Chemistry Commons^™

Statistical Comparison Of Results Of Redox Titrations Using K-2 Cr-2o-7 And Kio-3 In The Undergraduate Analytical Chemistry Lab, David W. Randall, Luis K. Garibay

Faculty Publications

Reducing the quantity of hazardous substances used and hazardous waste generated by under- graduate laboratory experiments is important. However, simply replacing hazardous compounds with less hazardous reagents may not retain the pedagogical (or analytical) goal of the experiment if the chemistry does not fundamentally work. We evaluated several literature-based replacement oxidants for K2Cr2O7 (potassium dichromate) and identified KIO3 (potassium iodate) as the only che- mically viable alternative for thiosulfate standardizations, consistent with use of iodate by others. Using ANOVA analysis, two years of student results where K2Cr2O7 was used as the oxidant were compared with two years of student results …

Mineralogical Transformation And Electrochemical Nature Of Magnesium-Rich Primers During Natural Weathering, Shashi S. Pathak, Michael D. Blanton, Sharathkumar K. Mendon, James W. Rawlins

Faculty Publications

Magnesium-rich primers (MgRP) have generated great interest as a promising alternative to chromium-based primers for the protection of aluminum substrates but their performance during exterior exposure has not been well documented. This paper focuses on the evaluation of MgRP during natural weathering to gain insight into its mineralogical phase transformation and electrochemical nature. Control studies were conducted on Mg and AA2024-T3 coupons. The results indicate that Mg particles in MgRP transform into a variety of hydroxide, carbonate, and hydroxy carbonates. During natural weathering, CO₂ inhibited the dissolution of both Mg and AA2024-T3 as a result of protective carbonate layer …

A Td-Dft Study Of The Absorption Spectra Of Mono-Nitrated Fluoranthenes [Abstract], Kefa Karimu Onchoke

Faculty Publications

No abstract provided.

Uv Curable Coatings For Improved Gas Barrier Properties Of Poly(Ethylene Terephthalate), Ethem Kaya, Tara Smith, Lon J. Mathias

Faculty Publications

A new high-barrier coating based on methyl (alpha-hydroxymethyl)acrylate (MHMA) for poly(ethylene terephthalate) (PET) was developed along with the process for preform dipping and cure prior to blow molding into bottles. The UV curable coating gives excellent gas barrier improvement when coated onto PET biaxially oriented thin films. Blown bottle side walls from coated PET preforms also show 2-3 times improvement over uncoated side walls. The effect of photoinitiator concentration, initiator types, and temperature on photopolymerization kinetics of MHMA was investigated. Once the photoinitiator, lrgacure 819 (R), concentration became larger than 1 mol%, a decrease in rate of propagation was observed. …

Sustainable Thermoplastic Elastomers Derived From Renewable Cellulose, Rosin And Fatty Acids, Y. Liu, K. Yao, Xiaoming Chen, Jifu Wang, Zhongkai Wang, Harry J. Ploehn, C. Wang, F. Chu, Chuanbing Tang

Faculty Publications

Two series of graft copolymers, cellulose-g-poly(n-butyl acrylate-co-dehydroabietic ethyl methacrylate) (Cell-g-P(BA-co-DAEMA)) and cellulose-g-poly(lauryl methacrylate-co-dehydroabietic ethyl methacrylate) (Cell-g-P(LMA-co-DAEMA)), were prepared by “grafting from” atom transfer radical polymerization (ATRP). In these novel graft copolymers, cellulose, DAEMA (derived from rosin), and LMA (derived from fatty acids) are all sourced from renewable natural resources. The “grafting from” ATRP strategy allows the preparation of high molecular weight graft copolymers consisting of a cellulose main chain with acrylate copolymer side chains. By manipulating the monomer ratios in the P(BA- …

Tuning The Underwater Oleophobicity Of Graphene Oxide Coatings Via Uv Irradiation, H. Li, Yi Huang, Y. Mao, W. Xu, Harry J. Ploehn, Miao Yu

Faculty Publications

Ultraviolet (UV) irradiation was utilized to gradually modify the chemistry and structure of graphene oxide (GO) flakes, as confirmed by XPS and AFM. Ultrathin GO coatings/membranes, made of UV-irradiated flakes, showed tunable underwater oleophobicity. UV-treated, superoleophobic GO membranes exhibited excellent antifouling capability for oil/water separation.

Hydrogen Evolution Reaction Measurements Of Dealloyed Porous Nicu, Kyla Koboski, Evan Nelsen, Jennifer R. Hampton

Faculty Publications

Porous metals are of interest for their high surface area and potential for enhanced catalytic behavior. Electrodeposited NiCu thin films with a range of compositions were electrochemically dealloyed to selectively remove the Cu component. The film structure, composition, and reactivity of these samples were characterized both before and after the dealloying step using scanning electron microscopy, energy-dispersive spectroscopy, and electrochemical measurements. The catalytic behavior of the dealloyed porous Ni samples towards the hydrogen evolution reaction was measured and compared to that of the as-deposited samples. The dealloyed samples were generally more reactive than their as-deposited counterparts at low overpotentials, making …

Acoustic Droplet Vaporization In Biology And Medicine, Chung-Yin Lin, William G. Pitt

Faculty Publications

This paper reviews the literature regarding the use of acoustic droplet vaporization (ADV) in clinical applications of imaging, embolic therapy, and therapeutic delivery. ADV is a physical process in which the pressure waves of ultrasound induce a phase transition that causes superheated liquid nanodroplets to form gas bubbles. The bubbles provide ultrasonic imaging contrast and other functions. ADV of perfluoropentane was used extensively in imaging for preclinical trials in the 1990s, but its use declined rapidly with the advent of other imaging agents. In the last decade, ADV was proposed and explored for embolic occlusion therapy, drug delivery, aberration correction, …

Short, Strong Halogen Bonding In Co-Crystals Of Pyridyl Bis-Urea Macrocycles And Iodoperfluorocarbons, Michael F. Geer, James Mazzuca, Mark D. Smith, Linda S. Shimizu

Faculty Publications

No abstract provided.

A Supramolecular Strategy To Assemble Multifunctional Viral Nanoparticles, Limin Chen, Xia Zhao, Yuan Lin, Yubin Huang, Qian Wang

Faculty Publications

Using a one-pot approach driven by the supramolecular interaction between β-cyclodextrin and adamantyl moieties, multifunctional viral nanoparticles can be facilely formulated for biomedical applications.

Cross-Species Malaria Immunity Induced By Chemically Attenuated Parasites, Michael F. Good, Jennifer M. Reiman, I. Bibiana Rodriguez, Koichi Ito, Stephanie K. Yanow, Ibrahim M. El-Deeb, Michael R. Batzloff, Danielle I. Stanisic, Christian Engwerda, Terry Spithill, Stephen L. Hoffman, Moses Lee, Virginia Mcphun

Faculty Publications

Vaccine development for the blood stages of malaria has focused on the induction of antibodies to parasite surface antigens, most of which are highly polymorphic. An alternate strategy has evolved from observations that low-density infections can induce antibody-independent immunity to different strains. To test this strategy, we treated parasitized red blood cells from the rodent parasite Plasmodium chabaudi with secocyclopropyl pyrrolo indole analogs. These drugs irreversibly alkylate parasite DNA, blocking their ability to replicate. After administration in mice, DNA from the vaccine could be detected in the blood for over 110 days and a single vaccination induced profound immunity to …

Electron Transfer By Excited Benzoquinone Anions: Slow Rates For Two-Electron Transitions, Matibur Zamadar, Andrew R. Cook, Anna Lewandowska-Andralojc, Richard Holroyd, Yan Jiang, Jin Bikalis, John R. Miller

Faculty Publications

Electron transfer (ET) rate constants from the lowest excited state of the radical anion of benzoquinone, BQ−•*, were measured in THF solution. Rate constants for bimolecular electron transfer reactions typically reach the diffusion-controlled limit when the free-energy change, ΔG°, reaches −0.3 eV. The rate constants for ET from BQ−•* are one-to-two decades smaller at this energy and do not reach the diffusion-controlled limit until −ΔG° is 1.5−2.0 eV. The rates are so slow probably because a second electron must also undergo a transition to make use of the energy of the excited state. Similarly, ET, from solvated electrons to neutral …

Vpt2+K Spectroscopic Constants And Matrix Elements Of The Transformed Vibrational Hamiltonian Of A Polyatomic Molecule With Resonances Using Van Vleck Perturbation Theory, Andreana M. Rosnik, William F. Polik

Faculty Publications

Vibrational levels of polyatomic molecules are analysed with Van Vleck perturbation theory to connect experimental energy levels to computed molecular potential energy surfaces. Vibrational matrix elements are calculated from a quartic potential function via second-order Van Vleck perturbation theory, a procedure that treats both weak and strong interactions among vibrational states by approximately block-diagonalising the vibrational Hamiltonian. A clear and complete derivation of anharmonic and resonance constants as well as general expressions for both on- and off-diagonal matrix elements of the transformed Hamiltonian is presented. The equations are written in partial fraction form and as a constant multiplied by a …

Observation Of Ground-State Two-Neutron Decay, M Thoennessen, Z Kholey, A Spyrou, E Lunderberg, Paul A. Deyoung, H Attanayake, T Baumann, D Bazin, B A. Brown, G Christian, D Divaratne, S M. Grimes, A Haagsma, J E. Finck, N Frank, B Luther, S Mosby, T Nagi, Graham F. Peaslee, W A. Peters, A Schiller, J K. Smith, J Snyder, M Strongman, A Volya

Faculty Publications

Neutron decay spectroscopy has become a successful tool to explore nuclear properties of nuclei with the largest neutron-to-proton ratios. Resonances in nuclei located beyond the neutron dripline are accessible by kinematic reconstruction of the decay products. The development of two-neutron detection capabilities of the Modular Neutron Array (MoNA) at NSCL has opened up the possibility to search for unbound nuclei which decay by the emission of two neutrons. Specifically, this exotic decay mode was observed in¹⁶Be and ²⁶O.

Toward Designed Singlet Fission: Solution Photophysics Of Two Indirectly Coupled Covalent Dimers Of 1,3-Diphenylisobenzofuran, Justin C. Johnson, Akin Akdag, Matibur Zamadar, Xudong Chen, Andrew F. Schwerin, Irina Paci, Millicent B. Smith, Zdenek Havlas, John R. Miller, Mark A. Ratner, Arthur J. Nozik, Josef Michl

Faculty Publications

In order to identify optimal conditions for singlet fission, we are examining the photophysics of 1,3- diphenylisobenzofuran (1) dimers covalently coupled in various ways. In the two dimers studied presently, the coupling is weak. The subunits are linked via the para position of one of the phenyl substituents, in one case (2) through a CH2 linker and in the other (3) directly, but with methyl substituents in ortho positions forcing a nearly perpendicular twist between the two joint phenyl rings. The measurements are accompanied with density functional theory (DFT) and timedependent DFT (TD-DFT) calculations. Although in neat solid state, 1 …

A Dft Study Of Vibrational Spectra And Mutagenicity Predictions Of Mononitrated Fluoranthenes [Abstract], Kefa Karimu Onchoke, Jorge Ojeda

Faculty Publications

No abstract provided.

Ammonium Sulfate Precipitation Combined With Liquid Chromatography Is Sufficient For Purification Of Bovine Serum Albumin That Is Suitable For Most Routine Laboratory Applications, Odutayo O. Odunuge, Alina Shazhko

Faculty Publications

The use of bovine serum albumin (BSA) in routine biochemical assays such as restriction enzyme digestion and immunodetection is plagued largely by two common contaminants, DNase and immunoglobulins G (IgGs). Acetylation of BSA to inactivate DNase limits its use as a protein standard due to interference with color development in assays such as Lowry’s. In spite of the availability of inexpensive BSA, its purification involves several cumbersome and time-consuming steps. In this work, we employed a modified strategy of ammonium sulfate precipitation coupled with liquid chromatography to purify BSA that is free of DNase and IgGs. Purified BSA tested negative …

Oxidation Of Gold Clusters By Thiols, Brian M. Barngrover, Christine M. Aikens

Faculty Publications

The formation of gold–thiolate nanoparticles via oxidation of gold clusters by thiols is examined in this work. Using the BP86 density functional with a triple ζ basis set, the adsorption of methylthiol onto various gold clusters Au_n^Z (n = 1–8, 12, 13, 20; Z = 0, −1, +1) and Au₃₈⁴⁺ is investigated. The rate-limiting step for the reaction of one thiol with the gold cluster is the dissociation of the thiol proton; the resulting hydrogen atom can move around the gold cluster relatively freely. The addition of a second thiol can lead to H_{2 …}

On The Currents And Transports Connected With The Atlantic Meridional Overturning Circulation In The Subpolar North Atlantic, X. Xu, H. E. Hurlburt, W. J. Schmitz Jr., R. Zantopp, J. Fischer, P.J. Hogan

Faculty Publications

Results from an interannually forced, 0.08 degrees eddy-resolving simulation based on the Hybrid Coordinate Ocean Model, in conjunction with a small but well-determined transport database, are used to investigate the currents and transports associated with the Atlantic meridional overturning circulation (AMOC) in the subpolar North Atlantic (SPNA). The model results yield a consistent warming in the western SPNA since the early 1990s, along with mean transports similar to those observed for the trans-basin AMOC across the World Ocean Circulation Experiment hydrographic section AR19 (16.4 Sv) and boundary currents at the exit of the Labrador Sea near 53 degrees N (39.0 …

An Acid Catalyzed Reversible Ring-Opening/Ring-Closure Reaction Involving A Cyano-Rhodamine Spirolactam, H. Li, H. Guan, X. Duan, J. Hu, Guiren Wang, Qian Wang

Faculty Publications

Cyanamide was introduced into the rhodamine spirolactam framework to produce a colorless and non-fluorescent compound RBCN. It shows a reversible ring-opening/ring-closure process in response to the solution pH, which exhibits an “ON/OFF” switching in its fluorescence. Different from other rhodamine-type dyes, the ring-open form of RBCN is stable in protic solvents under neutral, near neutral and basic conditions, showing a pink color and very strong fluorescence. We also demonstrated the potential of RBCN in live cell imaging.

A Comparison Of Boltzmann And Gibbs Definitions Of Microcanonical Entropy For Small Systems, Randall B. Shirts

Faculty Publications

Two different definitions of entropy, S= klnW, in the microcanonical ensemble have been competing for over 100 years. The Boltzmann/Planck definition is that W is the number of states accessible to the system at its energy E (also called the surface entropy). The Gibbs/Hertz definition is that W is the number of states of the system up to the energy E (also called the volume entropy). These two definitions agree for large systems but differ by terms of order N^-1 for small systems, where N is the number of particles in the system. For three analytical …

Dissolved Organic Matter Composition And Bioavailability Reflect Ecosystem Productivity In The Western Arctic Ocean, Yuan Shen, Cedric Fichot, Ronald Benner

Faculty Publications

Dissolved organic carbon (DOC) and total dissolved amino acids (TDAA) were measured in high (Chukchi Sea) and low (Beaufort Sea) productivity regions of the western Arctic Ocean to investigate the composition and bioavailability of dissolved organic matter (DOM). Concentrations and DOC-normalized yields of TDAA in Chukchi surface waters were relatively high, indicating an accumulation of bioavailable DOM. High concentrations and yields of TDAA were also observed in the upper halocline of slope and basin waters, indicating off-shelf transport of bioavailable DOM from the Chukchi Sea. In contrast, concentrations and yields of TDAA in Beaufort surface waters were relatively low, indicting …

Magnesium-Based Sacrificial Anode Cathodic Protection Coatings (Mg-Rich Primers) For Aluminum Alloys, Shashi S. Pathak, Sharathmukar K. Mendon, Michael D. Blanton, James W. Rawlins

Faculty Publications

Magnesium is electrochemically the most active metal employed in common structural alloys of iron and aluminum. Mg is widely used as a sacrificial anode to provide cathodic protection of underground and undersea metallic structures, ships, submarines, bridges, decks, aircraft and ground transportation systems. Following the same principle of utilizing Mg characteristics in engineering advantages in a decade-long successful R&D effort, Mg powder is now employed in organic coatings (termed as Mg-rich primers) as a sacrificial anode pigment to protect aerospace grade aluminum alloys against corrosion. Mg-rich primers have performed very well on aluminum alloys when compared against the current chromate …

Incorporation Of Quantum Effects For Selected Degrees Of Freedom Into The Trajectory-Based Dynamics Using Spatial Domains, Sophya V. Garashchuk, Mikhail V. Volkov

Faculty Publications

The approach of defining quantum corrections on nuclear dynamics of molecular systems incorporated approximately into selected degrees of freedom, is described. The approach is based on the Madelung-de-Broglie-Bohm formulation of time-dependent quantum mechanics which represents a wavefunction in terms of an ensemble of trajectories. The trajectories follow classical laws of motion except that the quantum potential, dependent on the wavefunction amplitude and its derivatives, is added to the external, classical potential. In this framework the quantum potential, determined approximately for practical reasons, is included only into the “quantum” degrees of freedom describing light particles such as protons, while neglecting with …

Breast Tumour Initiating Cell Fate Is Regulated By Microenvironmental Cues From An Extracellular Matrix, Sharmistha Saha, Pang-Kuo Lo, Xinrui Duan, Hexin Chen, Qian Wang

Faculty Publications

Cancer stem cells, also known as tumour-initiating cells (TICs), are identified as highly tumorigenic population within tumours and hypothesized to be main regulators in tumour growth, metastasis and relapse. Evidence also suggests that a tumour microenvironment plays a critical role in the development and progression of cancer, by constantly modulating cell–matrix interactions. Scientists have tried to characterize and identify the TIC population but the actual combination of extracellular components in deciphering the fate of TICs has not been explored. The basic unanswered question is the phenotypic stability of this TIC population in a tissue extracellular matrix setting. The in vivo …

Expanding And Testing A Computational Method For Predicting The Ground State Reduction Potentials Of Organic Molecules On The Basis Of Empirical Correlation To Experiment, Eugene J. Lynch, Amy L. Speelman, Bryce A. Curry, Charles S. Murillo, Jason G. Gillmore

Faculty Publications

A method for predicting the ground state reduction potentials of organic molecules on the basis of the correlation of computed energy differences between the starting S-0 and one-electron-reduced D-0 species with experimental reduction potentials in acetonitrile has been expanded to cover 3.5 V of potential range and 74 compounds across 6 broad families of molecules. Utilizing the conductor-like polarizable continuum model of implicit solvent allows a global correlation that is computationally efficient and has improved accuracy, with r(2) > 0.98 in all cases and root mean square deviation errors of(mean absolute deviationsmV) for either B3LYP/6-311+G(d,p) or B3LYP//6-31G(d) with an appropriate choice …

Discrimination Of Colon Cancer Stem Cells Using Noncanonical Amino Acid, Xinrui Duan, Honglin Li, Hexin Chen, Qian Wang

Faculty Publications

Cancer stem cells (CSCs) may be responsible for tumor recurrence. Metabolic labelling of newly synthesized proteins with non-canonical amino acids allows us to discriminate CSCs in mixed populations due to the quiescent nature of these cells.

Il-6 Regulation On Skeletal Muscle Mitochondrial Remodeling During Cancer Cachexia In The ApcMin/+ Mouse, James P. White, Melissa J. Puppa, Shuichi Sato, Song Gao, Robert L. Price, John W. Baynes, Matthew C. Kostek, Lydia E. Matesic, James A. Carson

Faculty Publications

BACKGROUND:

Muscle protein turnover regulation during cancer cachexia is being rapidly defined, and skeletal muscle mitochondria function appears coupled to processes regulating muscle wasting. Skeletal muscle oxidative capacity and the expression of proteins regulating mitochondrial biogenesis and dynamics are disrupted in severely cachectic Apc^Min/+ mice. It has not been determined if these changes occur at the onset of cachexia and are necessary for the progression of muscle wasting. Exercise and anti-cytokine therapies have proven effective in preventing cachexia development in tumor bearing mice, while their effect on mitochondrial content, biogenesis and dynamics is not well understood. The purposes of …

Specific Soluble Oligomers Of Amyloid-Β Peptide Undergo Replication And Form Non-Fibrillar Aggregates In Interfacial Environments, Amit Kumar, Lea C. Paslay, Daniel Lyons, Sarah E. Morgan, John J. Correia, Vijayaraghavan Rangachari

Faculty Publications

Aggregates of amyloid-β (Aβ) peptides have been implicated in the etiology of Alzheimer disease. Among the different forms of Aβ aggregates, low molecular weight species ranging between ∼2- and 50-mers, also called “soluble oligomers,” have emerged as the species responsible for early synaptic dysfunction and neuronal loss. Emerging evidence suggests that the neurotoxic oligomers need not be formed along the obligatory nucleation-dependant fibril formation pathway. In our earlier work, we reported the isolation of one such “off-pathway” 12–18-mer species of Aβ42 generated from fatty acids called large fatty acid-derived oligomers (LFAOs) (Kumar, A., Bullard, R. L., Patel, P., Paslay, L. …

Synthesis, Characterisation, And Preliminary In Vitro Studies Of Vanadium(Iv) Complexes With A Schiff Base And Thiosemicarbazones As Mixed Ligands, Nerissa A. Lewis, Fange Liu, Luke Seymour, Anthony Magnusen, Travis R. Erves, Jessa Faye Arca, Floyd A. Beckford, Ramaiyer Venkatraman, Antonio González-Sarrías, Frank R. Fronczek, Don G. Vanderveer, Navindra P. Seeram, Aimin Liu, William L. Jarrett, Alvin A. Holder

Faculty Publications

[VO(sal‐L‐tryp)(H₂O)] (1, sal‐L‐tryp = N‐salicylidene‐L‐tryptophanate) was used as a precursor to produce the new complexes [VO(sal‐L‐tryp)(MeATSC)]·1.5C₂H₅OH [2, MeATSC = 9‐Anthraldehyde‐N(4)‐methylthiosemicarbazone], [VO(sal‐L‐tryp)(N‐ethhymethohcarbthio)]·H₂O [3, N‐ethhymethohcarbthio = (E)‐N‐ethyl‐2‐(4‐hydroxy‐3‐methoxybenzylidene)hydrazinecarbothioamide] and [VO(sal‐L‐tryp)(acetylethTSC)]·C₂H₅OH {4, acetylethTSC = (E)‐N‐ethyl‐2‐[1‐(thiazol‐2‐yl)ethylidene]hydrazinecarbothioamide} by reaction with the respective thiosemicarbazone. The chemical and structural properties of these ligands and complexes were characterised by elemental analysis, ESI‐MS, FTIR, UV/Vis, ESR and ¹H and …