Chemistry Commons^™

Chelating Agent Free Solid Phase Extraction (Caf-Spe) Method For Separation And/Or Preconcentration Of Iron(Iii) Ions, Özcan Yalçinkaya, Orhan Murat Kalfa, Ali̇ Rehber Türker

Turkish Journal of Chemistry

This paper presents a chelating agent free solid phase extraction (CAF-SPE) method for the separation and/or preconcentration of trace iron(III) ions. This method is based on the sorption of Fe(III) ions without using any chelating agent onto Amberlyst 36 resin. A good relative standard deviation (3%), high recovery (>95%), high enrichment factor (100), and low detection limit (0.32 \mu g L^{-1}) were obtained. The adsorption capacity of resin was 117 mg g^{-1} for iron(III). The method was applied for the determination of iron various in water and commercial tea bag samples. The accuracy of the method was confirmed by …

Comparative Kinetic Studies On The Alkaline Hydrolysis Of Halogen Substituted Isocoumarins, Hafiz Badaruddin Ahmad, Muhammad Aslam Malana, Muhammad Yousaf, Muhammad Rehan, Mazhar Abbas

Turkish Journal of Chemistry

Kinetics of the hydrolysis of 3-(2'-chloro-6'-fluorobenzyl) isocoumarin (1), 3-(4'-fluorophenyl)isocoumarin (3), 3-(2'- fluorophenyl)isocoumarin (5), 3-(2'-chlorophenyl)isocoumarin (7), and 3-(4'-chlorophenyl)isocoumarin (9) were studied spectrophotometrically in the presence of aqueous solution of potassium hydroxide. The rates of hydrolyses for these isocoumarins were compared. The data for isocoumarin (1) were further investigated to probe the reaction mechanism. The dependence of pseudo-first order rate constant k_{obs} on hydroxide ion concentration is fitted by the expression k_{obs} = k_o + k_1[OH] + k_2 [OH]^2, showing the formation of monoanionic and dianionic tetrahedral intermediates during the course of reaction. The magnitude of k_o shows significant participation of solvent …

Mannich Base Derivatives Of 3-Hydroxy-6- Methyl-4h-Pyran-4-One With Antimicrobial Activity, Demet Us, Barkin Berk, Eni̇se Ece Gürdal, Ni̇han Ayteki̇n, Zühtü Tanil Kocagöz, Berrak Çağlayan, Işil Kurnaz, Di̇lek Demi̇r Erol

Turkish Journal of Chemistry

A series of 3-hydroxy-6-methyl-2-[(substitutedpiperidine-1-yl) methyl]-4H-pyran-4-one structured compounds were synthesized by reacting 5-hydroxy-2-methyl-4H-pyran-4-one with suitable piperidine derivatives using Mannich reaction conditions. Antibacterial activities of the compounds for E. coli ATCC 25922, S. paratyphi ATCC BAA-1250, S. flexneri ATCC 12022, E. gergoviae ATCC 33426, and M. smegmatis ATCC 14468 were assessed in vitro by the broth dilution method for determination of minimum inhibitory concentration (MIC). In addition, their inhibitory effects over DNA gyrase enzyme were evaluated using a DNA gyrase supercoiling assay. All the synthesized compounds showed a MIC value of either 8 or 16 \mu g/mL for M. smegmatis, whereas minimum …

(E)-3-[(3-(Trifluoromethyl)Phenylimino)Methyl] Benzene-1,2-Diol: X-Ray And Dft Calculated Structures, Başak Koşar, Çi̇ğdem Albayrak, Mustafa Odabaşoğlu, Orhan Büyükgüngör

Turkish Journal of Chemistry

The crystal structure of (E)-3-[(3-(Trifluoromethyl)phenylimino)- methyl]benzene-1,2-diol was determined using X-ray diffraction and the molecular structure was investigated with density functional theory (DFT). The X-ray study showed that the title compound has a strong intramolecular O-H...N hydrogen bond and 3-dimensional crystal networks are primarily determined by O-H...O intermolecular hydrogen bonds and weak van der Waals interactions. The strong O-H...N bond is evidence of the preference for the phenol-imine tautomeric form in the solid state. Optimized molecular geometry was calculated with DFT at the B3LYP/6-31G(d,p) level. The results from both experiment and theoretical calculations for the title compound are compared with each …

Synthesis And Characterization Of Novel Triazol Compounds Containing A Thiophen Ring As Potential Antifungal Agents And The Structure Of 2-(2-Hydroxy-2-P-Tolyethyl)-5-(Thiophen-2-Ylmethyl)- 4-(4h-1,2,4-Triazol-4-Yl)-2h-1,2,4-Triazol-3(4h)-One, Yasemi̇n Ünver, Esra Düğdü, Kemal Sancak, Mustafa Er, Reşat Ustabaş

Turkish Journal of Chemistry

A series of new 4-(3,5-disubstitue-4H-1,2,4-triazol-4-yl)- 5-(thiophen-2-yl-methyl)-2H-1,2,4-triazol-3(4H)-ones (3a-c) were obtained by reaction N'-1-ethoxy-2-thiophen-2-yl-ethylydene hydrazino carboxylic acid ethyl ester (1) and 4-amino-4H-1,2,4-triazoles (2). 4-(3,5-disubstitue-4H-1,2,4-triazol-4-yl)-2-(2-oxo-2-arylethyl)-5- (thiophen-2-yl-methyl)-2H-1,2,4-triazol-3(4H)-ones (4a-e) and ethyl 2-(4-(3,5-disubstitue-4H-1,2,4-triazol-4-yl)-5-oxo-3-(thiophen-2-ylmethyl)- 4,5-dihydro-1,2,4-triazol-1-yl)acetates (6a-c) were obtained by reaction of compounds 3 and bromoacetophenon derivatives and bromo ethylacetate, respectively. Compounds 5a-e were synthesized from the reaction of corresponding compounds 4a-e with NaBH_4. Compounds 7a-c were obtained by the reaction compounds 6 and LiAlH_4. Seventeen new compounds were synthesized and characterized by elemental analyses, IR, ^1H-NMR, and ^{13}C-NMR spectral data. The structure of compound 5d was inferred through IR, ^1H-, ^{13}C-NMR, elemental analyses, and X-ray spectral techniques. …

A Simple And Efficient Procedure For Synthesis Of Optically Active 1,3,4-Oxadiazole Derivatives Containing L-Amino Acid Moieties, Naser Foroughifar, Akbar Mobinikhaledi, Sattar Ebrahimi

Turkish Journal of Chemistry

Some new unsymmetrical and optically active 2,5-disubstituted 1,3,4-oxadiazoles 5a-j were efficiently synthesized by cyclization reaction of diacylhydrazides 4a-j. The synthesis of the title compounds was achieved by the reaction of acyl hydrazides 3a-b and N-phetaloyl-L-amino acids 1a-e in the presence of the phosphoroxy chloride (POCl_3) as an anhydrous reagent.

Sulfonic Acid-Functionalized Silica: A Remarkably Efficient Heterogeneous Reusable Catalyst For The One-Pot Synthesis Of 1,4-Dihydropyridines, Behzad Mohammadi, Sayyed Mohammad Hosseini Jamkarani, Taghi A. Kamali, Mahmoud Nasrollahzadeh, Ali Mohajeri

Turkish Journal of Chemistry

An efficient one-pot method for the synthesis of 1,4-dihydropyridines from \beta-dicarbonyl compounds, aldehyde, and ammonium acetate is reported using sulfonic acid-functionalized silica at 90 °C under solvent-free conditions with good to excellent yields. The catalyst is easily prepared, stable (up to 300 °C), reusable, and efficiently used under reaction conditions.

Synthesis And Surfactant Properties Of N-Acylation Compounds Derived From Hydrolysis Degradation Products Of N-(\Beta-Cianoethyl)-\Epsilon-Caprolactam, Andreea Bondarev

Turkish Journal of Chemistry

N-acyl amino acids can be used as active surface agents in the detergents industry, as well as in the pharmaceutical industry and cosmetics. Properties of these compounds are superior to those of fatty acids soaps and they are not toxic to the environment and have low Kraft points, because of peptide bonds (CO-NH). Acylation at the nitrogen atom can be performed with good yields without catalysts, for strong nucleophilic derivatives. The synthesis of some derivatives of 4-azasebacic acid, which are hydrolysis degradation products from N-(\beta -cianoethyl)-\epsilon -caprolactam, has been described and the N-acylation processes for these compounds are also presented. …

Synthesis And Characterization Of Ba/Mcm-41, Emi̇ne Kaya, Nuray Oktar, Gürkan Karakaş, Kirali̇ Mürtezaoğlu

Turkish Journal of Chemistry

Mesoporous Ba/MCM-41 type materials (Ba/MCM-41) with high Ba/Si molar ratios between 0.025 and 0.1 were synthesized by direct hydrothermal synthesis. The samples were characterized by XRD, nitrogen adsorption, TGA-DTA, FTIR, SEM-EDS, and TEM techniques. BET surface areas of samples with various Ba loadings were found between 722 and 931 m^2/g with 28 Å average pore size, which is consistent with the pore size of 30 Å for pure MCM-41 samples synthesized by the same procedure. The crystal structures of synthesized MCM-41 and Ba/MCM-41 were confirmed by XRD analysis. Among the investigated Ba/MCM-41 samples, the formation of barium oxide and barium …

Experimental Determination Of The Weiss Temperature Of Mn12-Ac And Mn12-Ac-Meoh, Christos Lampropoulos, Shiqi Li, Lin Bo, Bo Wen, M P. Sarachik, P Subedi, A D. Kent, Y Yeshurun, A J. Millis, S Mukherjee, G Christou

Chemistry Faculty Research and Scholarship

We report measurements of the susceptibility in the temperature range from 3.5 to 6.0 K of a series of Mn₁₂-ac and Mn₁₂-ac-MeOH samples in the shape of rectangular prisms of length l_c and square cross section of side l_a. The susceptibility obeys a Curie-Weiss law, χ=C/(T−θ), where θ varies systematically with sample aspect ratio. Using published demagnetization factors, we obtain θ for an infinitely long sample corresponding to intrinsic ordering temperatures T_c≈0.85 K and ≈0.74 K for Mn₁₂-ac and Mn₁₂-ac-MeOH, respectively. The difference in T_c for …

Energy Of The Conduction Band In Near Critical Point Fluids, Cherice M. Evans, G. L. Findley

Publications and Research

The study of the evolution of the conduction band in dense gases and supercritical fluids near the critical point has been complicated by a lack of precise experimental measurements. Both photoemission from an electrode immersed in the fluid and field ionization of a molecule doped into the fluid have been used to probe solvent density effects on the energy of an excess electron as a function of fluid number density and temperature. In this perspective, we present recent experimental results that show a strong critical point effect on the minimumconduction band energy near the critical density and temperature of a …

Synthesis And Conjugation Of Terminal Α-Galactose Containing, Roger Allan Ashmus

Open Access Theses & Dissertations

Over 16 million people in Latin America are infected with the protozoan parasite Trypanosoma cruzi (T. cruzi), the causative agent of Chagas disease, and up to 50,000 infected people die annually due to complications during the chronic stage of the disease. To date, there are no vaccines or effective drugs to treat chronic Chagas disease. It is known that T. cruzi contains cell surface mucin-like glycoproteins with terminal α-galactosyl residues, and it is well established that they are highly immunogenic. The exact structure of the immunogenic carbohydrate epitopes, however, remains unknown. To determine which epitopes have the ability to interact …

Development Of A Laser-Induced Breakdown Spectrometer For Lead-Free Gunshot Residue Analysis, Ryan Alexander Gregg

Honors Theses

Research has demonstrated that Laser‐Induced Breakdown Spectroscopy (LIBS) can be used as an effective method of screening for the common elemental components in gunshot residue. Barium (Ba), lead (Pb), and antimony (Sb) make up the primer cap of most ammunition involved in forensic gunshot residue analysis. Recently, ammunition manufacturers have started producing and popularizing ammunition with zinc (Zn), titanium (Ti), and gadolinium (Gd) primer components that are non‐toxic to the environment. This paper discusses the development of the Ole Miss Department of Chemistry and Biochemistry's first LIBS instrument for forensic analysis of lead‐free using Gd as a tracer element for …

Developing The Techniques For Raman, Surface-Enhanced Raman Scattering (Sers), And Fluorescence Spectroscopies Of Organic Molecules In Isolation, Jonathan Wolfe

Honors Theses

The nature of matter and light has been a subject of philosophical debate since antiquity. However, by the end of the nineteenth century, much of the scientific community believed that most of the significant principles that govern the natural world had been discovered. Classical physics was able to explain complex phenomena such as planetary motions, elasticity, and hydrodynamics. The field of thermodynamics had been developed nearly to completion by James Joule, Sadi Carnot, Josiah Gibbs, et al. The magnetic and electronic nature of light had been demonstrated by James Clerk Maxwell's famous equations. In the neighboring field of chemistry, a …

Immobilization Of Mercury And Arsenic Through Covalent Thiolate Bonding For The Purpose Of Environmental Remediation, Lisa Y. Blue

University of Kentucky Doctoral Dissertations

Mercury and arsenic are widespread contaminants in aqueous environments throughout the world. The elements arise from multiple sources including mercury from coal-fired power plants and wells placed in natural geological deposits of arseniccontaining minerals. Both elements have significant negative health impacts on humans as they are cumulative toxins that bind to the sulfhydryl groups in proteins, disrupting many biological functions. There are currently no effective, economical techniques for removing either mercury or arsenic from aqueous sources. This thesis will demonstrate a superior removal method for both elements by formation of covalent bonds with the sulfur atoms in N,N’-Bis(2-mercaptoethyl)isophthalamide (commonly called …

Stability Of Spore-Based Sensing Systems, Abhishek Sangal

University of Kentucky Master's Theses

The full exploitation of bacterial whole-cell biosensing systems in field applications requires the survival of bacterial cells and long term-preservation of their sensing ability during transportation and on-site storage of such analytical systems. Specifically, there is a need for rapid, simple and inexpensive biosensing systems for monitoring human health and the environment in remote areas which often suffer from harsh atmospheric conditions and inadequate commercial distribution and storage facilities. Our laboratory has previously reported the successful use of bacterial spores as vehicles for the long-term preservation and storage of whole-cell biosensing systems at room temperature.

In the present research, we …

Functionalization Of Multi-Walled Carbon Nanotubes And The Interactions Of Multi-Walled Carbon Nanotubes In Epoxy Composites, Christopher Fitzwater

University of Kentucky Master's Theses

Multi-walled carbon nanotubes (MWNTs) are a relatively new allotrope of carbon that have potentially useful properties that may improve polymer composites. The work of this thesis explores the interactions between MWNTs and functionalized MWNTs within epoxy matrix and the properties of the MWNT/epoxy composite. These interactions were characterized with an emphasis on finding how well the MWNT/epoxy composite flows and how conductive it is after curing.

Synthesis, Characterization And Development Of Catalysts For Co2 Capture, Anitha Suhas Wishrojwar

University of Kentucky Master's Theses

Fossil fuel and advanced industrialization techniques contribute to global warming through emissions of greenhouse gases such as CO₂. In order to mitigate climate change, there is a desperate need to reduce CO₂ emissions from different sources. CO₂ capture and sequestration (CCS) play an important role in these reductions.

Naturally occurring enzymes, e.g., carbonic anhydrase (CA), can catalyze these reactions in living systems. Much effort has been focused on complexes of zinc with ligands such as teta, cyclen and tripodal ligands including BIMA and Trispyrazolylborates. These complexes have many interesting CO₂ capture properties, but maintain toxic …

Opioid-Cannabinoid Codrugs With Enhanced Analgesic And Pharmacokinetic Profile, Harpreet Kaur Dhooper

University of Kentucky Doctoral Dissertations

The central hypothesis of the dissertation is that “the design and synthesis of a codrug of an opiate and a cannabinoid can be achieved which is stable in the gastrointestinal tract and shows a superior pharmacological and pharmacokinetic profile when compared to a physical mixture of the two parent drugs.” To prove the hypothesis, a series of novel codrugs were prepared by conjugation of the opiate drug codeine with Δ⁹-tetrahydrocannabinol (Δ⁹-THC), cannabidiol, abn-cannabidiol and an opiate prodrug 3-O-acetylmorphine with Δ⁹-THC. Codeine-cannabinoid codrugs were evaluated for analgesic activity in the rat after oral administration. The …

Hrc Enews — 2010 Winter, Megan K. Svarz

Publications (HRC)

This issue contains staff accomplishments and announcements, event listings, a "new faces" listing for new staff, affiliates, and researchers, and an "on the move" section listing new developments.

Investigating Fabrication Methods For Micro Single-Chamber Solid Oxide Fuel Cells, Man Yang

Dissertations

A Solid Oxide Fuel Cell (SOFC) is a green energy technology that offers a cleaner and efficient alternative to fossil fuels. The efficiency and utility of SOFCs can be enhanced by fabricating miniaturized component structures within the fuel cell footprint. This research focuses on the microfabrication of parallel-connected inter-digitized design of micro single chamber SOFC (µ-SC-SOFCs). In this dissertation, candidate micro/nano fabrication techniques to precisely fabricate micro patterns on planar substrates have been studied. These include EBL, soft lithography, photolithography, and direct-writing. After analyzing preliminary results, two combinational approaches were further investigated. The first method involves the combination of the …

Polarization Dependent Two-Photon Absorption Properties Of Chiral Molecules, Carlos Toro

Electronic Theses and Dissertations

Molecules that are non-superimposable on their mirror image are named chiral or optically active compound. Over the years, molecular chirality has played an essential role in the understanding of fundamental aspects associated the origin of life, drug and food technologies and, asymmetric catalysis, among others. Moreover, most of the groundbreaking discoveries and advances made in this field have happened due to the development of spectroscopic techniques based on the natural asymmetry of the enantiomers and their ability to preferentially absorb right or left polarized light. For instance, circular dichroism (CD), which measures the difference in absorption between these two states …

Effluent Organic Nitrogen (Eon): Bioavailability And Photochemical And Salinity-Mediated Release, Deborah A. Bronk, Quinn N. Roberts, Marta P. Sanderson, Elizabeth A. Canuel, Patrick G. Hatcher, Rajaa Mesfioui, Katherine C. Filippino, Margaret R. Mulholland, Nancy G. Love

Chemistry & Biochemistry Faculty Publications

The goal of this study was to investigate three potential ways that the soluble organic nitrogen (N) fraction of wastewater treatment plant (WWTP) effluents, termed effluent organic N (EON), could contribute to coastal eutrophication - direct biological removal, photochemical release of labile compounds, and salinity-mediated release of ammonium (NH₄+). Effluents from two WWTPs were used in the experiments. For the bioassays, EON was added to water from four salinities (∼0 to 30) collected from the James River (VA) in August 2008, and then concentrations of N and phosphorus compounds were measured periodically over 48 h. Bioassay results, based …

Sequence And Structural Analysis Of The Chitinase Insertion Domain Reveals Two Conserved Motifs Involved In Chitin Binding, Hai Li, Lesley H. Greene

Chemistry & Biochemistry Faculty Publications

Background: Chitinases are prevalent in life and are found in species including archaea, bacteria, fungi, plants, and animals. They break down chitin, which is the second most abundant carbohydrate in nature after cellulose. Hence, they are important for maintaining a balance between carbon and nitrogen trapped as insoluble chitin in biomass. Chitinases are classified into two families, 18 and 19 glycoside hydrolases. In addition to a catalytic domain, which is a triosephosphate isomerase barrel, many family 18 chitinases contain another module, i.e., chitinase insertion domain. While numerous studies focus on the biological role of the catalytic domain in chitinase activity, …

Investigations Of Structure / Property Interrelationships Of Organic Thin Films Using Scanning Probe Microscopy And Nanolithography, Zorabel Mallorca Lejeune

LSU Doctoral Dissertations

Studies of the surface assembly and molecular organization of organic thin films were studied using scanning probe microscopy (SPM) and scanning probe lithography (SPL). Systems of organic thin films such as n-alkanethiols and pyridyl functionalized porphyrins were characterized at the molecular level, and measurements of the conductive properties of polythiophenes containing in-chain cobaltabisdicarbollides were accomplished. Understanding the self-organization and mechanisms of self-assembly of organic molecules provides fundamental insight for structure/property interrelationships. Investigations of the surface assembly of 5,10-diphenyl-15,20-di-pyridin-4-yl-porphyrin (DPP) on Au(111) were done using SPL methods of nanoshaving and nanografting. Automated computer designs were developed for nanofabrication to provide local …

Studies Of Nanoparticles From A Group Of Uniform Materials Based On Organic Salts (Gumbos), Aaron Tesfai

LSU Doctoral Dissertations

Tesfai, Aaron, B.S., B.A., University of Missouri, Columbia, 2003 Doctor of Philosophy, Spring Commencement 2010 Major: Chemistry Studies of Nanoparticles from a Group of Uniform Materials Based on Organic Salts (GUMBOS) Dissertation directed by Professor Isiah M. Warner Pages in dissertation, 101. Words in abstract, 271. Ionic liquids (ILs) are defined as organic salts composed of ions with melting points at or below 100 °C. ILs have gained considerable attention because of their desirable properties such as low volatility, high thermal stability, and tunability. GUMBOS are an emergent class of organic salts, many of which are ionic liquids (ILs). However, …

Particle Analysis In Infrared Laser Desorption And Ablation, Xing Fan

LSU Doctoral Dissertations

The fundamental physical processes of mid infrared laser ablation in the context of laser desorption mass spectrometry were investigated. Understanding the mechanisms of infrared laser desorption and ablation can lead to improvements in these techniques and expand their applications. Particles were generated from glycerol irradiated at atmospheric pressure using a tunable infrared laser at wavelengths between 2.6 and 3.8 µm. The wavelength dependence of size distributions of ablated particles was measured. The particle concentration roughly tracked the infrared absorption spectrum of glycerol and the mean particle size tracked the inverse of the IR absorption. A novel approach, post ablation particle …

Molecular Dynamics Studies Of Simple Model Fluids And Water Confined In Carbon Nanotube, Jun Wang

Department of Chemistry: Dissertations, Theses, and Student Research

Molecular Dynamics (MD) simulation is one of the most important computational techniques with broad applications in physics, chemistry, chemical engineering, materials design and biological science. Traditional computational chemistry refers to quantum calculations based on solving Schrodinger equations. Later developed Density Functional Theory (DFT) based on solving Kohn-Sham equations became the more popular ab initio calculation technique which could deal with ~1000 atoms by explicitly considering electron interactions. In contrast, MD simulation based on solving classical mechanics equations of motion is a totally different technique in the field of computational chemistry. Electron interactions were implicitly included in the empirical atom-based potential …

Oxidation Of Dibenzothiophene To Dibenzothiophene Using Metal Nanoparticles Supported On Silica, Karina Castillo

Open Access Theses & Dissertations

Silica and nanoparticles of Pt, Au, and Ag supported on silica were tested for the ability to oxidize dibenzothiophene (DBT) to sulfone. High performance liquid chromatography was used to study the removal of DBT from solution. In addition, X- ray diffraction, infrared spectroscopy and Raman Spectroscopy were used to characterize the product of the oxidation reaction. Further studies involved the use X-ray absorption spectroscopy to characterize the nanoparticle catalysts before and after the oxidation reaction.

To better understand the reaction, silica was synthesized at different pHs using three different acids. The acids used to synthesize the silica were HCl, HNO3, …

Synthesis And Manufacture Of Photocrosslinkable Poly(Caprolactone)-Based 3d Scaffolds For Tissue Engineering Applications, Nathan Jonathan Castro

Open Access Theses & Dissertations

It is known that the body can efficiently repair hard tissue (bone) micro fractures by suturing the defect through the deposition of minerals resulting in an area that is stronger post-injury. Larger defects, however, generally cause more trouble since the body is incapable of repairing them. Bone defects can occur as a result of congenital abnormalities, trauma, or disease. Traditional methods for addressing these defects have involved the use of acellular cadaverous bone or autologous bone. Both contain innate problems associated with them; the former method can result in disease transmission, as well as very low integration with the host …