cigarette liquids and vapor have been flawed. We employed the exchange-averaged …

Facile Synthesis Of Ligand-Free Iridium Nanoparticles And Their In Vitro Biocompatibility, Anna L. Brown, Hayden Winter, Andrea M. Goforth, Gaurav Sahay, Conroy Sun

Chemistry Faculty Publications and Presentations

High-density inorganic nanoparticles have shown promise in medical applications that utilize radiation including X-ray imaging and as radiation dose enhancers for radiotherapy. We have developed an aqueous synthetic method to produce small (~ 2 nm) iridium nanoparticles (IrNPs) by reduction of iridium(III) chloride using a borohydride reducing agent. Unlike other solution-based synthesis methods, uniform and monodispersed IrNPs are produced without the use of surfactants or other solubilizing ligands. These nanoparticles are highly crystalline as observed by X-ray diffraction and high-resolution transmission electron microscopy (TEM). In vitro metabolic toxicity assays using hepatocyte and macrophage cells demonstrate that both IrNPs and iridium(III) …

Boiling Points Of The Propylene Glycol + Glycerol System At 1 Atmosphere Pressure: 188.6–292 °C Without And With Added Water Or Nicotine, Anna K. Duell, James F. Pankow, Samantha M. Gillette, David H. Peyton

Chemistry Faculty Publications and Presentations

No abstract provided.