Analytical Chemistry Commons^™

Effect Of Dissolved Salts On The Physiochemical Properties Of Deep Eutectic Solvents, Eleanor Haeska, Megan Radtke

The Journal of Undergraduate Research

Green chemistry seeks to make chemical procedures safer, improve reaction efficiency, and utilize environmentally safe reagents. Deep eutectic solvents (DES) have recently become of great interest due to their eco-friendly nature and functionality as solvent for various chemical processes. One key characteristic of DES is their conductive nature and depressed melting point. This project sought to determine the effect of the addition of aqueous solutions of halides on the conductivity of two selected types of DES. Also assessed were the polarity and viscosity of the DES. It can be concluded that aqueous halides had no measureable effect on the conductivity …

Increased Perchlorate In The Environment Following The 1600 C.E. Huaynaputina Volcanic Eruption, Joseph Gibson, Amanda Shea

The Journal of Undergraduate Research

Perchlorate is an environmental contaminant that can have adverse health effects on humans. Although our knowledge about how natural perchlorate is formed is very limited, volcanic eruptions are believed to play an important role. An ice core obtained from Summit Station, Greenland was used to study the effects of the Huaynaputina eruption on the amount of perchlorate in the environment. The section of ice core sampled was determined to span the years 1594 through 1610. The results indicate that the Huaynaputina eruption caused a temporary but significant increase in the amount of perchlorate in the atmosphere.

Atomic Force Microscopy Tip-Enhanced Laser Ablation, Fan Cao

LSU Doctoral Dissertations

In the present work, an apertureless atomic force microscope (AFM) tip-enhanced laser ablation (TELA) system was developed and investigated. An AFM was coupled to an optical parametric oscillator (OPO) wavelength tunable laser for sample ablation with a submicron sampling size. The AFM was used to image the surface and hold the AFM tip 10 nm above the sample surface. The AFM tip is coated with a layer of gold with a thickness of 35 nm. The incident laser wavelength was tuned in the visible and near-infrared (IR) region and focused on the AFM tip. With the tip-enhancement effect, ablation craters …

Toward The Impact Of Particulate Matter On Human Health: Evaluation Of Fluorescent Environmentally Persistent Free Radical (Epfr) Surrogates, Ansonia Badgett

LSU Doctoral Dissertations

Environmentally persistent free radicals (EPFRs)—a newly discovered pollutant associated with particulate matter (PM)—form during combustion and thermal processes, such as the incineration of hazardous waste. Various chlorine- and hydroxy-substituted benzenes chemisorb on the surface of metal oxides (e.g., NiO, CuO, and Fe₂O₃) and then form EPFRs, stabilized radical species, as the result of the transfer of electrons between the adsorbate and the metal ion of the metal oxide. Previous studies have shown direct correlations between ultra-fine (d < 0.1 mm) particulate matter (PM_0.1) exposure and adverse pulmonary health effects. PM_0.1 has the potential …

Reaction Mechanism Between Small-Sized Ce Clusters And Water Molecules: An Ab Initio Investigation On CeN+H2O, Rulong Zhou, Yang Yang, Seema Pande, Bingyan Qu, Dongdong Li, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Reactions of small-sized cerium clusters Ce_n (n = 1–3) with a single water molecule are systematically investigated theoretically. The ground state structures of the Ce_n/H₂O complex and the reaction pathways between Ce_n + H₂O are predicted. Our results show the size-dependent reactivity of small-sized Ce clusters. The calculated reaction energies and reaction barriers indicate that the reactivity between Ce_n and water becomes higher with increasing cluster size. The predicted reaction pathways show that the single Ce atom and the Ce₂ and Ce₃ clusters can all easily react with H …

Role Of Water On The Rotational Dynamics Of The Organic Methylammonium Cation: A First Principles Analysis, Ross D. Hoehn, Joseph S. Francisco, Sabre Kais, Ali Kachmar

Department of Chemistry: Faculty Publications

Understanding the degradation mechanisms of lead-halide perovskites (CH₃NH₃PbI₃) under exposure to liquid/aerosol water is an essential problem within the photovoltaic community. Herein we investigate both the static and the dynamic properties of the methylammonuim cation (MA) as it coordinates with invading water molecules (MA.(H₂O)_n, n = 1, 2, 3, 4) using both stationary state quantum mechanics and first principle molecular dynamics simulations. Various solvation structures of MA were characterized by their stabilization energies, dipoles, and Maximally-Localized Wannier Function (MLWF) centers. Calculation – and analysis – of vibrational shifts in the …

Structural Basis Of 7sk Rna 5′ Γ-Phosphate Methylation And Retention By Mepce, Yuan Yang, Catherine D. Eichhorn, Yaqiang Wang, Duilio Cascio, Juli Feigon

Department of Chemistry: Faculty Publications

Among RNA 5′-cap structures, γ-phosphate monomethylation is unique to a small subset of noncoding RNAs, 7SK and U6 in humans. 7SK is capped by methylphosphate capping enzyme (MePCE), which has a second non-enzymatic role as a core component of the 7SK RNP that is an essential regulator of RNA transcription. We report 2.0 and 2.1 Å X-ray crystal structures of human MePCE methyltransferase domain bound to S-adenosylhomocysteine (SAH) and uncapped or capped 7SK substrates, respectively. 7SK recognition is achieved by protein contacts to a 5′ hairpin-single-stranded RNA region, explaining MePCE specificity for 7SK and U6. The structures reveal SAH and …

Molecular Insights Into Cage Occupancy Of Hydrogen Hydrate: A Computational Study, Rui Ma, Hong Zhong, Jinxiang Liu, Jie Zhong, Youguo Yan, Jun Zhang, Jiafang Xu

Department of Chemistry: Faculty Publications

Density functional theory calculations and molecular dynamics simulations were performed to investigate the hydrogen storage capacity in the sII hydrate. Calculation results show that the optimum hydrogen storage capacity is ~5.6 wt%, with the double occupancy in the small cage and quintuple occupancy in the large cage. Molecular dynamics simulations indicate that these multiple occupied hydrogen hydrates can occur at mild conditions, and their stability will be further enhanced by increasing the pressure or decreasing the temperature. Our work highlights that the hydrate is a promising material for storing hydrogen.

Brush-Arm Star Polymer Imaging Agents And Uses Thereof, Jeremiah A. Johnson, Hung Vanthanh Nguyen, Andrzej Rajca

Department of Chemistry: Faculty Publications

Disclosed are methods, compositions, reagents, systems, and kits to prepare nitroxide-functionalized brush-arm star polymer organic radical contrast agent (BASP-ORCA) as well as compositions and uses thereof. Various embodiments show that BASP-ORCA display unprecedented per-nitrox-ide and per-molecule transverse relaxivities for organic radical contrast agents, exceptional stability, high water solubility, low in vitro and in vivo toxicity, and long blood compartment half-life. These materials have the potential to be adopted for tumor imaging using clinical high-field ¹H MRI techniques.

Growth Of Carbon Dioxide Whiskers, Avinash Kumar Both, Chin Li Cheung

Department of Chemistry: Faculty Publications

We report the growth of carbon dioxide (CO₂) whiskers at low temperatures (–70 °C to –65 °C) and moderate pressure (4.4 to 1.0 bar). Their axial growth was assessed by optical video analysis. The identities of these whiskers were confirmed as CO₂ solids by Raman spectroscopy. A vapor– solid growth mechanism was proposed based on the influence of the relative humidity on the growth.

Role Of Water On The Rotational Dynamics Of The Organic Methylammonium Cation: A First Principles Analysis, Ross D. Hoehn, Joseph S. Francisco, Sabre Kais, Ali Kachmar

Department of Chemistry: Faculty Publications

Understanding the degradation mechanisms of lead-halide perovskites (CH₃NH₃PbI₃) under exposure to liquid/aerosol water is an essential problem within the photovoltaic community. Herein we investigate both the static and the dynamic properties of the methylammonuim cation (MA) as it coordinates with invading water molecules (MA.(H₂O)_n, n = 1, 2, 3, 4) using both stationary state quantum mechanics and first principle molecular dynamics simulations. Various solvation structures of MA were characterized by their stabilization energies, dipoles, and Maximally-Localized Wannier Function (MLWF) centers. Calculation – and analysis – of vibrational shifts in the …

Indole Reverses Intrinsic Antibiotic Resistance By Activating A Novel Dual-Function Importer, Yan Wang, Tian Tian, Jingjing Zhang, Xin Jin, Huan Yue, Xiao-Hua Zhang, Liangcheng Du, Fan Bai

Department of Chemistry: Faculty Publications

Bacterial antibiotic resistance modulation by small signaling molecules is an emerging mechanism that has been increasingly reported in recent years. Several studies indicate that indole, an interkingdom signaling molecule, increases bacterial antibiotic resistance. However, the mechanism through which indole reduces antibiotic resistance is largely unknown. In this study, we demonstrated a novel mechanism for indole-mediated reversal of intrinsic antibiotic resistance in Lysobacter. This reversal was facilitated by a novel BtuD-associated dual-function importer that can transfer both vitamin B₁₂ and antibiotics. Indole stimulated btuD overexpression and promoted efficient absorption of extracellular vitamin B₁₂; meanwhile, the weak selectivity …

High Initial Reversible Capacity And Long Life Of Ternary Sno2‑Co‑Carbon Nanocomposite Anodes For Lithium‑Ion Batteries, Pan Deng, Jing Yang, Shengyang Li, Tian-E Fan, Hong-Hui Wu, Yun Mou, Hui Huang, Qiaobao Zhang, Dong-Liang Peng, Baihua Qu

Department of Chemistry: Faculty Publications

The two major limitations in the application of SnO₂ for lithium-ion battery (LIB) anodes are the large volume variations of SnO₂ during repeated lithiation/delithiation processes and a large irreversible capacity loss during the first cycle, which can lead to a rapid capacity fade and unsatisfactory initial Coulombic efficiency (ICE). To overcome these limitations, we developed composites of ultrafine SnO₂ nanoparticles and in situ formed Co(CoSn) nanocrystals embedded in an N-doped carbon matrix using a Co-based metal–organic framework (ZIF-67). The formed Co additives and structural advantages of the carbon-confined SnO₂/ Co nanocomposite effectively inhibited Sn coarsening …

Au60–: The Smallest Gold Cluster With The High-Symmetry Icosahedral Core Au13, Seema Pande, Xingao Gong, Lai-Sheng Wang, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Among coinage metal nanoclusters with 55 atoms, only Ag₅₅^– and Cu₅₅^– are the geometric magic-number clusters, as both exhibit icosahedral symmetry. Au₅₅^–, however, exhibits much lower symmetry due largely to the strong relativistic bonding effect. In this study, we collect a much larger population (>10,000 isomers) of low-energy isomers of Au₅₅^– to Au₆₀^– by using the combined density-functional theory and basin-hopping global optimization method. We also include the spin−orbit effect in the density-functional theory computation to achieve simulated photoelectron spectra in quantitative fashion. Remarkably, we uncover that the …

Modification Of Bruker Amazon Etd And Solarix Mass Spectrometers Towards Infrared Multiple Photon Dissociation: Structural Characterization Of Modified Nucleosides, Lucas Ash Hamlow

Wayne State University Dissertations

Infrared ion spectroscopy has become an increasingly powerful tool for examining

the intrinsic structures of gas-phase ions. Infrared multiple photon dissociation (IRMPD)

action spectroscopy has been particularly successful. Several free electron laser (FEL)

facilities across the world have helped facilitate the growth of the IRMPD technique and

increasing interest has driven the development of more accessible IRMPD

instrumentation. The development of one such IRMPD instrumentation system is

described in this work, based around commercially available 3D quadrupole ion trap mass

spectrometers and Fourier-transform ion cyclotron resonance mass spectrometers.

The intrinsic gas-phase structures of nucleic acid monomers have been

extensively studied …

Fluorescence Quenching-Based Mechanism For Determination Of Hypochlorite By Coumarin-Derived Sensors, Karolina Starzak, Arkadiusz Matwijczuk, Bernadette Creaven, Alicja Matwijczuk, Sławomir Wybraniec, Dariusz Karcz

Articles

A fluorescence quenching-based mechanism for the determination of hypochlorite was proposed based on spectroscopic and chromatographic studies on the hypochlorite-sensing potency of three structurally similar and highly fluorescent coumarins. The mode of action was found to rely upon a chlorination of the coumarin-based probes resulting from their reaction with sodium hypochlorite. Importantly, the formation of chlorinated derivatives was accompanied by a linear decrease in the fluorescence intensities of the probes tested. The results obtained suggest the applicability of a coumarin-dependent hypochlorite recognition mechanism for the detection of, as well as for quantitative determination of, hypochlorite species in vitro.

Spheroid-3d And Monolayer-2d Intestinal Electrochemical Biosensor For Toxicity/Viability Testing: Applications In Drug Screening, Food Safety, And Environmental Pollutant Analysis, Evangelia Flampouri, Shahzad Imar, Kieran O'Connell, Baljit Singh

Articles

The rise of three-dimensional cell culture systems that provide in vivo-like environments for pharmaco-toxicological models has prompted the need for simple and robust viability assays suitable for complex cell architectural structures. This study addresses that challenge with the development of an in vitro enzyme based electrochemical sensor for viability/cytotoxicity assessment of two-dimensional (2D) monolayer and three-dimensional (3D) spheroid culture formats. The biosensor measures the cell viability/toxicity via electrochemical monitoring of the enzymatic activity of nonspecific esterases of viable cells, through the hydrolysis of 1-naphthyl acetate to 1-naphthol. The proposed sensor demonstrated strong correlation (r = 0.979) with viable …

Highly Stable And Efficient All-Inorganic Lead-Free Perovskite Solar Cells With Native-Oxide Passivation, Min Chen, Ming-Gang Ju, Hector F. Garces, Alexander D. Carl, Luis K. Ono, Zafer Hawash, Yi Zhang, Tianyi Shen, Yabing Qi, Ronald L. Grimm, Domenico Pacifici, Xiao Cheng Zeng, Yuanyuan Zhou, Nitin P. Padture

Department of Chemistry: Faculty Publications

There has been an urgent need to eliminate toxic lead from the prevailing halide perovskite solar cells (PSCs), but the current lead-free PSCs are still plagued with the critical issues of low efficiency and poor stability. This is primarily due to their inadequate photovoltaic properties and chemical stability. Herein we demonstrate the use of the lead-free, allinorganic cesium tin-germanium triiodide (CsSn_0.5Ge_0.5I₃) solid-solution perovskite as the light absorber in PSCs, delivering promising efficiency of up to 7.11%. More importantly, these PSCs show very high stability, with less than 10% decay in efficiency after 500 h …

Urease Is An Essential Component Of The Acid Response Network Of Staphylococcus Aureus And Is Required For A Persistent Murine Kidney Infection, Chunyi Zhou, Fatema Bhinderwala, Mckenzie K. Lehman, Vinai C. Thomas, Sujata S. Chaudhari, Kelsey J. Yamada, Kirk W. Foster, Robert Powers, Tammy Kielian, Paul D. Fey

Department of Chemistry: Faculty Publications

Staphylococcus aureus causes acute and chronic infections resulting in significant morbidity. Urease, an enzyme that generates NH₃ and CO₂ from urea, is key to pH homeostasis in bacterial pathogens under acidic stress and nitrogen limitation. However, the function of urease in S. aureus niche colonization and nitrogen metabolism has not been extensively studied. We discovered that urease is essential for pH homeostasis and viability in urea-rich environments under weak acid stress. The regulation of urease transcription by CcpA, Agr, and CodY was identified in this study, implying a complex network that controls urease expression in response to changes …

Properties And Applications Of Tetraalkylphosphonium Alkylsulfate Ionic Liquids And 3d Printed Polymerized Ionic Liquids, Mustafa Mohammed Alhussain

Murray State Theses and Dissertations

Ionic liquids (ILs) are defined as pure salts with a melting temperature below 100 °C with a subset called room-temperature ILs (RTILs) with melting temperatures at or below room temperature. The sizes of the cation and anion play a critical role in determining the properties, with smaller ions forming stronger ionic forces and packing better, raising viscosity and lowering conductivity of the IL. At the same time, intermolecular forces such as van der Waals and hydrogen bonding can play a role in IL properties as well. Our research described herein is focused on three tetraalkylphosphonium-based cations coupled with three alkylsulfate …