Chemistry Commons^™

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 …

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.

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 …

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. …

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 …

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 …

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) …

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 …

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 …

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.

Copper Nanowires Synthesis And Self-Assembly For Interconnect Applications, Srikar Rao Darmakkolla

Dissertations and Theses

One-dimensional (1D) nanomaterial self-assembly offers an excellent approach to the fabrication of highly complex nanodevices. Despite considerable effort and research, precisely controlling the orientation and positioning of nanowires (NWs) on a large-scale area and assembling into a functional device is still a state of the art problem. This thesis focuses on the dimensionally controlled copper nanowires (Cu NWs) synthesis, and magnetic field assisted self-assembly of cupronickel nanowires (Cu/Ni NWs) into interconnect structures on a carbon doped silicon dioxide (CDO) wafer.

CDO is a low dielectric constant (k) material used for copper interconnects in multilayered complex integrated circuits (ICs). …

Investigation Of Aerosol Optical And Chemical Properties Using Humidity Controlled Cavity Ring-Down Spectroscopy, Xijing Zhu

Dissertations and Theses

Scientists have been observing a change in the climate since the beginning of the 20^th century that cannot be attributed to any of the natural influences of the past. Natural and anthropogenic substances and processes perturb the Earth's energy budget, contributing to climate change. In particular, aerosols (particles suspended in air) have long been recognized to be important in processes throughout the atmosphere that affect climate. They directly influence the radiative balance of the Earth's atmosphere, affect cloud formation and properties, and are also key air pollutants that contribute to a variety of respiratory and cardiovascular diseases. Despite their …

Analysis Of The Acid-Base Balance Of Mainstream Tobacco Smoke And Its Effect On The Gas/Particle Partitioning Of Nicotine, Amy Kathleen Devita-Mcbride

Dissertations and Theses

Tobacco smoke particulate matter (PM) is a complex mixture of condensed organic compounds, with about 5 to 10% water. Its general properties are similar in some respects to that of atmospheric organic aerosol PM and thus provides a useful surrogate when studying atmospheric PM. Due to its ability to undergo acid-base chemistry, nicotine is of particular interest in the tobacco smoke system. The gas/particle partitioning of nicotine depends on the protonation state of nicotine in the particles, so the distribution of nicotine between these phases provides a means of understanding the acid-base balance in the tobacco smoke system. The goal …

Controlling Water Exchange Kinetics And Improving Paracest Imaging, Jacqueline R. Slack

Dissertations and Theses

Generating MR image contrast from exogenous contrast media through chemical exchange saturation transfer (CEST) offers several exciting new possibilities, such as multicolored imaging, the interleaving of pre- and post-contrast images, and the potential to perform ratiometric metabolic imaging. The major limitation of the deployment of CEST imaging is the comparatively high detection limits of exogenous agents and particularly at the low B_¹ power levels required to meet SAR requirements. The large chemical shifts afforded by paramagnetic (paraCEST) agents permit more rapid exchange kinetics and therefore potentially more effective contrast agents. Despite comparatively large chemical shifts, many Ln³⁺ DOTA-tetraamide …

Toxicant Formation In Dabbing: The Terpene Story, Jiries Meehan-Attrash, Wentai Luo, Robert M. Strongin

Chemistry Faculty Publications and Presentations

Inhalable, noncombustible cannabis products are playing a central role in the expansion of the medical and recreational use of cannabis. In particular, the practice of “dabbing” with butane hash oil has emerged with great popularity in states that have legalized cannabis. Despite their growing popularity, the degradation product profiles of these new products have not been extensively investigated. The study herein focuses on the chemistry of myrcene and other common terpenes found in cannabis extracts. Methacrolein, benzene, and several other products of concern to human health were formed under the conditions that simulated realworld dabbing. The terpene degradation products observed …

Investigations Of Electronic Cigarette Chemistry: 1. Formation Pathways For Degradation Products Using Isotopic Labeling; And 2. Gas/Particle Partitioning Of Nicotine And Flavor Related Chemicals In Electronic Cigarette Fluids, Kilsun Kim

Dissertations and Theses

Use of electronic cigarettes (e-cigarettes) is rapidly growing around the world. E-cigarettes are commonly used as an alternative nicotine delivery system, and have been advocated as generating lower levels of harmful chemicals compared to conventional cigarettes. Cigarette smoke-like aerosols are generated when e-cigarettes heat e-liquids. The main components of e-cigarette liquids are propylene glycol (PG) and glycerol (GL) in a varying ratio, plus nicotine and flavor chemicals. Both PG and GL are considered safe to ingest in foods and beverages, but the toxicity of these chemicals in aerosols is unknown. Current studies of e-cigarettes have mainly focused on dehydration and …

How To Be A Successful Organic Chemist, Alexander H. Sandtorv

PDXOpen: Open Educational Resources

How to be a successful organic chemist is meant as an introductory text for undergraduates taking organic chemistry teaching labs. The text is a clear and practical introduction to safety, chemical handling, organic chemistry techniques, and lab reports.

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Lyapunov Exponents And The Belousov-Zhabotinsky Oscillator: An Interactive Computational Approach, Matthew W. Eskew, Reuben H. Simoyi

Chemistry Faculty Publications and Presentations

The Belousov-Zhabotinsky (BZ) chemical oscillator is the most studied oscillator. It has been modelled on the basis of single-step mechanisms which have been continuously refined since the seminal manuscript by Field, Koros and Noyes in 1972. This manuscript reports on a unique way of modelling the global dynamics of the oscillator by assuming that the BZ oscillator has shown chaotic behaviour. The unique mathematical definition of chaos is very stringent, and, in this manuscript, we attempt to trace this unique exotic behaviour by the use of ‘onto’ maps of the interval onto itself which are known to exhaustively show a …

Formaldehyde Hemiacetal Sampling, Recovery, And Quantification From Electronic Cigarette Aerosols, James C. Salamanca, Ian Munhenzva, Jorge O. Escodedo, R. Paul Jensen, Angela Shaw, Robert Campbell, Wentai Luo, David H. Peyton, Robert Strongin

Chemistry Faculty Publications and Presentations

The electronic cigarette solvents propylene glycol and glycerol are known to produce toxic byproducts such as formaldehyde, acetaldehyde and acrolein. However, the aerosol toxin yield depends upon a variety of chemical and physical variables. The formaldehyde hemiacetals derived from these solvents were reported as major electronic cigarette aerosol components by us in 2015. In the study described herein, the formaldehyde hemiacetals were found at higher levels than those of free formaldehyde via an orthogonal sample collection protocol. In addition, the common aldehyde collection methods for electronic cigarettes, such as impingers and sorbent tubes containing DNPH, significantly underestimate the levels of …