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The Effects Of Reactant Concentration And Air Flow Rate In The Consumption Of Dissolved O2 During The Photochemistry Of Aqueous Pyruvic Acid, Alexis J. Eugene, Marcelo I. Guzman 2019 University of Kentucky

The Effects Of Reactant Concentration And Air Flow Rate In The Consumption Of Dissolved O2 During The Photochemistry Of Aqueous Pyruvic Acid, Alexis J. Eugene, Marcelo I. Guzman

Chemistry Faculty Publications

The sunlight photochemistry of the organic chromophore pyruvic acid (PA) in water generates ketyl and acetyl radicals that contribute to the production and processing of atmospheric aerosols. The photochemical mechanism is highly sensitive to dissolved oxygen content, [O2(aq)], among other environmental conditions. Thus, herein we investigate the photolysis (λ ≥ 305 nm) of 10–200 mM PA at pH 1.0 in water covering the relevant range 0 ≤ [O2(aq)] ≤ 1.3 mM. The rapid consumption of dissolved oxygen by the intermediate photolytic radicals is monitored in real time with a dissolved oxygen electrode. In addition, the rate ...


Scale Up Isolation Of Aaptamine For In Vivo Evaluation Indicates Its Neurobiological Activity Is Linked To The Delta Opioid Receptor, Nicole L. McIntosh, Eptisam Lambo, Laura Millan-Lobo, Fei Li, Li He, Phillip Crews, Jennifer L. Whistler, Tyler Johnson 2019 Dominican University of California

Scale Up Isolation Of Aaptamine For In Vivo Evaluation Indicates Its Neurobiological Activity Is Linked To The Delta Opioid Receptor, Nicole L. Mcintosh, Eptisam Lambo, Laura Millan-Lobo, Fei Li, Li He, Phillip Crews, Jennifer L. Whistler, Tyler Johnson

Tyler Johnson

Opioid receptors belong to the large superfamily of seven transmembrane-spanning (7TM) G protein-coupled receptors (GPCRs). As a class, GPCRs are of fundamental physiological importance mediating the actions of the majority of known neurotransmitters and hormones. The Mu, Delta, and Kappa (MOP, DOP, KOP) opioid receptors are particularly intriguing members of this receptor family as they are the targets involved in many neurobiological diseases such as addiction, pain, stress, anxiety, and depression. Recently we discovered that the aaptamine class of marine sponge derived natural products exhibit selective agonist activity in vitro for the DOP versus MOP receptor. Our findings may explain ...


Synthesis Of A Sulfur Variant For Treatment Of Trypanosomiasis, Carlos Vera-Esquivel 2019 University of Nebraska at Omaha

Synthesis Of A Sulfur Variant For Treatment Of Trypanosomiasis, Carlos Vera-Esquivel

Student Research and Creative Activity Fair

Previous work in our lab has found diphenyl ether benzylamines showed a successful response with a micromolar concentration of our lead compound to treat the deadly Trypanosamiosis rhodesience. Furthermore, mammalian cell lines saw promising resistance towards damages. The goal of this study was to synthesize a diphenyl thio benzylamine variant. This variant was more active toward T. b. rhodesience but showed more toxicity to both rat 10 (IC50 mM) and human cell lines (HFF, HC-04, U-2 OS, and HEK293). The selectivity index (ratio of toxicity to activity in the same concentration units (SI)) varied from 55 ...


Facile And Efficient Synthesis Of Thiosemicarbazone Derivatives With Functionalized Pendant Amines., Anna E Davis 2019 University of Louisville

Facile And Efficient Synthesis Of Thiosemicarbazone Derivatives With Functionalized Pendant Amines., Anna E Davis

College of Arts & Sciences Senior Honors Theses

Bis-thiosemicarbazones are an important class of ligands for the synthesis of transition metal complexes with applications in medicine and electrochemistry.1,2 Among the most studied of these complexation ligands is diacetyl-2,3-bis(N4-methyl-3-thiosemicarbazone) (denoted as ATSM, 1, Figure 1).2,3 Derivatives of 1 with various amines in place of the methylamine of ATSM have previously been reported, including diacetyl (N4-methylthiosemicarbazone-N4′-dimethylthio-semicarbazone) (denoted as ATSM/DM, 2).4 In this work, we pursue the development of a library of ATSM derivatives with a variety of functionalized pendant amines with a range of electronic ...


Seasonal Origins Of Soil Water Used By Trees, Scott T. Allen, James W. Kirchner, Sabine Braun, Rolf T. W. Siegwolf, Gregory R. Goldsmith 2019 ETH Zurich

Seasonal Origins Of Soil Water Used By Trees, Scott T. Allen, James W. Kirchner, Sabine Braun, Rolf T. W. Siegwolf, Gregory R. Goldsmith

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Rain recharges soil water storages and either percolates downward into aquifers and streams or is returned to the atmosphere through evapotranspiration. Although it is commonly assumed that summer rainfall recharges plant-available water during the growing season, the seasonal origins of water used by plants have not been systematically explored. We characterize the seasonal origins of waters in soils and trees by comparing their midsummer isotopic signatures (δ2H) to seasonal isotopic cycles in precipitation, using a new seasonal origin index. Across 182 Swiss forest sites, xylem water isotopic signatures show that summer rain was not the predominant water source for ...


Development Of In Situ Forming Hydrogels For Intra-Articular Drug Delivery, Andy Prince 2019 The University of Western Ontario

Development Of In Situ Forming Hydrogels For Intra-Articular Drug Delivery, Andy Prince

Electronic Thesis and Dissertation Repository

Hydrogels are 3-dimensional crosslinked polymer networks that can absorb significant amounts of water. The physical properties associated with hydrogels affords them resemblance to biological tissues making them good candidates for biomedical applications. Many pharmaceuticals, specifically non-steroidal anti-inflammatory drugs (NSAIDs), have poor aqueous solubility, which limits their bioavailability and efficacy. People suffering from chronic osteoarthritis (OA) are required to frequently take large doses to mitigate pain, which can lead to serious side effects. Hydrogels are good strategies to deliver NSAIDs via articular injection because they can form solid gels in situ. This thesis describes the synthesis, formulation, mechanical testing, in vitro ...


Ring Expansion Of Alkylidenecarbenes Derived From Lactams, Lactones, And Thiolactones Into Strained Heterocyclic Alkynes: A Theoretical Study, N. N. Thu Le, J. Just, J. M. Pankauski, Paul R. Rablen, D. M. Thamattoor 2019 Swarthmore College

Ring Expansion Of Alkylidenecarbenes Derived From Lactams, Lactones, And Thiolactones Into Strained Heterocyclic Alkynes: A Theoretical Study, N. N. Thu Le, J. Just, J. M. Pankauski, Paul R. Rablen, D. M. Thamattoor

Chemistry & Biochemistry Faculty Works

Strained cycloalkynes are of considerable interest to theoreticians and experimentalists, and possess much synthetic value as well. Herein, a series of cyclic alkylidenecarbenes—formally obtained by replacing the carbonyl oxygen of four-, five-, and six-membered lactams, lactones, and thiolactones with a divalent carbon—were modeled at the CCSD(T)/cc-pVTZ//B3LYP/6-311+G** and CCSD(T)/cc-pVTZ//CCSD/6-311+G** levels of theory. The singlet carbenes were found to be more stable than the triplets. The strained heterocyclic alkynes formed by ring expansion of these singlet carbenes were also modeled. Interestingly, the C≡C bonds in the five-membered heterocycles, obtained ...


Bisthioether Stapled Peptides Targeting Polycomb Repressive Complex 2 Gene Repression, Gan Zhang 2019 The Graduate Center, City University of New York

Bisthioether Stapled Peptides Targeting Polycomb Repressive Complex 2 Gene Repression, Gan Zhang

All Dissertations, Theses, and Capstone Projects

Interactions between proteins play a key role in nearly all cellular process, and therefore, disruption of such interactions may lead to many different types of cellular dysfunctions. Hence, pathologic protein-protein interactions (PPIs) constitute highly attractive drug targets and hold great potential for developing novel therapeutic agents for the treatment of incurable human diseases. Unfortunately, the identification of PPI inhibitors is an extremely challenging task, since traditionally used small molecule ligands are mostly unable to cover and anchor on the extensive flat surfaces that define those binary protein complexes. In contrast, large biomolecules such as proteins or peptides are ideal fits ...


Multidimensional Mass Spectrometry Of Chemonic™ Ccg-6 Nonionic Surfactant With Separation By Polarity And Shape, Charles Johnson 2019 The University of Akron

Multidimensional Mass Spectrometry Of Chemonic™ Ccg-6 Nonionic Surfactant With Separation By Polarity And Shape, Charles Johnson

Williams Honors College, Honors Research Projects

Chemonic™ CCG-6 surfactant is a water-soluble poly(ethylene glycol) (PEG) conjugated alkyl glyceride emollient. This surfactant exists as a complex mixture of a glycerol cores conjugated with poly(ethylene glycol) branches (PEGylation) that were partially esterified with caprylic (C8) and capric (C10) acids. These may be esterified on one, two, or all three arms of the glyceride. The architecture of the structures in this mixture was studied using multidimensional mass spectrometry (MS). Mass spectrometry was interfaced with ultra-performance liquid chromatography (UPLC) and ion mobility (IM) separation. The mixture was separated by reversed-phase LC, oligomers of the star-branched polymer were separated ...


Functionality Of Membrane Proteins Overexpressed And Purified From E. Coli Is Highly Dependent Upon The Strain, Khadija Mathieu, Waqas Javed, Sylvain Vallet, Christian Lesterlin, Marie-Pierre Candusso, Feng Ding, Xiaohong Nancy Xu, Christine Ebel, Jean-Michel Jault, Cédric Orelle 2019 Old Dominion University

Functionality Of Membrane Proteins Overexpressed And Purified From E. Coli Is Highly Dependent Upon The Strain, Khadija Mathieu, Waqas Javed, Sylvain Vallet, Christian Lesterlin, Marie-Pierre Candusso, Feng Ding, Xiaohong Nancy Xu, Christine Ebel, Jean-Michel Jault, Cédric Orelle

Chemistry & Biochemistry Faculty Publications

Overexpression of correctly folded membrane proteins is a fundamental prerequisite for functional and structural studies. One of the most commonly used expression systems for the production of membrane proteins is Escherichia coli. While misfolded proteins typically aggregate and form inclusions bodies, membrane proteins that are addressed to the membrane and extractable by detergents are generally assumed to be properly folded. Accordingly, GFP fusion strategy is often used as a fluorescent proxy to monitor their expression and folding quality. Here we investigated the functionality of two different multidrug ABC transporters, the homodimer BmrA from Bacillus subtilis and the heterodimer PatA/PatB ...


Design, Synthesis And Biological Evaluation Of (+)-Discodermolide And Synthetic Study Towards (–)-Pterocidin, Nan Zhang 2019 University of Pennsylvania

Design, Synthesis And Biological Evaluation Of (+)-Discodermolide And Synthetic Study Towards (–)-Pterocidin, Nan Zhang

Publicly Accessible Penn Dissertations

ABSTRACT

DESIGN, SYNTHESIS AND BIOLOGICAL EVALUATION

OF (+)-DISCODERMOLIDE ANALOGS

AND

SYNTHETIC STUDY TOWARDS (–)-PTEROCIDIN

Nan Zhang

Amos B. Smith, III

Chapter one describes the design and synthesis of novel (+)-discodermolide analogs, that featured different saturation degrees of the terminal diene system and various lactone moieties. Biological evaluation via multiparameter dose-response analysis identified analog B2 as lead congener with superior efficacy towards different cancer cell lines. The high-resolution crystal structure of the B2-tubulin complex was obtained, shedding light on future design of new (+)-discodermolide analogs based on a better understanding of binding mechanism at molecular level.

Chapter two describes a “high-risk ...


Expanding Peptide Stapling With S-Tetrazine, Matthew Henry Bunner 2019 University of Pennsylvania

Expanding Peptide Stapling With S-Tetrazine, Matthew Henry Bunner

Publicly Accessible Penn Dissertations

ABSTRACT

EXPANDING PEPTIDE STAPLING WITH s-TETRAZINE

Matthew H. Bunner

Professor Amos B. Smith, III

This dissertation presents efforts toward the extension of synthetic methods for the creation of peptide macrocycles via the addition of dichloro-s-tetrazine to peptide sequences containing lysine, serine, threonine, and tyrosine. Chapter one reviews the work and interest of the Smith group in the s-tetrazine chromophore and the history of stapled peptides in the chemical literature. Chapter two describes (A) the development of a synthetic protocol for the creation of peptide macrocycles from peptide sequences containing a single cysteine and a single lysine residue using dichloro-s-tetrazine including ...


Synthesis Of 1,3-Di(4-Pyridinyl)Acetone, Zachary Tyler Boggs 2019 Marshall University

Synthesis Of 1,3-Di(4-Pyridinyl)Acetone, Zachary Tyler Boggs

Theses, Dissertations and Capstones

Although isoelectronic to benzene, the reactivity of pyridine-derived compounds can be quite different. Notably, routes to prepare pyridyl analogs to known phenyl compounds can be very different from how the phenyl compounds are made, even when the nitrogen atom would appear to play an insignificant role in the reaction. This is the case for 1,3-di-4-pyridylacetone. Its phenyl analog has been known for over 90 years and is easily prepared, while the only reported synthesis of 1,3-di-4-pyridylacetone occurs in very low yield. We report a preliminary synthesis from common starting materials, albeit in low yield, and offer an explanation ...


Refinement Of Production Grade Biodiesel, Campbell Axt, Robert B. Hughley Jr., Sydney Ninneman, Jillian Turner 2019 GCSU

Refinement Of Production Grade Biodiesel, Campbell Axt, Robert B. Hughley Jr., Sydney Ninneman, Jillian Turner

The Corinthian

The modified Burton method for the thermal hydrogen-cracking of peanut oil has been investigated in McGill Research Group since 2009. The successful and reliable production of biodiesel has been achieved since 2014. A hydrocarbon with a viscosity similar to Production Grade Diesel will work in modern diesel engines. The current product has a viscosity significantly lower than production grade diesel. The starting material has a viscosity significantly higher than Production Grade Diesel. Current research is investigating methodologies to mix starting material and product to achieve target viscosity.


The Chemical Analysis And Biological Activities Of The Secondary Metabolites From Dalea Mollis And Dalea Albiflora, Nicholas Peter Hansen 2019 Central Washington University

The Chemical Analysis And Biological Activities Of The Secondary Metabolites From Dalea Mollis And Dalea Albiflora, Nicholas Peter Hansen

All Master's Theses

Multidrug resistance has increased since the introduction of drugs used to prevent growth and kill microorganisms in a host. This has caused a worldwide search to discover new drugs effective against microorganisms. Mechanisms of drug resistance include, but are not limited to, the production of biofilms and efflux pumps. Efflux pumps prevent antimicrobial drugs from reaching their biological target, so the coordinated use of efflux pump inhibitors and antimicrobial drugs has been identified as a potential treatment for multidrug-resistant microorganisms. The secondary metabolites of Dalea mollis and Dalea albiflora were tested against multidrug-resistant (MDR) and engineered strains of the fungi ...


Carl Bosch And The Haber-Bosch Process, Jacob Larkin 2019 Parkland College

Carl Bosch And The Haber-Bosch Process, Jacob Larkin

Natural Sciences Poster Sessions

This poster for the Natural Sciences Poster Session at Parkland College features organic chemist Carl Bosch, winner of the Nobel Prize of Chemistry in 1931 for his contribution to the development of chemical high pressure methods, Bosch built on Fritz Haber's process of fixing nitrogen using high pressure chemistry to industrialize the process on a large scale to mass produce fertilizer, now known as the Haber-Bosch process, which takes nitrogen from the air, bonds it with hydrogen from natural gases and converts it to ammonia.


Method Considerations For Compound Identification In Complex Mixtures Using Electrospray Ionization Ultrahigh Resolution Mass Spectrometry, Tyler Leverton 2019 Michigan Technological University

Method Considerations For Compound Identification In Complex Mixtures Using Electrospray Ionization Ultrahigh Resolution Mass Spectrometry, Tyler Leverton

Dissertations, Master's Theses and Master's Reports

Biomass burning aerosols are highly complex organic mixtures of thousands of components with consequences for global climate. Complex mixture component identification requires accurate mass measurement capability to separate components on a milli-Dalton scale, frequently using ultrahigh resolution mass spectrometry with electrospray ionization. Certain sample preparations and the ionization process may introduce artifacts that obscure the composition of the sample. Two method considerations were explored using isotopically labeled 15NH4OH and MeOH-d3 to track artifact formation in biomass burning samples. Informatics techniques and a custom molecular formula assignment software were used to identify the isotopic atoms in artifact ...


Ibuprofen As A Probe Of Lipid Metabolism, Jose Antonio Rosales 2019 University of Texas at El Paso

Ibuprofen As A Probe Of Lipid Metabolism, Jose Antonio Rosales

Open Access Theses & Dissertations

The hypothesis that deracemization of racemic ibuprofen (IBU) occurs via the enolization of a Candida rugosa lipase (CRL)-ibuprofen ester (Scheme 1.6.2) was disproven by reacting racemic IBU under the conditions that were used to deracemize ibuprofen methyl ester (IME), namely pH 7.6. At pH 7.6, IME through IBU butyl esters were not formed in-situ and racemic IBU was not deracemized by reacting the corresponding primary alcohol with racemic IBU in the presence of CRL.

At pH 7.6, hexyl through dodecyl IBU esters were formed in-situ by reacting the corresponding primary alcohol with racemic IBU ...


Synthesis Of Oligodeoxynucleotides Containing Sensitive Electrophiles, Shahien Shahsavari 2019 Michigan Technological University

Synthesis Of Oligodeoxynucleotides Containing Sensitive Electrophiles, Shahien Shahsavari

Dissertations, Master's Theses and Master's Reports

Oligodeoxynucleotides (ODNs) containing electrophilic groups are useful in many studies including antisense drug development and DNA/protein interaction. Due to the use of strong nucleophiles for cleavage and deprotection, traditional ODN synthesis methods are not suitable for their preparation. To solve this problem, a new ODN synthesis technology using the 1,3- dithiane-2-yl-methoxycarbonyl (Dmoc) function as protecting groups and linker has been developed. Furthermore, Dmoc-derivatives were developed to demonstrate the feasibility of the technology. The Dmoc and Dmoc derivative functions are stable under all ODN synthesis conditions using the phosphoramidite chemistry. Upon oxidation of the sulfides in them, because of ...


Design, Synthesis And Study Of Functional Amphiphilic Polymers And Their Applications, Huan He 2019 University of Massachusetts Amherst

Design, Synthesis And Study Of Functional Amphiphilic Polymers And Their Applications, Huan He

Doctoral Dissertations

Amphiphilic homopolymers with high densities of functional groups are synthetically challenging. Thiol-yne nucleophilic click reactions have been investigated to introduce multiple functional groups in polymers with high density. An electron deficient alkyne group bearing methacrylate monomer was polymerized using reversible addition−fragmentation chain-transfer (RAFT) polymerization. Subsequently, the electron deficient alkyne group on polymer side chain was readily reacted with a thiol reagent using triethylamine (TEA) as the organocatalyst. This reaction was found to be very efficient under mild conditions. The resultant homopolymer bearing thiol vinyl ether functional groups could perform a second thiol addition with a stronger base, such as ...


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