Digital Commons Network^™

Aerosol Mass And Optical Properties, Smoke Influence On O3, And High No3 Production Rates In A Western U.S. City Impacted By Wildfires, Vanessa Selimovic, Robert J. Yokelson, Gavin R. Mcmeeking, Sarah Coefield

Chemistry and Biochemistry Faculty Publications

Evaluating our understanding of smoke from wild and prescribed fires can benefit from downwind measurements that include inert tracers to test production and transport and reactive species to test chemical mechanisms. We characterized smoke from fires in coniferous forest fuels for >1,000 hr over two summers (2017 and 2018) at our Missoula, Montana, surface station and found a narrow range for key properties. ΔPM2.5/ΔCO was 0.1070 ± 0.0278 (g/g) or about half the age-independent ratios obtained at free troposphere elevations (0.2348 ± 0.0326). The average absorption Ångström exponent across both years was 1.84 ± 0.18, or about half the values …

An Investigation Of Antenna, Ligand Side-Chain, And Metal Ion Effects On The Optical And Mri Properties Of Bimodal Lanthanide (Iii) Complexes, Marisa Poveda

Master's Theses

Magnetic Resonance Imaging (MRI) is a leading anatomical imaging modality for disease diagnosis. With the aid of Gd³⁺ based contrast agents, high resolution images of biological structures can be obtained. However, there is an increased need for contrast agents that are responsive to specific analytes and chemical environments. Paramagnetic Chemical Exchange Saturation Transfer (PARACEST) agents that utilize a paramagnetic lanthanide ion chelated with a ligand have shown great promise in this area. Lanthanide ions also possess luminescence properties that do not suffer from common limitations of conventional optical imaging agents such as autofluorescence and photobleaching. The projects described in …

Designing A More Effective Mri Contrast Agent: Investigation Into Various Functionalization Strategies For Targeted Imaging, Lauren Nicole Rust

Dissertations and Theses

Magnetic resonance imaging (MRI) is a medical imaging technique that provides high-resolution images used for diagnostic medicine while maintaining a superior safety profile compared to other radiative techniques. The administration of gadolinium-based contrast agents (GBCAs) improves the diagnostic power of MRI and have been used clinically for over three decades. Although GBCAs are effective at improving the contrast in the image, their detection limits are high and require a large dose to generate an observable effect. This high dose is the consequence of the current available designs of clinical GBCAs; their structures are not tuned to generate optimal efficacy. Efficacy …

Functionalized Pyridine In Pyclen-Based Iron(Iii) Complexes: Evaluation Of Fundamental Properties, Magy A. Mekhail, Kristof Pota, Timothy M. Schwartz, Kayla N. Green

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

The use of tetra-aza pyridinophanes is of increasing interest in the fields of bioinorganic modeling, catalysis, and imaging. However, a full study of how modifications to the pyridyl moiety affect the characteristics of the daughter metal complexes, has not been explored. In this study, six tetra-aza macrocyclic ligands were metalated with Fe(iii) and were characterized for the first time. The pyridyl functional groups studied include: 4-hydroxyl (L1), 4-H (L2), 4-chloro (L3), 4-trifluoromethyl (L4), 4-nitrile (L5), and 4-nitro (L6) modified pyridyl on a pyclen base structure. The resulting iron …

Electrospun Zno/Poly(Vinylidene Fluoride-Trifluoroethylene) Scaffolds For Lung Tissue Engineering, Bahareh Azimi, Mohammad Sajad Sorayani Bafqi, Alessandra Fusco, Claudio Ricci, Giuseppe Gallone, Roohollah Bagherzadeh, Giovanna Donnarumma, M. Jasim Uddin, Masoud Latifi, Andrea Lazzeri, Serena Danti

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

Due to the morbidity and lethality of pulmonary diseases, new biomaterials and scaffolds are needed to support the regeneration of lung tissues, while ideally providing protective effects against inflammation and microbial aggression. In this study, we investigated the potential of nanocomposites of poly(vinylidene fluoride-co-trifluoroethylene) [P(VDF-TrFE)] incorporating zinc oxide (ZnO), in the form of electrospun fiber meshes for lung tissue engineering. We focused on their anti-inflammatory, antimicrobial and mechano-electrical character according to different fiber mesh textures (i.e., collected at 500 rpm and 4000 rpm) and compositions: (0/100) and (20/80) w/w% ZnO/P(VDF-TrFE), plain and composite, respectively. The scaffolds were characterized in terms …

Insights On Dissolved Organic Matter Production Revealed By Removal Of Charge-Transfer Interactions In Senescent Leaf Leachates, Karl M. Meingast, Brice K. Grunert, Sarah A. Green, Evan S. Kane, Nastaran Khademimoshgenani

Michigan Tech Publications, Part 1

Dissolved organic matter (DOM) is a critical part of the global carbon cycle. Currently, it is understood that at least a portion of the chromophoric DOM (CDOM) character can be described through an electronic interaction of charge transfer (CT) complexes. While much work has been done to understand the influence of CT on soil and aquatic reference standard DOM, little is known about the influence of CT in fresh terrestrially derived DOM. In this study, leaf litter leachates from three tree species were treated (reduced) with sodium borohydride to determine the contribution of CT on a source of fresh terrestrial …

Long Term Air Quality Analysis In Reference To Thermal Power Plants Using Satellite Data In Singrauli Region, India, H. K. Romana, Ramesh P. Singh, D. P. Shukla

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

The exponentially growing population and related anthropogenic activities have led to modifications in local environment. The change in local environment, evolving pattern of land use, concentrations of greenhouse gases and aerosols alter the energy balance of our climate system. This alteration in climate is leading to pre-mature deaths worldwide. This study analyses the air quality of Singrauli region, Madhya Pradesh, India for the past 15 years. Otherwise known as Urjanchal “the energy capital” of India has been declared as critically polluted by CPCB. The study provides an updated list of thermal power plants in the study area and their emission …

The Bach1/Nrf2 Axis In Brain In Down Syndrome And Transition To Alzheimer Disease-Like Neuropathology And Dementia, Marzia Perluigi, Antonella Tramutola, Sara Pagnotta, Eugenio Barone, D. Allan Butterfield

Chemistry Faculty Publications

Down syndrome (DS) is the most common genetic cause of intellectual disability that is associated with an increased risk to develop early-onset Alzheimer-like dementia (AD). The brain neuropathological features include alteration of redox homeostasis, mitochondrial deficits, inflammation, accumulation of both amyloid beta-peptide oligomers and senile plaques, as well as aggregated hyperphosphorylated tau protein-containing neurofibrillary tangles, among others. It is worth mentioning that some of the triplicated genes encoded are likely to cause increased oxidative stress (OS) conditions that are also associated with reduced cellular responses. Published studies from our laboratories propose that increased oxidative damage occurs early in life in …

High-Frequency Data Reveal Differential Dissolved And Suspended Solids Behavior From A Mixed Restored Prairie And Agricultural Catchment, Andrew Miller, Ashlee L. Dere, Tracy Coleman

Chemistry Faculty Publications

Quantifying temporal variability and fluxes within hydrologic catchments is critical to understanding the underlying chemical and physical processes leading to material transport. Measuring variability and fluxes requires sampling at time scales similar to the time scale of process occurrence. This demand has led to the development of automated sampling systems designed to sample at high frequencies, on the order of minutes. While widely deployed in a variety of systems, we installed two high-frequency sampling devices in a single drainage comprised of restored prairie and agricultural land uses in temperate Eastern Nebraska. The sampling systems determined flow rate, conductivity, and turbidity …

Effect Of Carbon Hybridization In C—F Bond As An Electron Donor In Triel Bonds, Qingqing Yang, Zongqing Chi, Qingzhong Li, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

The ability of the F atom of HC≡CF, H₂C=CHF and H₃CCH₂F to serve as an electron donor to the triel (Tr) atom of TrR₃ in the context of a triel bond is assessed by ab initio calculations. The triel bond formed by C_sp3—F is strongest, as high as 30 kcal/mol, followed by C_sp2—F, and then by C_sp—F whose triel bonds can be as small as 1 kcal/mol. The noncovalent bond strength diminishes in the order Tr = Al > Ga > B, consistent with the intensity of the π-hole …

The Bio3d Packages For Structural Bioinformatics, Barry J. Grant, Lars Skjærven, Xin-Qiu Joe Yao

Chemistry Faculty Publications

Bio3D is a family of R packages for the analysis of biomolecular sequence, structure, and dynamics. Major functionality includes biomolecular database searching and retrieval, sequence and structure conservation analysis, ensemble normal mode analysis, protein structure and correlation network analysis, principal component, and related multivariate analysis methods. Here, we review recent package developments, including a new underlying segregation into separate packages for distinct analysis, and introduce a new method for structure analysis named ensemble difference distance matrix analysis (eDDM). The eDDM approach calculates and compares atomic distance matrices across large sets of homologous atomic structures to help identify the residue wise …

Stay Calm And Focus On The Learning Outcomes: Tools For Taking Biophysical Chemistry Online, Maria Ballester, Brian L. Van Hoozen Jr., Arthur Sikora

Chemistry and Physics Faculty Articles

Course specific learning outcomes are an important tool to define the scope of a course and can be very helpful when designing experiments and assessments. With slight modification, these learning outcomes can serve as a guide when transitioning to the distance learning format especially in courses with a traditional lab. Here we present such an example for the biophysical chemistry course.

Development And Application Of Mass Spectrometry-Based Approaches For Protein Higher Order Structure Analysis And Protein-Protein Interaction Characterization, Mengru Zhang

Arts & Sciences Graduate Student Theses and Dissertations

Proteins, one of the most fundamental biomolecules, adopt unique higher order structures (HOS) to enable diverse biological functions. Deciphering protein HOS is crucial to gain deeper insights of their working mechanisms and to develop biotherapeutics. Mass spectrometry (MS)-based approaches evolved rapidly in the past 30 years and are now playing critical roles in protein HOS characterization. One of those approaches is MS-based footprinting whose principle is to map the solvent accessible surface area (SASA) to deliver structural information. Protein footprinting can be achieved by reversible labeling, e.g., hydrogen-deuterium exchange (HDX), and by irreversible labeling using radical-based reagents or other targeted …

Structural Organization And Chemical Activity Revealed By New Developments In Single-Molecule Fluorescence And Orientation Imaging, Tianben Ding

McKelvey School of Engineering Graduate Student Theses & Dissertations

Single-molecule (SM) fluorescence and its localization are important and versatile tools for understanding and quantifying dynamical nanoscale behavior of nanoparticles and biological systems. By actively controlling the concentration of fluorescent molecules and precisely localizing individual single molecules, it is possible to overcome the classical diffraction limit and achieve 'super-resolution' with image resolution on the order of 10 nanometers.

Single molecules also can be considered as nanoscale sensors since their fluorescence changes in response to their local nanoenvironment. This dissertation discusses extending this SM approach to resolve heterogeneity and dynamics of nanoscale materials and biophysical structures by using positions and orientations …

Production Of Medical Radioisotopes Using Titanium Accelerator Targets, Christopher Shaun Loveless

Arts & Sciences Graduate Student Theses and Dissertations

Theranostic radiopharmaceuticals enable diagnostic imaging and radionuclide therapy in patients using a single molecular agent labeled with a diagnostic-therapeutic pair (e.g., 68Ga/177Lu) or a theranostic radionuclide (e.g., 131I). This theranostic approach can help inform patient-specific treatment plans and improve clinical outcomes. Radionuclide pairs used in theranostic agents fall into two categories: pseudo matched-pairs (e.g., 68Ga/177Lu) and matched-pairs (e.g., 124I/131I). Pseudo matched-pair radionuclides have similar chemistries and pharmacokinetics when bound to the same bioconjugate molecule. In contrast, identical chemistries and pharmacokinetics can be obtained by using the matched-pair radionuclides.The isotopes of Sc include two diagnostic radioisotopes, 43Sc & 44Sc, and one …

Transition Metal Complexes Of Pyridyltriazole And Bipyridine Ligands, Sen Gao

LSU Doctoral Dissertations

Four Ni(II) complexes have been obtained with the pyridyltriazole ligand, bpt, or the bis(pyridyltriazole) ligand, m-xpt, in chapter 2. This work was carried out as a comparison with the previously established coordination chemistry of copper(II) with bpt and m-xpt. Initially, the reaction between Ni(II) and bpt only produced one mononuclear compound, [Ni(bpt)₂(H₂O)₂](NO₃)₂ (1). In order to study the formation of Ni-bpt and Ni-m-xpt complexes in solution, mixtures of Ni(NO₃)₂ and ligand (m-xpt or bpt) were prepared in different ratios and …

Highly Swelling Ph-Responsive Microgels For Dual Mode Near Infra-Red Fluorescence Reporting And Imaging, Mingning Zhu, Dongdong Lu, Qing Lian, Shanglin Wu, Wenkai Wang, L. Andrew Lyon, Weiguang Wan, Paulo Bártolo, Mark Dickinson, Brian R. Saunders

Engineering Faculty Articles and Research

Near infra-red (NIR) fluorescence is a desirable property for probe particles because such deeply penetrating light enables remote reporting of the local environment in complex surroundings and imaging. Here, two NIR non-radiative energy transfer (NRET) fluorophores (Cy5 and Cy5.5) are coupled to preformed pH-responsive poly(ethylacrylate-methacrylic acid-divinylbenzene) microgel particles (PEA-MAA-5/5.5 MGs) to obtain new NIR fluorescent probes that are cytocompatible and swell strongly. NIR ratiometric photoluminescence (PL) intensity analysis enables reporting of pH-triggered PEA-MAA-5/5.5 MG particle swelling ratios over a very wide range (from 1–90). The dispersions have greatly improved colloidal stability compared to a reference temperature-responsive NIR MG based on …

Second Harmonic Generation Spectroscopy And Microscopy Of Liposomes, Nanoparticles, And Cells, Prakash Hamal

LSU Doctoral Dissertations

Second harmonic generation (SHG) is used to investigate the factors that impact nanoparticle-based drug-delivery applications. In the first study, molecular adsorption and transport kinetics of a positively-charged dye, malachite green isothiocyanate (MGITC), is characterized at the surface of different colloidal liposomes in water using SHG spectroscopy. The molecular interactions of MGITC is compared to our previous investigations with malachite green (MG). In comparison to MG, MGITC demonstrates stronger adsorption and faster transport through lipid membranes. Correspondingly, the SHG experimental results are in excellent agreement with the molecular dynamics (MD) simulations results. A key finding illustrates the importance of functional groups, …

Near Simultaneous Laser Scanning Confocal And Atomic Force Microscopy (Conpokal) On Live Cells, Joree N. Sandin, Surya P. Aryal, Thomas E. Wilkop, Christopher I. Richards, Martha E. Grady

Physiology Faculty Publications

Techniques available for micro- and nano-scale mechanical characterization have exploded in the last few decades. From further development of the scanning and transmission electron microscope, to the invention of atomic force microscopy, and advances in fluorescent imaging, there have been substantial gains in technologies that enable the study of small materials. Conpokal is a portmanteau that combines confocal microscopy with atomic force microscopy (AFM), where a probe "pokes" the surface. Although each technique is extremely effective for the qualitative and/or quantitative image collection on their own, Conpokal provides the capability to test with blended fluorescence imaging and mechanical characterization. Designed …

Isolation, Structure Elucidation, And Synthesis Of Natural Products From Marine Cyanobacteria, Keren Solomon

Electronic Theses and Dissertations

This thesis describes the isolation, structure elucidation, and synthesis of natural products from marine cyanobacteria. A crude extract from a cyanobacterium collected in Curacao showed selective affinity for the dopamine D₅ receptor in a screen against a panel of CNS receptors. Due to the high similarity of the D₅ and D₁ receptor, to date there are no known ligands that differentiate them. Attempts to purify the compound responsible for this affinity led to the isolation of the known compound caylobolide A. A second extract from a cyanobacterium collected in Panama underwent bioassay-guided fractionation and yielded the novel …

Electrostatic Denaturation Of Dna-Cisplatin Adducts, Eddie Madrigal

Master's Theses

In this thesis, electrochemical approaches are used to determine the properties of deoxyribonucleic acid (DNA) by electrostatic denaturation. The electrochemical routine involves an application of a destabilization potential, an equilibration potential, and a square wave voltammogram (SWV) to monitor the extent of melting. Our method uses a monolayer consisting of thiol modified DNA and mercaptohexanol on a gold electrode. These electrodes are then incubated in a complementary sequence tagged with methylene blue. By using our electrostatic denaturation technique, different parameters are explored, such as surface densities, surface coverages, and ionic strengths. As proof of concept, these techniques were applied toward …

Electroactive Anion Receptor With High Affinity For Arsenate, Samuel I. Etkind, Douglas A. Vander Griend, Timothy M. Swager

University Faculty Publications and Creative Works

Herein, we present the synthesis and characterization of a macrocyclic polyamide cage that incorporates redox-active 1,4-dithiin units. UV/vis titration experiments with eight anions in acetonitrile revealed high affinity for H2AsO4− (log β2 = 10.4−+0.40.4) and HCO3− (log β2 = 8.3−+0.30.4) over other common anionic guests, such as Cl− (log K1:1 = 3.20−+0.030.02), HSO4− (log K1:1 = 3.57−+0.020.03), and H2PO4− (log K1:1 = 4.24−+0.050.04), by the selective formation of HG2 complexes. The recognition of arsenate over phosphate is rare among both proteins and synthetic receptors, and though the origin of selectivity is not known, exploiting the difference in the binding stoichiometry …

Structure And Function Of A Flavin-Dependent S-Monooxygenase From Garlic (Allium Sativum), Hannah Valentino, Ashley C. Campbell, Jonathan P. Schuermann, Nazneen Sultana, Han G. Nam, Sophie Leblanc, John J. Tanner, Pablo Sobrado

Chemistry Faculty Research & Creative Works

Allicin is a component of the characteristic smell and flavor of garlic (Allium sativum). A flavin-containing monooxygenase (FMO) produced by A. sativum (AsFMO) was previously proposed to oxidize S-allyl-L-cysteine (SAC) to alliin, an allicin precursor. Here, we present a kinetic and structural characterization of AsFMO that suggests a possible contradiction to this proposal. Results of steady-state kinetic analyses revealed that AsFMO exhibited negligible activity with SAC; however, the enzyme was highly active with L-cysteine, N-acetyl-L-cysteine, and allyl mercaptan. We found that allyl mercaptan with NADPH was the preferred substrate-cofactor combination. Rapid-reaction kinetic analyses showed that NADPH binds tightly (KD of …

Building An Ins-1 Cdna Library For A Genome-Wide Crispr-Cas9 Screen, Idongesit Ekpo

Undergraduate Honors Theses

By the year 2040, an estimated 642 million people are expected to have diabetes globally. Diabetes results from an elevation of metabolic stressors, such as glucotoxicity, lipotoxicity, oxidative stress and apoptosis. In type 2 diabetes, these stressful conditions contribute to the malfunction and loss of functional insulin-producing β-cells. Current treatment methods for diabetes include insulin therapy, islet transplant and anti-diabetes medication. These treatments are not curative and ignore other factors that contribute to the pathogenesis of diabetes beyond insulin resistance and islet β-cell failure. Previous research on β-cells has focused on ways to replace functional β-cell mass, trigger β-cell proliferation, …

Structure And Unprecedented Reactivity Of A Mononuclear Nonheme Cobalt(Iii) Iodosylbenzene Complex, J. Yang, M. S. Seo, K. H. Kim, Y. M. Lee, S. Fukuzumi, Jason M. Shearer, W. Nam

Chemistry Faculty Research

A mononuclear nonheme cobalt(III) iodosylbenzene complex, [Co^III(TQA)(OIPh)(OH)]²⁺ (1), is synthesized and characterized structurally and spectroscopically. While 1 is a sluggish oxidant in oxidation reactions, it becomes a competent oxidant in oxygen atom transfer reactions, such as olefin epoxidation, in the presence of a small amount of proton. More interestingly, 1 shows a nucleophilic reactivity in aldehyde deformylation reaction, demonstrating that 1 has an amphoteric reactivity. Another interesting observation is that 1 can be used as an oxygen atom donor in the generation of high-valent metal-oxo complexes. To our knowledge, we present the first crystal structure …

Synthesis And Assessment Of Radiotherapy-Enhancing Nanoparticles, Hayden Winter

Dissertations and Theses

Radiation Therapy (RT) is a common treatment for cancerous lesions that acts by ionizing matter in the affected tissue, causing cell death. The disadvantage of RT is that it is most often delivered via an external beam of radiation which must pass through healthy tissues to reach the target site, ionizing matter within healthy tissues as well. To address this drawback, techniques are being developed for increasing RT-induced cell death in a target tissue while minimizing cell death in surrounding tissues. This effect is known as radiation dose enhancement or RT enhancement.

The approach to RT enhancement studied in this …

Response Of Photoluminescence Of H-Terminated And Hydrosilylated Porous Si Powders To Rinsing And Temperature, Kurt W. Kolasinski, Joseph D. Swanson, Benjamin Roe, Teresa Lee

Chemistry Faculty Publications

The photoluminescence (PL) response of porous Si has potential applications in a number of sensor and bioimaging techniques. However, many questions still remain regarding how to stabilize and enhance the PL signal, as well as how PL responds to environmental factors. Regenerative electroless etching (ReEtching) was used to produce photoluminescent porous Si directly from Si powder. As etched, the material was H-terminated. The intensity and peak wavelength were greatly aected by the rinsing protocol employed. The highest intensity and bluest PL were obtained when dilute HCl(aq) rinsing was followed by pentane wetting and vacuum oven drying. Roughly half of the …

Synthesis Of Alpha-Methylselenocysteine, Its Relevant Analogues, And An Unnatural Glutathione Disulfide Core, Robert J. Wehrle

Dissertations

Selenoproteins, such as glutathione peroxidase, have gained interest for their ability to act as antioxidants, and their potential to act as anti-cancer agents. Synthesizing and studying selenoproteins can be problematic, however, due to their propensity to degrade from over-oxidation. The degradation from over-oxidation can be avoided by the incorporation of the unnatural amino acid, alpha-methylselenocysteine. A synthesis utilizing methyl malonic esters was used to synthesize protected (R)-alpha-methylselenocysteine efficiently (46% over four steps) and in high enantio-purity (88% enantiomeric excess). Using similar procedures, the (S)-enantiomer was also synthesized as well as a beta-analogue.

The use of enzymes …

Machine Learning Approaches For Improving Prediction Performance Of Structure-Activity Relationship Models, Gabriel Idakwo

Dissertations

In silico bioactivity prediction studies are designed to complement in vivo and in vitro efforts to assess the activity and properties of small molecules. In silico methods such as Quantitative Structure-Activity/Property Relationship (QSAR) are used to correlate the structure of a molecule to its biological property in drug design and toxicological studies. In this body of work, I started with two in-depth reviews into the application of machine learning based approaches and feature reduction methods to QSAR, and then investigated solutions to three common challenges faced in machine learning based QSAR studies.

First, to improve the prediction accuracy of learning …

New Strategies For Hydrosilylation Of Propargyl Alcohols, Olefin Polymerization And On-Chip Organic Synthesis, Udaya Sree Dakarapu

Chemistry & Biochemistry Dissertations - Archive

The research described in this dissertation is on three different projects namely i) design and synthesis of traceless hydrosilyl acetal-directed, exo-syn hydrosilylation of propargyl alcohols to produce α-hydroxy (E)-vinylsilanes, ii) alkali metal lewis base-catalyzed, complexation-induced hydrogen atom transfer (LBCI-HAT) olefin polymerization and iii) on-chip organic synthesis enabled by engine-and-cargo on an electrowetting-on-dielectric digital microfluidic (EWOD) device. The first chapter is focused on the design and synthesis of traceless hydrosilyl acetal-directed, exo-syn hydrosilylation of propargyl alcohols to produce α-hydroxy (E)-vinylsilanes. Transition metal-catalyzed regioselective intramolecular hydrosilylation of propargylic alcohols utilizing easily accessible, inexpensive, and readily installable hydrosilyl acetals as a directing group …