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, …

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 …

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 …

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.

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 …

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. …

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 …

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 …

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 …

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.

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 …

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. …

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) …