Chemistry Commons^™

Synthesis, Characterization, And Antiproliferative Activity Of Novel Chiral [Quinoxp*Aucl2]+ Complexes, Adedamola S. Arojojoye, R. Tyler Mertens, Samuel Ofori, Sean R. Parkin, Samuel G. Awuah

Chemistry Faculty Publications

Herein is reported the synthesis of two Au(III) complexes bearing the (R,R)-(–)-2,3-Bis(tert-butylmethylphosphino)quinoxaline (R,R-QuinoxP*) or (S,S)-(+)-2,3-Bis(tert-butylmethylphosphino)quinoxaline (S,S-QuinoxP*) ligands. By reacting two stoichiometric equivalents of HAuCl₄.3H₂O to one equivalent of the corresponding QuinoxP* ligand, (R,R)-(–)-2,3-Bis(tert-butylmethylphosphino)quinoxalinedichlorogold(III) tetrachloroaurates(III) (1) and (S,S)-(+)-2,3-Bis(tert-butylmethylphosphino)quinoxalinedichlorogold(III) tetrachloroaurates(III) (2) were formed, respectively, in moderate yields. The structure of (S,S)-(+)-2,3-Bis(tert-butylmethylphosphino)quinoxalinedichlorogold(III) tetrachloroaurates(III) (2) was further confirmed by X-ray crystallography. The antiproliferative activities of the two compounds were evaluated in a panel of cell lines and exhibited promising results comparable to auranofin and cisplatin with …

Cu(Ii), Mn(Ii), Ni(Ii) Complexes Of Mixed Amodiaquine And Paraaminobenzoic Acid: Synthesis, Characterization, Antimicrobial And Toxicological Activities In Wister Rats, Mercy O. Bamigboye, Ikechukwu P. Ejidike, Abdulbasit A. Aliyu

Al-Qadisiyah Journal of Pure Science

Four novel metal complexes of mixed amodiaquine and paraaminobenzoic acid have been synthesized using a standard method and confirmed by results of some physicochemical and spectroscopic techniques. Antimicrobial activities have been carried out on the complexes against some selected organisms: (antibacterial organisms: K. pneumonia, B. subtilis, E. coli, S. aureus, P. aeruginosa and S. faecalis) and (antifungal organisms: Candida albicans, Aspergillus niger and Penicillium chrysogenum) to determine their effectiveness. The complexes were evaluated for their toxicity level in wister rats. The Amodiaquine and Paraaminobenzoic acid produce complexes in ratio 1:1:1 in coordination with the metal ion. Octahedral geometry has been …

Aqueous Kinetics Of Α-Hydroxyhippuric Acid Derivatives Bearing Electron-Withdrawing Groups As A Function Of Ph And Buffer Catalysts, Mohamad Imad Rafie

Theses and Dissertations

It has been shown that carbinolamides are intermediates in the enzyme-catalyzed synthesis of -amidated peptides. Although carbinolamides are important intermediates in the production of these hormones and have roles in other biological venues, little attention has been given to their mechanisms of reaction in water, and, thus, it is difficult to speculate how their reaction would be enzymatically catalyzed. The purpose of the work presented here was to synthesize structural analogs of the biological intermediates and study their mechanism of breakdown in water. -Hydroxyhippuric acid, a substrate for the enzymatic system, provides an easily modified template for the study of …

I. Selective Chlorination And Fluorination Of Quinols Ii. Synthetic Study Of Strongylophorine-26, Sihan Li

Dissertations, Theses, and Capstone Projects

Organic compounds containing halogen are an important and useful class of intermediates that can be converted to other functionalities. This thesis describes our strategy in selective chlorination and fluorination of quinols to offer the corresponding aromatic structures. Quinols, or cyclohexadienones, as oxidized derivatives of phenols, have their remarkable chemical reactivities, including additions to enone, enolate alkylations, aldol reactions, cycloadditions, and rearrangements. Dienone-phenol rearrangement provides the asymmetric route since the stereocenters located in the six-membered ring of various cyclohexadienone were widely using in building larger chiral arrays for many total syntheses

Chapter one of this thesis discusses our new selective nucleophilic …

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 …

Influence Of The Nature Of The Medium On The Conformational States Of Macromolecules Of Anionic Polyelectrolytes And Their Flocculating Effect, Mapruza Dzhumamuratova, Amanbay Pirniyazov, Oleg Dormeshkin, Akhmed Reymov, Tleumuratov Kuanish, Saparbay Kalbaev

Karakalpak Scientific Journal

The properties of surfactants of anionic polyelectrolytes are investigated depending on the nature of the medium, conformational states neutralized by organic bases, differing in the length of the hydrocarbon radical. The concept of the role of the state of macromolecules in solution in the indicated processes has been developed. The anionic carboxyl-containing polyelectrolytes synthesized on the basis of methacrylic acid differed not only in the length of the hydrocarbon radical of the organic base - counterion, but also in their branching. The relationship between the state of polyelectrolyte macromolecules in solution and their ability to regulate the properties of natural …

Approaches Towards The Synthesis Of Ketamine Metabolites, Ann K. Patrick

Honors Theses

Major Depressive disorder (MDD) plagues society and stands at the forefront of research as MDD affects approximately 16% of the population. Pharmaceutical drugs, including the selective serotonin reuptake inhibitors (SSRIs), have been used for MDD treatment and remain a popular option today. However, current antidepressant treatments have proven to be ineffective in just less than half of the patients. Research continues with the goal to better understand the mechanisms of the pathology of depression and to search for other treatment options. For example, the stress-neurogenesis hypothesis investigates the role of stress and decreased neuroplasticity within MDD.

Supporting the stress-neurogenesis hypothesis, …

Silver-Catalyzed Synthesis Of Disubstituted Fluorinated Isoxazoles, Micah Stewart

Honors Theses

The presence of fluorine can provide organic compounds with useful biological properties, such as increased metabolic stability and drug uptake. Because of these advantages, fluorinated compounds make up about 30% of the drug industry. However, fluorination of complex molecules is difficult due to fluorine’s high electronegativity.

Fluorinated isoxazoles are of particular interest in the pharmaceutical industry. Isoxazoles are five-membered heterocycles with oxygen and nitrogen in the 1, 2 positions that are able to engage in interactions unavailable to other ring structures, conferring advantageous biological properties upon compounds containing them. However, there are limited synthetic routes for fluorinated isoxazoles, and those …

New Synthetic Transformations Utilizing Silyloxyallyl Cations And Epoxonium Ions As Reactive Intermediates, Alexander Houston Cleveland

LSU Doctoral Dissertations

The development of new chemical transformations is of paramount importance in organic chemistry. In fact the study and creation of new reactions often uncovers new chemical reactivities and creates a new area of chemistry. The purpose of this dissertation is to present the development of new synthetic reactions that were uncovered through previous discoveries. Additionally the underlying theme of this work relies on the intermediacy of cationic reactive intermediates such as silyloxyallyl cations and epoxonium ions. Chapters 1 and 2 present the reactivity of novel silyloxyallyl cations. These cationic species are generated via the mild ionization of a-hydroxy silylenol ethers …

Stereochemical Investigation Of A Novel Tandem Intramolecular Diels-Alder Reaction, Katie Pelham

Chemistry Senior Theses

The Diels-Alder reaction has become a prominent synthetic tool due to the effectiveness for which it facilitates the construction of new carbon-carbon bonds to form six-membered rings. Since first reported in 1952, Intramolecular Diels-Alder (IMDA) reactions have been widely employed for complex synthesis, especially for natural products. Our lab was the first to report a Tandem Intramolecular Diels-Alder (TIMDA) reaction, and TIMDA reactions have similarly proved powerful in the synthesis of natural products. Predicting the absolute stereochemistry of the major products of such intramolecular reactions is complicated by the competition between steric factors imposed by the necessary distortion of the …

Gold Nanoparticles: Core Conversion Of Au144(Sch2ch2ph)60 To Au99(Sph-Ch3)42 Using Aromatic Thiolate Ligands And Crystallization Of Au99(Sph-Ch3)42, Elizabeth Turnage

Honors Theses

The purpose of this thesis is to synthesize Au₁₄₄(SCH₂CH₂Ph)₆₀ using a two-step synthesis reaction, and then using this product to conduct a core conversion from Au₁₄₄(SCH₂CH₂Ph)₆₀ to Au₉₉(SPh-CH₃)₄₂. The Au₉₉(SPh-CH₃)₄₂ product will then be used to attempt to form crystals using five different crystal set-up methods. Au₁₄₄(SCH₂CH₂Ph)₆₀ is made with aliphatic thiolate ligands, and when it is placed in a mixture containing excess para-methyl benzenethiol, it undergoes a …

Synthesis Of Β-C-Glycosidic Ketones From Unprotected Sugars And Their Use In Aldol Condensations With Hydroxymethylfurfural, Jon Chiaramonte

Student Scholars Day Posters

C-glycosides are a growing interest in synthetic chemistry for their use in the pharmaceutical industry as important drug pharmacophores and their potential use in chemical industry as surfactants. Previous literature describes the synthesis of C-glycosides using many steps and toxic reagents, often involving the use of protecting groups. The extra steps result in lower yields, require more reagents and produce more waste, which limits the environmental sustainability of the overall synthesis. This study aimed to reproduce the literature synthesis of β-C-glycosidic ketones from acetylacetone and monosaccharides without the use of protecting groups. These ketones were further reacted in aldol condensations …

Versatile Bismuth Salts-Induced Reactions From Our Laboratory: A Perspective, Debasish Bandyopadhyay, Bimal Krishna Banik

Chemistry Faculty Publications and Presentations

Bismuth salts-mediated reactions are developed for the synthesis of diverse organic molecules of medicinal significance. Reactions conducted with bismuth salts are environmentally friendly and these may proceed due to the release of acids in the media. Bismuth salt may also act as a Lewis acid in these reactions. Versatile organic molecules in chiral and achiral forms are synthesized using bismuth salts-induced reactions at our research laboratory.

Sorting Out Sortases: Designing A Better Enzyme And Synthesizing Trapping Peptides Towards Capturing A Bound-State Structure, Katherine Johnston

WWU Honors College Senior Projects

Sortase A is a powerful protein engineering tool that cleaves proteins and attaches them to an acyl acceptor of choice. However, the most active wild type variants of sortase A only show high activity at a limited number of cleavage motifs, and so work is underway to create a variant of sortase A that shows high activity at a greater variety of cleavage sites. Additionally, current studies attempting to optimize the enzyme require a way to stabilize an unstructured loop for the crystallization, in order to collect X-ray diffraction structural data. Here, preliminary results from the design of an “loop-swapped” …

Design Of Novel Substituted Phthalocyanines; Synthesis And Fluorescence, Dft,Photovoltaic Properties, Mehmet Sali̇h Ağirtaş, Derya Güngördü Solğun, Ümi̇t Yildiko, Abdullah Özkartal

Turkish Journal of Chemistry

The 4-(2-[3,4-dimethoxyphenoxy] phenoxy) phthalonitrile was synthesized as the starting material of new syntheses. Zinc, copper, and cobalt phthalocyanines were achieved by reaction of starting compound with Zn(CH3COO)2, CuCl2, and CoCl2 metal salts. Basic spectroscopic methods such as nuclear magnetic resonance electronic absorption, mass and infrared spectrometry were used in the structural characterization of the compounds. Absorption, excitation, and emission measurements of the fluorescence zinc phthalocyanine compound were also investigated in THF. Then, structural, energy, and electronic properties for synthesized metallophthalocyanines were determined by quantum chemical calculations, including the DFT method. The bandgap of HOMO and LUMO was determined to be …

Synthesis Of Bio-Based Polymer Products, Joshua Sukie

Williams Honors College, Honors Research Projects

The project covers the synthesis of two bio-based polymers. One aspect of the research investigates the synthesis of materials for use in vegetable oil-based UV-curable coating, and the subsequent polymerization of the materials into a coating film. The second aspect of the research follows the synthesis of a functionalized cellulose material for use as a reinforcer in a vegetable oil-based composite. Both products are subsequently analyzed by various methods.

Synthesis, Characterization, And Biological Activity Of Imidazolium Salts, David Weader

Williams Honors College, Honors Research Projects

Nonmuscle invasive bladder cancer (NMIBC) inflicts thousands of Americans annually, and is typically treated with the immunotherapy BCG. However, due to a BCG shortage, there is a new need for novel treatments of NMIBC. Addressing this issue, several imidazolium salt derivatives were synthesized and characterized with the intent of treatment within the bladder. These imidazolium salts were tested against different human bladder cancer cell lines in vitro to determine their reactivity and cytotoxicity. Among these results are GI50 concentrations for each drug, which is the concentration of drug needed to see growth inhibition in 50% of treated cells. Previous published …

Greener Synthesis Of Chlorophosphazenes, Andrew Mcgee

Williams Honors College, Honors Research Projects

This project will attempt to synthesize chlorophosphazene molecules in the absence of solvents by using mechanochemical techniques in order to create a more environmentally friendly synthesis route. In this pursuit, various parameters will be changed including the milling ball to reagent ratios, the molar ratios of the reactants, and the addition of different catalysts. The products of each reaction will be characterized in order to determine success. This work builds upon existing efforts to utilize mechanochemical techniques in main group chemistry. The output of this project will be a report in ACS style and a poster to be presented for …

Syntheses And Antibacterial Activities Of 4 Linear Nonphenolic Diarylheptanoids, Şemsi̇ Betül Demi̇r, Hati̇ce Seçi̇nti̇, Nesli̇han Çelebi̇oğlu, Murat Özdal, Alev Sezen, Özlem Gülmez, Ömer Faruk Algur, Hasan Seçen

Turkish Journal of Chemistry

Four linear nonphenolic diarylheptanoids were synthesized and their antibacterial activities were studied. ($S)$-2-Me-CBS-catalysed reduction of alnustone with BH$_{3}$.SMe$_{2}$ gave ($R)$(-)(4$E$,6$E)$-1,7-diphenylhepta-4,6-dien-3-ol, a natural product. Reduction of alnustone with Na in t-BuOH at -15 $^{\circ}$C under NH$_{3}$ atm gave ($E)$-1,7-diphenylhept-5-en-3-one as a Birch-type reduction product. $t$-BuOK catalysed condensation of benzalacetone with propionyl chloride gave (4$Z$,6$E)$-5-hydroxy-1,7-diphenylhepta-4,6-dien-3-one, a natural product. (1$E$,4$Z$,6$E)$-5-Hydroxy-4-phenethyl-1,7-diphenylhepta-1,4,6-trien-3-one, a curcuminoid, was synthesized starting from pentan-2,4-dione in 3 steps. The synthesized chemical compounds were applied against 2 gram-positive bacteria (Bacillus cereus and Arthrobacter agilis), 4 gram-negative bacteria (Pseudomonas aeruginosa, Xanthomonas campestris, Klebsiella oxytoca and Helicobacter pylori), and 1 yeast (Candida albicans) by …

Synthesis And Effect Of Substituent Position, Metal Type On The Electrochemical Properties Of (3-Morpholin-4-Ylpropoxy) Groups Substituted Cobalt, Manganese Phthalocyanines, Zekeri̇ya Biyiklioğlu, Hüseyi̇n Baş

Turkish Journal of Chemistry

In this work, 4-(3-morpholin-4-ylpropoxy)phthalonitrile 2, 3-(3-morpholin-4-ylpropoxy)phthalonitrile 3, Co(II)Pc and Mn(III)Pcs containing (3-morpholin-4-ylpropoxy) groups at peripheral and nonperipheral positions were synthesized. Phthalonitrile derivatives (2 and 3), Co(II)Pc and Mn(III)Pcs (2a, 2b, 3a, 3b) were characterized by using FT-IR, NMR (only for 2 and 3), mass and UV-Vis (except 2 and 3) spectral data techniques. Also, electrochemistry of (3-morpholin-4-ylpropoxy) group substituted Co(II)Pc and Mn(III)Pcs were inspected by using cyclic voltammetry. Electrochemical studies show that (3-morpholin-4-ylpropoxy) group substituted Co(II)Pc and Mn(III)Pcs electropolymerized on the Pt working electrode.

Synthesis And Electrochemical Properties Of Copper(Ii), Manganese(Iii) Phthalocyanines Bearing Chalcone Groups At Peripheral Or Nonperipheral Positions, Hüseyi̇n Baş, Nuran Kahri̇man, Zekeri̇ya Biyiklioğlu

Turkish Journal of Chemistry

In this study, new chalcone compound 1, new phthalonitrile derivatives 2 and 3, new copper(II), manganese(III) phthalocyanines bearing chalcone groups at peripheral or nonperipheral positions were synthesized. Electrochemistry of tetra-(4- {(2E)-3-[2-fluoro-4-(trifluoromethyl)phenyl]prop-2-enoyl}phenoxy) substituted Co(II)Pc and Mn(III)Pcs were studied with cyclic voltammetry (CV) to determine the redox properties of the phthalocyanines. According to the results, while the CuPcs 2a and 3a showed two Pc based reduction reactions and one Pc based oxidation reaction, MnPcs 2b and 3b gave two metal-based reduction reactions. All the redox processes are shifted toward positive potentials as a result of the increased electron-withdrawing ability of the trifluoromethyl …

Selective Modifications At The Different Positions Of Cyclodextrins: A Review Of Strategies, Jia Yue Liu, Xiao Zhang, Bingren Tian

Turkish Journal of Chemistry

Cyclodextrins (CDs) are natural, nontoxic, and biodegradable macrocyclic oligosaccharides. As supramolecular hosts, CDs have numerous applications in many aspects. However, nonsubstituted CDs have the disadvantages of solubility, unspecific recognition sites, and weak interactions with guest molecules. Therefore, new CD-based derivatives are successfully designed, synthesized, and widely used in various fields. This contribution outlines the research progress in CD derivatives. In particular, this review emphasizes the synthesis and application of CDs modified through functionalization in definite positions, random substitution, and reconstruction of the skeleton. At the end of this review, a summary and future directions are presented.