Physical Sciences and Mathematics Commons^™

Sustainable Approaches To Photo-, Thermo-, And Electro-Chemical Reactions Of Amines, James David Sitter

Theses and Dissertations

In recent years, sustainable routes for chemical synthesis have garnered renewed interest. As the world continues to fight pollution and rising costs, it is imperative that new routes of synthesis that continuously fight the issues of pollution and waste are discovered, defined and explored. While traditional synthesis routes that require energy input typically require the burning of fossil fuels to produce heat, the amount of resources that go into the production of these fossil fuels and the sequestration of its waste to minimize its impact on the carbon footprint is enormous. Furthermore, sustainable chemistry research aims to decrease and minimize …

Synthesis And Study Of Anticancer And Antioxidant Activities Of 2-Oxoquinoline Hydrazide Derivatives, Marwa Khalil Mohamed, Ezzeldin Mohamed S. Salem, Ibrahim Ahmed I. Ali

Makara Journal of Science

In this work, hydrazone, thiosemicarbazide, diamide, and dipeptide derivatives were prepared from the glycine and β-alanine hydrazide of 4-hydroxy-2-oxoquinoline. The desired derivative resulted from substitution, hydrazinolysis, condensation, and azide coupling reactions. The fabricated derivatives were screened for anticancer characteristics toward human’s colon carcinoma (HCT-116) cell line using the 3-[4,5-dimethylthiazol-2-yl]-2,5 diphenyl tetrazolium bromide viability assay, while antioxidant property was examined using an in vitro H₂O₂ scavenging method. The β-alanine hydrazide derivative 3a showed a remarkable IC₅₀ value of 18.8 μg/mL, whereas its corresponding thiosemicarbazide 5b exhibited moderate activeness with an IC₅₀ value of 26.89 μg/mL. Conversely, …

Synthesis, Characterization, And Catalytic Activity Of Functionalized Metal Bis(Thiosemicarbazones)., Caleb Aaron Calvary

Electronic Theses and Dissertations

Bis-(thiosemicarbazones) are a class of ligands that have found a wide range of uses from electrocatalysts to medicinal and diagnostic reagents. These ligands contain a diimine backbone, N₂S₂ chelating core, and pendent amines. In order to further explore this class of ligands, the previously underreported transamination reaction, which exchanges one pendent amine group for another, was utilized to create several derivatives using aliphatic and aromatic amines. The transamination reaction is appealing alternative to making the desired thiosemicarbazide. Further appeals come from the fact that it is a one-pot reaction that gives highly pure products in good yields. …

Synthesis Of Some Nh- And Nh,S- Substituted 1,4-Quinones, Ayşeci̇k Kaçmaz

Turkish Journal of Chemistry

A series of NH-substituted-1,4-quinones, possessing one, two, three or not chlorine, were synthesized by the reaction between different quinones (p-chloranil (1), p-toluquinone (2), or 2,3-dichloro-1,4-naphthoquinone (3)) and (-)-cis-myrtanylamine (5) via nucleophilic reactions. Moreover, 2-bromo-1,4-naphthoquinone (4) was reacted with 2-(methylthio)ethylamine (11) to produce aminosubstituted naphthoquinones (12 and 13), bearing with bromine and not bromine. In addition, 2-bromo-1,4-naphthoquinone (4) was reacted with 4?-aminodibenzo-18-crown-6 (14) and 4'-aminobenzo-18-crown-6 (16) to yield crown-containing 1,4-naphthoquinones (15 and 17), respectively. New compounds were characterized, providing 1H NMR, 13C NMR, FTIR, MS-ESI, UV/Vis and elemental analysis.

Reactivity Of Photogenerated Amine Radical Cations, Qile Wang

Graduate Theses and Dissertations

Recently photoredox catalysis has emerged as a powerful tool in organic synthesis led by Professor McMillan, Stephenson, Yoon. Upon absorption of visible light, photocatalyst can be excited to its singlet state followed by intersystem crossing to form a long lived excited triplet state. While amine serves as electron donor, single electron transfer (SET) can happen between excited triplet photocatalyst and nitrogen atom on amine to give a reduced photocatalyst and amine radical cation.

Cyclopropylamines or cyclobutylamines can be oxidized by excited photocatalyst to generate amine radical cations and due to the ring strain, subsequent C-C bond cleavages can lead to …

The Investigation Of Secondary Particle Formation Initiated By Non-Prototypical Sources And The Role Of Amines In The Atmosphere, Emily Burrell

Theses and Dissertations

This dissertation is a collection of works that investigate non-prototypical sources leading to new particle formation in the atmosphere. Particles play a major role in atmospheric chemistry. For example, particles are a component of smog and are commonly found in high concentrations under conditions of atmospheric inversions. In order to reconcile the difference between measured and modeled particle concentrations new mechanisms from non-prototypical sources for particle formation need to be determined. Formation of particles has frequently been modeled using classical nucleation theory (CNT). The first step in CNT is the nucleation step where molecular clusters form. In a second step, …

Isolation And Characterization Of Novel Arginine-Derived Heterocyclic Amines, Nathaniel Srikureja

Honors Theses

Most known heterocyclic amines (HCAs) are potent mutagens present at significant concentrations in cooked meats, and can be synthesized from burned mixtures of L-creatin(in)e with various amino acids. We hypothesize that novel mutagenic HCAs may be synthesized from a heated plant-based food simulating binary amino acid mL'\:ture: L-arginine and L-threonine. A two-part solid phase extraction was used to separate nitrogen heterocycles from byproducts followed by prep­ HPLC and the Ames mutagenicity assay using Salmonella TA98 to determine the mutagenicity of various isolates. The results indicate that this binary amino acid mixture does not yield a mutagenic sample.

Evaluating Mutagenicity Of Burned Arginine-Based Heterocyclic Amines And Anti-Mutagenicity Effect Of Chinese Medicinal Herbs, Rayford C. Alva

Honors Theses

From the unexpected finding that cooked grains and meat substitutes elicit a mutagenic response in Salmonella typhimurium TA98, our work has been aimed at deconstructing this finding via a survey of heated binary amino acid combinations, involving arginine, a plant-based amino acid. secondly, our work has looked towards sing phytochemical extracts from traditional Chinese medicinal herbs to inhibit the mutagenic activity of heterocyclic amines (main culprit for mutagenicity in meat). Two fractions from the burned products of arginine and phenylalanine (RF-HCA-06 and -07) were statistically significant inducers of mutagenesis; Scutellaria barbata and Oldenlandia diffusa, both separately and together, were statistically …

Informing Efforts To Develop Nitroreductase For Amine Production, Anne-Frances Miller, Jonathan T. Park, Kyle L. Ferguson, Warintra Pitsawong, Andreas S. Bommarius

Chemistry Faculty Publications

Nitroreductases (NRs) hold promise for converting nitroaromatics to aromatic amines. Nitroaromatic reduction rate increases with Hammett substituent constant for NRs from two different subgroups, confirming substrate identity as a key determinant of reactivity. Amine yields were low, but compounds yielding amines tend to have a large π system and electron withdrawing substituents. Therefore, we also assessed the prospects of varying the enzyme. Several different subgroups of NRs include members able to produce aromatic amines. Comparison of four NR subgroups shows that they provide contrasting substrate binding cavities with distinct constraints on substrate position relative to the flavin. The unique architecture …

Spectroscopic And Computational Characterization Of Lanthanum-Mediated C-H And N-H Bond Activation Of Amines, Silver Nyambo, Yuchen Zhang, Dong-Sheng Yang

Commonwealth Computational Summit

Metal-mediated bond activation of small organic and inorganic molecules plays critical roles in chemical transformation of small molecules into value-added products.

This is because few of such chemical reactions would occur under mild conditions without the metal activation.

In this work, lanthanum atom reactions with alkylamines are carried out in a laser-ablation supersonic molecular beam source; C-H and N-H bond activation in these species is investigated.

The reaction products are observed with photoionization time-of-flight mass spectrometry and characterized by mass-analyzed threshold ionization (MATI) spectroscopy and theoretical calculations.

Adiabatic ionization energy and metal-ligand and ligand-based vibrational frequencies of several short-lived lanthanum …

Electrical Properties Of Covalently Functionalized Graphene, Paul Plachinda, David Evans, Raj Solanki

Physics Faculty Publications and Presentations

We have employed first-principle calculations to study transformation of graphene’s electronic structure under functionalization by covalent bonds with different atomic and molecular groups - epoxies, amines, PFPA. It is shown that this functionalization leads to an opening in the graphene’s band gap on order of tens meV, but also leads to reduction of electrical conductivity. We also discuss the influence of charge exchange between the functionalizing molecule and graphene’s conjugated electrons on electron transport properties.

Copper Salt-Catalyzed Formation Of A Novel Series Of Triazole-Spirodienone Conjugates With Potent Anticancer Activity., L. Gu, P. Wang, Qiu Zhong, Y. Deng, J. Xie, F. Liu, F. Xiao, Shilong Zheng, Y. Chen, Guangdi Wang, L. He

Faculty and Staff Publications

Copper salt-catalyzed oxidative amination resulted in the formation of a novel series of triazole-spirodienone conjugates, 4-triazolyl-1-oxa-4-azaspiro[4,5]deca-6,9-dien-3,8-diones and 4-triazolyl-1-oxa-4-azaspiro[4,5]deca-6,9-dien-8-ones. A single crystal of compound 1p among them was grown and analyzed by X-ray crystallography. These compounds were evaluated for their antiproliferative activities against MDA-MB-231, HeLa, A549 and MCF-7 cell lines. Most of them showed moderate to high anticancer potency in the four cancer cell lines. The discovery of the triazole-spirodienone conjugates as cytotoxic agents against cancer cells may open up a new field in which these novel small molecules could be further explored as promising anticancer agents.

Graphite Oxide Catalyzed Synthesis Of $\Beta $-Amino Alcohols By Ring-Opening Of Epoxides, Maryam Mirza-Aghayan, Farzaneh Alvandi, Mahdieh Molaee Tavana, Rabah Boukherroub

Turkish Journal of Chemistry

Graphite oxide as a heterogeneous and recyclable solid acid catalyzed a simple and efficient method for the synthesis of $\beta $-amino alcohols by ring opening of epoxides with amines. This method is effective with various aromatic and aliphatic amines under solvent-free conditions. The corresponding $\beta $-amino alcohols are obtained in high yields (56%-95%) and short reaction times (15-30 min) with high regio- and chemoselectivity under metal-free conditions.

Catalytic Transfer Hydrogenation Of Nitroalkenes To Primary Amines, Brendan Phillips

Chemistry Honors Papers

This work describes synthetic methodology development in organic chemistry. The goal of this work is to demonstrate new ways of making biologically-relevant molecules that are in line with the principles of green chemistry (chemical practices which seek to be, regarding human and environmental health, benign by design). To this end, a new method has been developed toward the introduction of primary amine functionalities into organic molecules from readily-available aldehydes, via reduction of nitroalkene intermediates. Traditional methods of reducing nitroalkenes to primary amines require harsh conditions, often produce stoichiometric amounts of metal salt waste, and present significant safety challenges to the …

Multivalent Recognition Of Peptides By Modular Self-Assembled Receptors, Joseph Reczek, Aimee Kennedy, Brian Halbert, Adam Urbach

Adam R Urbach

Developing nontraditional approaches to the synthesis and characterization of multivalent compounds is critical to our efforts to study and interface with biological systems and to build new noncovalent materials. This paper demonstrates a biomimetic approach to the construction of discrete, modular, multivalent receptors via molecular self-assembly in aqueous solution. Scaffolds presenting 1−3 viologen groups recruit a respective 1−3 copies of the synthetic host, cucurbit[8]uril, in a noncooperative manner and with a consistent equilibrium association constant (Ka) value of 2 × 106 M−1 per binding site. The assembled mono-, di-, and trivalent receptors bind to their cognate target peptides containing 1−3 …

Phase Considerations In The Gas/Particle Partitioning Of Organic Amines In The Atmosphere, James F. Pankow

Chemistry Faculty Publications and Presentations

Amines in the atmosphere are of interest because of their likely role in new particle formation, and because of anthropogenic emissions of amines at post-combustion carbon capture (PCCC) facilities. A conceptual framework for considering the partitioning of a monobasic amine (Am = unprotonated "free-base form) from the gas phase to atmospheric particulate matter (PM) is presented for cases when the PM may be composed of multiple liquid phases. Three types of liquid phases are considered as being individually or simultaneously possible for absorptive uptake of atmospheric amines: w) a mostly water phase; α ) a mostly (by mass) organic phase …

Microwave-Assisted Synthesis Of Ss-Amino Alcohols, Hinalbahen Sanket Desai

Master's Theses and Doctoral Dissertations

ß-amino alcohols are common substructures in many biologically active compounds and can also be used as catalysts for asymmetric reactions. One common method for forming these moieties is by ring opening of unsymmetrical epoxides using amines via a substitution reaction. However, the majority of these methods requires excess of reagents, inorganic initiators, and/or extended reaction times. We have developed an efficient, regioselective route to synthesize amino alcohols via microwave-assisted aminolysis of several hindered and unhindered epoxides using amine nucleophiles of varying strengths. Microwave reactions can be done without Lewis acids or promoters, even for the most hindered trisubstituted epoxides. In …

Total Synthesis Of Clavatadine A, Stephanie J. Conn, Shannon M. Vreeland, Alexandra N. Wexler, Rebecca H. Pouwer, Ronald J. Quinn, Stephen Chamberland

All Faculty Scholarship for the College of the Sciences

The first total synthesis of the potent and selective human blood coagulation factor XIa inhibitor clavatadine A (1) is described. Direct, early-stage guanidinylation enabled rapid, convergent access to an immediate clavatadine A precursor. Concomitant lactone hydrolysis and guanidine deprotection with aqueous acid cleanly provided clavatadine A (1) in only four steps (longest linear sequence, 41–43% overall yield).

Brust-Schiffrin Synthesis Of Catalytic Bipodal Pdpt Nanoparticles With Some Mechanistic Insights, Sangbum Han, Vara P. Sheela, Wei Cao, Balasubramanian Ramjee

Applied Research Center Publications

Brust–Schiffrin reduction of Pd and Pt precursors in the presence of resorcinarene amine surfactant led to the formation of substantially Pt rich, PdPt bimetallic nanoparticles of a V-shape or variants on the V-shape. New insights into this reaction are provided on the basis of reversed Brust–Schiffrin syntheses, DLS, UV-vis, and NMR analysis. Based on our experiments we conclude that the resorcinarene amine surfactant is part of the inverse micelle formed from TOABr and it also selectively complexes with the Pd salts prior to their reduction. Remarkably, the composition of the bipodal nanoparticles could be varied substantially by varying the reaction …

Asymmetric Synthesis Of \Alpha-(Heteroaryl)Alkylamines And \Alpha -Amino Acids Via Nucleophilic 1,2-Addition Of Lithiated Heterocycles To Aldehyde Samp-Hydrazones, Dieter Enders, Giuseppe Del Signore, Gerhard Raabe

Turkish Journal of Chemistry

The asymmetric synthesis of \alpha-(heteroaryl)alkylamines was accomplished by employing a diastereoselective nucleophilic 1,2-addition of lithiated aromatic heterocycles to aldehyde SAMP-hydrazones, followed by BH_3 . THF or SmI_2 promoted removal of the chiral auxiliary. The CBz or benzoyl-protected amines were obtained in good yields (40\%--78\%) and excellent enantiomeric excesses (ee = 88\%--99\%). The methodology can be applied to the synthesis of highly enantioenriched \alpha-amino acids (ee = 90\%--99\%).

Synthesis And Application Of L-Proline And R-Phenylglycine Derived Organocatalysts For Direct Asymmetric Michael Addition Of Cyclohexanone To Nitroalkenes, Hayri̇ye Nevi̇n Naziroğlu, Abdulkadi̇r Sirit

Turkish Journal of Chemistry

Novel R-phenylglycine derived organocatalysts were prepared from the reaction of Cbz-R-phenylglycine with indoline, pyrrolidine, or (S)-(-)-2-(diphenylmethyl)pyrrolidine in 3 steps. The asymmetric Michael addition of cyclohexanone to nitroolefins was investigated using R-phenylglycine derivatives along with L-prolinamides as chiral catalysts. The desired products were obtained in excellent yields with enantioselectivities up to 90% ee and diastereomeric ratio up to 98:2 of the syn }addition product.

Facile And Rapid Synthesis Of Some Novel Polysubstituted Imidazoles By Employing Magnetic Fe_3o_4 Nanoparticles As A High Efficient Catalyst, Bahador Karami, Khalil Eskandari, Abdolmohammad Ghasemi

Turkish Journal of Chemistry

Multicomponent, one-pot, highly efficient, and environmentally adapted synthesis of some novel polysubstituted imidazoles by the use of various aldehydes, benzil, aliphatic, and aromatic primary amines and ammonium acetate in the presence of Fe_3O_4 nanoparticles as catalyst under solvent-free condition is explained. A highly efficient role of Fe_3O_4 nanoparticles as catalyst in this synthesis was shown. By this advantage, several polysubstituted imidazoles as pharmaceutical important molecules can be prepared in high yield and high purity. This method is very easy and rapid for the synthesis of imidazole derivatives. All products were deduced from their IR and NMR spectroscopic data. The Fe_3O_4 …

Studies On Vinamidinium Salt Amine Exchange Reactions, Borohydride Reductions, And Subsequent Transformations, Xian Jia

Honors Theses

This research would not have been possible without the extraordinary guidance of Dr. John Gupton who I like to think of as the brains behind the operation. In addition, Dr. Nakul Telang, a postdoctoral fellow in Dr. Gupton’s research lab, has provided great support, assistance and humor throughout my undergraduate research career. The other student members of the lab that I would like to recognize for their support and contribution to this project are Ben Giglio, James Eaton, Peter Barelli, Mona Hovaizi, Kayleigh Hall, Scott Welden, Kara Finzel. We also thank the National Institutes of Health (grant no. R15‐CA67236) for …

An Effective Microwave-Induced Iodine-Catalyzed Method For The Synthesis Of Quinoxalines Via Condensation Of 12-Diamines With 12-Dicarbonyl Compounds, Debasish Bandyopadhyay, Sanghamitra Mukherjee, Robert R. Rodriguez, Bimal K. Banik

Chemistry Faculty Publications and Presentations

A microwave-induced iodine-catalyzed simple, rapid and convenient synthesis of different types of quinoxalines via condensation of 1,2-diamines with 1,2-dicarbonyl compounds has been accomplished with an excellent yield.

Multivalent Recognition Of Peptides By Modular Self-Assembled Receptors, Joseph J. Reczek, Aimee A. Kennedy, Brian T. Halbert, Adam R. Urbach

Chemistry Faculty Research

Developing nontraditional approaches to the synthesis and characterization of multivalent compounds is critical to our efforts to study and interface with biological systems and to build new noncovalent materials. This paper demonstrates a biomimetic approach to the construction of discrete, modular, multivalent receptors via molecular self-assembly in aqueous solution. Scaffolds presenting 1−3 viologen groups recruit a respective 1−3 copies of the synthetic host, cucurbit[8]uril, in a noncooperative manner and with a consistent equilibrium association constant (K_a) value of 2 × 10⁶ M⁻¹ per binding site. The assembled mono-, di-, and trivalent receptors bind to their …

Sources And Source Processes Of Organic Nitrogen Aerosols In The Atmosphere, Mark E. Erupe

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The research in this dissertation explored the sources and chemistry of organic nitrogen aerosols in the atmosphere. Two approaches were employed: field measurements and laboratory experiments. In order to characterize atmospheric aerosol, two ambient studies were conducted in Cache Valley in Northern Utah during strong winter inversions of 2004 and 2005. The economy of this region is heavily dependent on agriculture. There is also a fast growing urban population. Urban and agricultural emissions, aided by the valley geography and meteorology, led to high concentrations of fine particles that often exceeded the national ambient air quality standards. Aerosol composition was dominated …

Spectroscopic And X-Ray Crystallographic Characterization Of Bestatin Bound To The Aminopeptidase From Aeromonas (Vibrio) Proteolytica, Carin C. Stamper, David L. Bienvenue, Brian Bennett, Dagmar Ringe, Gregory A. Petsko, Richard C. Holz

Physics Faculty Research and Publications

Binding of the competitive, slow-binding inhibitor bestatin ([(2S,3R)-3-amino-2-hydroxy-4-phenylbutanoy]-leucine) to the aminopeptidase from Aeromonas proteolytica (AAP) was examined by both spectroscopic and crystallographic methods. Electronic absorption spectra of the catalytically competent [Co_(AAP)], [CoCo(AAP)], and [ZnCo(AAP)] enzymes recorded in the presence of bestatin revealed that both of the divalent metal ions in AAP are involved in binding bestatin. The electron paramagnetic resonance (EPR) spectrum of the [CoCo(AAP)]−bestatin complex exhibited no observable perpendicular- or parallel-mode signal. These data indicate that the two Co^II ions in AAP are antiferromagnetically coupled yielding an S = 0 ground state and suggest …

The Kinetics Of The Photochemical Reaction Of Methylene Green With Methylamine And Ethylamine, Rehana Saeed, Fahim Uddin, Zahida Khalid

Turkish Journal of Chemistry

The photochemical reduction of methylene green with methylamine and ethylamine in 50% aqueous isopropanol was studied. The photochemical reduction was carried out in a special type of optical processor associated with a deoxygenating system, a temperature controlling unit and a magnetic stirring system. A monochromatic light of 657 nm wavelength was used for irradiation of oxygen free reaction solutions in a double walled reaction cell. The transmitted light was measured and recorded in terms of electrical signals with the help of a calibrated galvanometer. Acidities of the solutions were measured with the help of a spectrophotometer based on the Hammet …

Relationship Between Alkaline Pulp Yield And The Mass Fraction And Degree Of Polymerization Of Cellulose In Pulp, Mehmet Sefik Tunc

Electronic Theses and Dissertations

Wood as a raw material is generally the dominant cost factor for the production of chemical pulp. Therefore, an increase in pulp yield has a major impact on the competitiveness of a mill. In order to optimize pulp yield, for example by changing operating conditions, a mill must be able to monitor the yield accurately. However, an accurate "real-time" pulp yield measurement method is not available at the present time. Pulping yield is presently measured from the amount of pulp produced from a given quantity of wood consumed over a 3 to 6 month time frame. This method is obviously …

A New Layered Iron Fluorophosphates, Amitava Choudhury

Chemistry Faculty Research & Creative Works

A new iron fluorophosphate of the composition, [C₆N₄H₂₁] [Fe₂F₂(HPO₄)₃][H₂PO₄]·2H₂O, I. has been prepared by the hydrothermal route. This compound contains iron fluorophosphate layers and the H₂PO₄^- anions are present in the interlayer space along with the protonated amine and water molecules. The compound crystallizes in the monoclinic space group P2₁/c. (a = 13.4422(10) Å, b = 9.7320(10) Å, c = 18.3123(3) Å, ? = 92.1480°, V = 2393.92(5) ų, Z = 4, …