Chemistry Commons^™

Alignment Of Theoretically Grounded Constructs For The Measurement Of Science And Chemistry Identity, Kathryn Nicole Hosbein, Jack Barbera

Chemistry Faculty Publications and Presentations

Identity has been theorized to aid in student persistence within STEM disciplines. In this study, science and chemistry identity were defined as being recognized as a science or chemistry person within the classroom. To generalize the effects that identity has on student persistence, a measurable construct must be defined, operationalized, and tested in multiple settings with different populations. This project addressed the first step in the process, defining the construct and grounding it in an established theoretical framework. This qualitative project utilized a previously described physics identity framework, with sub-constructs of performance/competence, recognition, and interest, as a starting point for …

Iodane-Guided C-H Cleavage To Synthesize Densely Functionalized Arenes, Aleksandra Nilova, Paul A. Sibbald, Edward J. Valente, Gisela Gonzalez-Monteil, H. Camille Richardson, Kevin S. Brown, Paul Cheong, David Stuart

Chemistry Faculty Publications and Presentations

We describe a strategy for the iodane-guided functionalization of sterically congested C-H bonds, which is distinct from electronic, steric or proximity guided C-H functionalization methods. Readily accessible aryl(Mes)iodonium salts serve as the starting materials in these reactions and produce complex 1,2,3,4-substituted arenes via aryne intermediates. This approach is especially powerful when coupled with the innate C-H functionalization reactivity of simple arenes, to replace two C-H bonds with two C-C or C-heteroatom bonds while over-riding steric effects that typically inhibit such reactions. DFT stud-ies reveal a contribution of inductive, resonance, and steric effects on the regioselectivity of C-H cleavage and aryne …

Convective Instabilities Derived From Dissipation Of Chemical Energy, Reuben H. Simoyi, Matthew W. Eskew

Chemistry Faculty Publications and Presentations

Oxidation reactions of a series of organosulfur compounds by chlorite are excitable, autocatalytic, and exothermic and generate a lateral instability upon being triggered by the autocatalyst. This article reports on the convective instabilities derived from the reaction of chlorite and thiourea in a Hele-Shaw cell. Reagent concentrations used for the development of convective instabilities delivered a temperature jump at the wave front of 2.1 K. The reaction zone was 2 mm and due to normal cooling after the wave front, this induced a spike rather than the standard well-studied front propagation. Localized spatiotemporal patterns develop around the wave front. This …

Assessing Affective Differences Between A Virtual General Chemistry Experiment And A Similar Hands-On Experiment, Cory Hensen, Jack Barbera

Chemistry Faculty Publications and Presentations

To date, few general chemistry laboratory studies have included affective measures despite calls for more research on aspects of this domain. This shortage of studies may be partially due to the scarcity of affective measures that have been designed for, or tested in, the college laboratory setting. To provide measures for use in this environment, several existing affective scales were adapted for this new context. Before data from the scales were utilized to study the environment, evidence was provided for the validity and reliability of the data generated from them. Once sufficient evidence was provided, it was possible to determine …

E-Cigarette Chemistry And Analytical Detection, Robert M. Strongin

Chemistry Faculty Publications and Presentations

The study of e-cigarette aerosol properties can inform public health while longer-term epidemiological investigations are ongoing. The determination of aerosol levels of known toxins, as well as of molecules with unknown inhalation toxicity profiles, affords specific information for estimating the risks of e-cigarettes and for uncovering areas that should be prioritized for further investigation.

Crystal Structures Of Dotma Chelates From Ce³+ To Yb³+ : Evidence For A Continuum Of Metal Ion Hydration States, Mark Woods, Katherine M. Payne, Edward J. Valente, Benjamin E. Kucera, Victor G. Young

Chemistry Faculty Publications and Presentations

The crystal structures of chelates formed between each stable paramagnetic lanthanide ion and DOTMA are described. A total of 23 individual chelates structures were obtained, in each chelate the coordination geometry around the metal ion is best described as a twisted square antiprism (torsion angle -25.0° – - 31.4°). Despite the uniformity of the general coordination geometry provided by the DOTMA ligand, there is a considerable variation in the hydration state of each chelate. The early Ln3⁺ chelates are associated with a single inner sphere water molecule, the Ln-OH₂ interaction is remarkable for being very long. After a …

Spontaneous Advent Of Genetic Diversity In Rna Populations Through Multiple Recombination Mechanisms, Benedict A. Smail, Bryce E. Clifton, Ryo Mizuuchi, Niles Lehman

Chemistry Faculty Publications and Presentations

There are several plausible abiotic synthetic routes from prebiotic chemical materials to ribonucleotides and even short RNA oligomers. However, for refinement of the RNA World hypothesis to help explain the origins of life on the Earth, there needs to be a manner by which such oligomers can increase their length and expand their sequence diversity. Oligomers longer than at least 10-20 nucleotides would be needed for raw material for subsequent natural selection. Here, we explore spontaneous RNA-RNA recombination as a facile means by which such length and diversity enhancement could have been realized. Motivated by the discovery that RNA oligomers …

Metrics And Methods Used To Compare Student Performance Data In Chemistry Education Research Articles, Michael R. Mack, Cory Hensen, Jack Barbera

Chemistry Faculty Publications and Presentations

Quasi-experiments are common in studies that estimate the effect of instructional interventions on student performance outcomes. In this type of research, the nature of the experimental design, the choice in assessment, the selection of comparison groups, and the statistical methods used to analyze the comparison data dictate the validity of causal inferences. Therefore, gathering and reporting validity evidence in causal studies is of utmost importance, especially when conclusions have real policy implications for students and faculty, among other stakeholders. This review examines 24 articles that reported quantitative investigations of the effect of instructional interventions on performance-based outcomes conducted within undergraduate …

Conformational Communication Mediates The Reset Step In T6a Biosynthesis, Amit Luthra, Naduni Paranagama, William Swinehart, Susan Bayooz, Phuc Phan, Vanessa Quach, Jamie M. Schiffer, Boguslaw Stec, Dirk Iwata-Reuyl, Manal A. Swairjo

Chemistry Faculty Publications and Presentations

The universally conserved N 6-threonylcarbamoylade nosine (t 6 A) modification of tRNA is essential for translational fidelity. In bacteria, t 6 A biosynthesis starts with the TsaC/TsaC2-catalyzed synthesis of the intermediate threonylcarbamoyl adenylate (TC-AMP), followed by transfer of the threonylcarbamoyl (TC) moiety to adenine-37 of tRNA by the TC-transfer complex comprised of TsaB, TsaD and TsaE sub-units and possessing an ATPase activity required for multi-turnover of the t 6 A cycle. We report a 2.5-˚ A crystal structure of the T. maritima TC-transfer complex (TmTsaB 2 D 2 E 2) bound to Mg 2+-ATP in the AT-Pase site, and substrate …

Elq-331 As A Prototype For Extremely Durable Chemoprotection Against Malaria, Martin J. Smilkstein, Sovitj Pou, Alina Krollenbrock, Lisa A. Bleyle, Rozalia A. Dodean, Lisa Frueh, David J. Hinrichs, Multiple Additional Authors

Chemistry Faculty Publications and Presentations

The potential benefits of long-acting injectable chemoprotection (LAI-C) against malaria have been recently recognized, prompting a call for suitable candidate drugs to help meet this need. On the basis of its known pharmacodynamic and pharmacokinetic profiles after oral dosing, ELQ-331, a prodrug of the parasite mitochondrial electron transport inhibitor ELQ-300, was selected for study of pharmacokinetics and efficacy as LAI-C in mice.

Four trials were conducted in which mice were injected with a single intramuscular dose of ELQ-331 or other ELQ-300 prodrugs in sesame oil with 1.2% benzyl alcohol; the ELQ-300 content of the doses ranged from 2.5 to 30 …

Limited Sequence Diversity Within A Population Supports Prebiotic Rna Reproduction, Ryo Mizuuchi, Niles Lehman

Chemistry Faculty Publications and Presentations

The origins of life require the emergence of informational polymers capable of reproduction. In the RNA world on the primordial Earth, reproducible RNA molecules would have arisen from a mixture of compositionally biased, poorly available, short RNA sequences in prebiotic environments. However, it remains unclear what level of sequence diversity within a small subset of population is required to initiate RNA reproduction by prebiotic mechanisms. Here, using a simulation for template-directed recombination and ligation, we explore the effect of sequence diversity in a given population for the onset of RNA reproduction. We show that RNA reproduction is improbable in low …

Spatial Fingerprinting Of Biogenic And Anthropogenic Volatile Organic Compounds In An Arid Unsaturated Zone, Christopher T. Green, Wentai Luo, Christopher H. Conaway, Karl B. Haase, Ronald J. Baker

Chemistry Faculty Publications and Presentations

Subsurface volatile organic compounds (VOCs) can pose risks to human and environmental health and mediate biological processes. Volatile organic compounds have both anthropogenic and biogenic origins, but the relative importance of these sources has not been explored in subsurface environments. This study synthesized 17 yr of VOC data from the Amargosa Desert Research Site in Nevada with the goal of improving understanding of spatial and temporal variations that distinguish sources of VOCs from a landfill and from ambient sources including biogenic VOCs (bVOCs). Gas samples were collected from 1999 to 2016 from an array of shallow sample points (0.5- and …

Targeting Mitochondria In Cancer Therapy Could Provide A Basis For The Selective Anticancer Activity, Dmitri Rozanov, Anton Cheltsov, Aaron Nilsen, Christopher Boniface, Isaac Forquer, James Korkola, Joe Gray, Multiple Additional Authors

Chemistry Faculty Publications and Presentations

To determine the target of the recently identified lead compound NSC130362 that is responsible for its selective anti-cancer efficacy and safety in normal cells, structure-activity relationship (SAR) studies were conducted. First, NSC13062 was validated as a starting compound for the described SAR studies in a variety of cell-based viability assays. Then, a small library of 1,4-naphthoquinines (1,4-NQs) and quinoline-5,8-diones was tested in cell viability assays using pancreatic cancer MIA PaCa-2 cells and normal human hepatocytes. The obtained data allowed us to select a set of both non-toxic compounds that preferentially induced apoptosis in cancer cells and toxic compounds that induced …

Aerosol Gas-Phase Components From Cannabis E‑Cigarettes And Dabbing: Mechanistic Insight And Quantitative Risk Analysis, Jiries Meehan-Atrash, Wentai Luo, Kevin J. Mcwhirter, Robert M. Strongin

Chemistry Faculty Publications and Presentations

Consumption of cannabis by nontraditional methods has surged since the advent of legalization in North America and worldwide. Inhaling cannabis extracts using vaporizers and via dabbing has risen in popularity, while concerns over product safety have not hindered their proliferation. The work herein is the first step toward assessing the safety of vaporizing and dabbing concentrated cannabis extracts as a function of gas-phase reaction products. The gas-phase thermal degradants of Δ9- tetrahydrocannabinol (THC) have not been previously investigated. It was found that users may be exposed to concerning degradants such as methacrolein, benzene, and methyl vinyl ketone when using cartridge …

Synthesis Of 4-Methylbenzoate(2ʹ,4ʹ,6ʹ-Trimethoxyphenyl) Iodonium Tosylate, Thomas Ludwig Seidl, Aaron Moment, Charles Orella, Thomas Vickery, David R. Stuart

Chemistry Faculty Publications and Presentations

Hypervalent iodine continues to intrigue organic chemists with its diverse breadth of reactivity. The use of diaryliodonium salts as aryltransfer reagents has increased dramatically in the past decade as they have become more available by the development of efficient “one-pot” synthesis methods. Unsymmetrical diaryliodonium salts that selectively, and predictably, transfer one aryl group over the other are particularly desirable reagents, especially for the transfer of elaborate aryl groups to nucleophilic moieties. While the mesityl (Mes; 2,4,6-trimethylphenyl) group effectively serves as a general auxiliary in metal-catalyzed reactions of diaryliodonium salts, a broadly applicable auxiliary has not been adopted in metal-free reactions. …

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 …

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 …

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. …

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 …

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) …