Chemistry Commons^™

Laser Ablation Sample Transfer For Mass Spectrometry, Sung-Gun Park

LSU Doctoral Dissertations

In this research, a new ambient sampling technique for mass spectrometry was developed that uses an infrared laser to ablate materials under ambient conditions that are captured in a solvent or on a surface. An infrared optical parametric oscillator (OPO) laser system at 3 μm wavelength was focused onto samples for ablation at atmospheric pressure. The ablated materials were transferred to a solvent or surface. For off-line electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) analysis, the ablated material was captured in a static solvent droplet that was deposited on a MALDI target or flow-injected into a nanoelectrospray source. The …

Studies Of Core-Shell Nanogumbos And Liposomal Ionogels, Ashleigh Renee' Wright

LSU Doctoral Dissertations

The work presented in this dissertation is a description of novel core-shell nanomaterials derived from a group of uniform materials based on organic salts (GUMBOS) and the synthesis and characterizations of novel liposomal ionogels (LIGs). These GUMBOS are an extension of ionic liquids (ILs) which are organic salts with melting points between 25 °C and 100 °C. Ionic liquids have high thermal stability, low vapor pressure, and tunable physiochemical and functional properties. All of the properties of ILs are controlled by the chosen cation and anion pair. Similarly to ILs, GUMBOS possess the same qualities; however, they have melting points …

Luminescence Studies : Part I. Lanthanide Nanogumbos Part Ii. Near Infrared Photothermal Nanogumbos, Jonathan Carver Dumke

LSU Doctoral Dissertations

Group of Uniform Materials Based on Organic Salts (GUMBOS) are a class of molten salts that have been focused to be specifically tailored towards applications. Primitively, from Davy to Walden molten salts were desirable for organic synthesis due to the properties. GUMBOS have been synthesized into nanoparticles (nanoGUMBOS) by various methods to be used for lanthanide luminescence and hyperthermal cancer therapeutics. Lanthanide photochemistry has been frequently studied for its high luminescence intensity, narrow emission band, and stable luminescent lifetime decay. Aerosol-derived europium nanoGUMBOS were characterized using electron microscopy (39.5 ± 8.4 nm), XPS, and spectroscopic techniques. Spectroscopic measurements indicated intense …

Gumbos And Nanogumbos: Applications As Photosensitizers In Dye-Sensitized Solar Cells, Atiya Nicole Jordan

LSU Doctoral Dissertations

Renewable energy is a major concern due to increased world energy consumption. In particular, solar energy is a type of renewable energy source that uses devices known as solar cells to convert sunlight to electricity. Specifically, devices referred to as dye-sensitized solar cells (DSSCs) employ dyes to absorb solar energy. Dyes derived from ruthenium complexes have been typically used in DSSCs. Unfortunately, several disadvantages are associated with current ruthenium complex photosensitizers, which can be attributed to limited supply and expense of metals, as well as reduced absorption in the near-infrared region of the electromagnetic spectrum. Accordingly, this dissertation is a …

Kamlet Laboratories And Clinitest: Idea To Product, Dean F. Martin, Brodie A. Reiger

Chemistry Faculty Publications

This paper examines the process of development of Clinitest pills that could be used in clinics or physicians' offices for rapid, convenient analysis of glucose and other components of clinical interest. It was invented by Dr. Jonas Kamlet. We were able to follow the process because his papers are accessible (as The Kamlet Laboratories Collection) at the University of South Florida Library. The accessibility of these papers gives an opportunity to see steps in the development of a successful product from conception to patent and commercialization. Kamlet, a consulting chemist, took the invention to Miles Laboratories of Elkhart, Indiana, in …

Investigating The Interaction Of Zinc-Finger Peptides And Nicked Dna Using Phage Display, Rachel Maria Guerra

Honors Theses

Recognition of structural features of DNA such as gaps, nicks and abasic sites is critical for many DNA-binding proteins, such as those involved in DNA damage repair. This study explores a novel strategy to model these protein-DNA interactions using phage display. Phage display has been commonly used to identity zinc fingers that bind to DNA sequences, but selection of peptides that binding to specific DNA structures has not been reported in the literature. A phage library of 109 variants was created based on one of three zinc finger domains of the DNA repair protein poly (ADP-ribose) polymerase I. The library, …

Studies Of The Structural Boundaries Of Solid-State Photodimerization Reactions Via Isocoumarins And Heteromeric Assemblies, Mihiri S. Weerasinghe

Masters Theses

The study of molecules in crystals has gained considerable attention in the field of structural chemistry. Much interest has focused on the use of molecular crystals for the construction of materials with specific functional properties. Because the design of such materials requires a critical understanding of intermolecular interactions, use of the building-block approach continues to offer an important strategy to multimolecular frameworks. Though the use of template and metal-ligand interactions has provided successful opportunities to organize chemical reactions in solids, these methods require secondary molecules and are limited to achiral starting materials. As such, exploring chiral synthesis with simplified precursors …

From Half-Rotaxanes To Poly-Rotaxane Architectures, Heather Renee Schoonover

Masters Theses

The host-guest abilities of macrocyclic compounds made them important players in the field of supramolecular chemistry, especially those studying mechanical bonds. Rotaxanes and catenanes are among the most well-known examples of mechanically interlocked molecules. Our approach in the synthesis of poly-rotaxane systems involves the preparation of pseudorotaxanes with donor capabilities and then use metallic centers to assemble the poly-rotaxane architectures.

A pyridine-based half-rotaxane has been synthesized and the subsequent solution studies revealed a large association constant. ¹H-NMR studies show that these interlocked species exhibit a slow exchange on the NMR timescale. Using the single point method and VT-NMR several …

The Effects Of Chemical Treatment And Light Exposure On Pah Concentrations In Biochar, Fathima Nadheesha Muhammed Khalid

Masters Theses

A series of experiments quantifying extractable polycyclic aromatic hydrocarbons (PAHs) in biochar before and after various treatments were conducted. The analytical approach included solvent extraction of PAHs with toluene, further isolation and column cleanup before gas chromatography mass spectroscopy (GC-MS) analysis. The treatment methods include exposing biochar samples to sunlight and UV radiation with and without additives and reacting with hydrogen peroxide.

Two biochar samples from the Eastern Illinois University bench-type gasifier and commercial biochar were analyzed. Analyzing of three biochar types revealed that plant biochar has lower total PAH concentration than wood (W) biochar or wood and plant (giant …

Membrane Surface Charges Attracted Protons Are Not Relevant To Proton Motive Force, James Weifu Lee

Chemistry & Biochemistry Faculty Publications

[First Paragraph] Only a half-century ago, British scientist Peter Mitchell proposed the conceptual scheme known as "chemiosmotic theory" that identified the role of proton coupling in the formation of ATP in cells [1,2]. Mitchell's delocalized proton-coupling chemiosmotic theory was initially quite controversial. But it would win for him the Nobel Prize in Chemistry in 1978. However, questions about Mitchell's chemiosmotic hypothesis have never gone away and a number of credible studies indicated the full extent of Mitchell's idea didn't always hold up to experience.

Hci And Cio Profiles Inside The Antarctic Vortex As Observed By Smiles In November 2009: Comparisons With Mls And Ace-Fts Instruments, T. Sugita, Y. Kasai, Y. Terao, S. Hayashida, G. L. Manney, W. H. Daffer, H. Sagawa, M. Suzuki, M. Shiotani, K. A. Walker, C. D. Boone, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

We present vertical profiles of hydrogen chloride (HCl) and chlorine monoxide (ClO) as observed by the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) on the International Space Station (ISS) inside the Antarctic vortex on 19-24 November 2009. The SMILES HCl value reveals 2.8-3.1 ppbv between 450K and 500K levels in potential temperature (PT). The high value of HCl is highlighted since it is suggested that HCl is a main component of the total inorganic chlorine Cl_y, defined as Cl_y similar or equal to HCl + ClO + chlorine nitrate ClONO₂, inside the Antarctic vortex in spring, owing …

Stratospheric Loss And Atmospheric Lifetimes Of Cfc-11 And Cfc-12 Derived From Satellite Observations, K. Minschwaner, L. Hoffmann, A. Brown, M. Riese, R. Müller, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

The lifetimes of CFC-11 and CFC-12 have been evaluated using global observations of their stratospheric distributions from satellite-based instruments over the time period from 1992 to 2010. The chlorofluorocarbon (CFC) datasets are from the Cryogen Limb Array Etalon Spectrometer (CLAES), the Cryogenic Infrared Spectrometers and Telescopes for the Atmosphere (CRISTA-1 and CRISTA-2), the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS), and the Atmospheric Chemistry Experiment (ACE). Stratospheric loss rates were calculated using an ultraviolet radiative transfer code with updated cross section and solar irradiance data. Mean steady-state lifetimes based on these observations are 44.7 (36-58) yr for CFC-11 and 106.6 …

Observations Of Peroxyacetyl Nitrate (Pan) In The Upper Troposphere By The Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (Ace-Fts), K. A. Tereszchuk, D. P. Moore, J. J. Harrison, C. D. Boone, M. Park, J. J. Remedios, W. J. Randel, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

Peroxyacetyl nitrate (CH₃CO·O₂NO₂, abbreviated as PAN) is a trace molecular species present in the troposphere and lower stratosphere due primarily to pollution from fuel combustion and the pyrogenic outflows from biomass burning. In the lower troposphere, PAN has a relatively short lifetime and is principally destroyed within a few hours through thermolysis, but it can act as a reservoir and carrier of NO_x in the colder temperatures of the upper troposphere, where UV photolysis becomes the dominant loss mechanism. Pyroconvective updrafts from large biomass burning events can inject PAN into the upper troposphere …

Investigation Of Co, C2h6 And Aerosols In A Boreal Fire Plume Over Eastern Canada During Bortas 2011 Using Ground- And Satellite-Based Observations And Model Simulations, D. Griffin, K. A. Walker, J. E. Franklin, M. Parrington, C. Whaley, J. Hopper, J. R. Drummond, P. I. Palmer, K. Strong, T. J. Duck, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

We present the results of total column measurements of CO, C₂H₆ and fine-mode aerosol optical depth (AOD) during the "Quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites" (BORTAS-B) campaign over eastern Canada. Ground-based observations, using Fourier transform spectrometers (FTSs) and sun photometers, were carried out in July and August 2011. These measurements were taken in Halifax, Nova Scotia, which is an ideal location to monitor the outflow of boreal fires from North America, and also in Toronto, Ontario. Measurements of fine-mode AOD enhancements were …

The Effect Of Electrochemical Modification On The Surface Topography And Chemical Make-Up Of Strontium Titanate, Kelly J. Harmon

Masters Theses

Previous research into the oxidation and reduction of strontium titanate and the changes that result from this has been carried out. The oxidation and reduction of strontium titanate at high temperatures and high pressures has been investigated for the effect that it has upon the surface topography of strontium titanate and the chemical makeup of the strontium titanate. Research into the electrochemical oxidation of perovskites, similar in structure to that of strontium titanate, have even provided evidence pointing to the identity of the oxygen species being incorporated into the strontium titanate.

This research seeks to investigate what changes occur to …

Fabrication Of Layer-By-Layer Deposited Films Containing Carbon Nanotubes And Poly(Malachite Green) As A Sensor For Simultaneous Determination Of Ascorbic Acid, Epinephrine, And Uric Acid, Jahan Bakhsh Raoof, Reza Ojani, Mehdi Baghayeri

Turkish Journal of Chemistry

A simple approach to constructing a double-layer voltammetric sensor is described. The poly(malachite green) (PMG) and multiwalled carbon nanotubes (MWCNTs) were coimmobilized at the surface of the glassy carbon electrode (GCE) for fabrication of PMG/MWCNT/GCE. The modified electrode was characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), differential pulse voltammetry (DPV), and chronoamperometric techniques. Using DPV, the obtained catalytic peak current was linearly dependent on the ascorbic acid (AA), epinephrine (EP), and uric acid (UA) concentrations in the ranges of 0.4-100.0, 0.1-100.0, and 0.3-90.0 \muM, respectively. The resultant detection limits for AA, EP, and UA were 0.23, 0.0820, and …

Mechanochemical Modification Method Used In The Development Of New Composite Materials Based On Epoxy Binder And Natural Minerals, Umida Ziyamukhamedova, Dilshod Djumabaev, Botirali Shaymardanov

Turkish Journal of Chemistry

This article highlights the results of a mechanochemical modification method of epoxy composite materials and coatings on their base. It proves the mechanochemical activated components of composition to be the most acceptable for structuring when producing composite materials. It also states the increase of mechanical properties of epoxy heterocomposite coatings with mechanically activated particles by 25%-40%.

Disposable Carbon Electrodes As An Alternative For The Direct Voltammetric Determination Of Alkyl Phenols From Water Samples, Iulia Gabriela David, Irinel Adriana Badea, Gabriel Lucian Radu

Turkish Journal of Chemistry

Disposable sensors based on a pencil graphite electrode were described for detection of alkyl phenols. The performances of the disposable bare pencil graphite electrode (PGE) and PGE modified with carbon nanotubes, regarding the cyclic and differential pulse voltammetric determination of 4-nonylphenol, 4-octylphenol, and 4-tert-octylphenol, were compared. Some experimental variables of the electrode surface pretreatment and measurement parameters were optimized. Using a phosphate buffer solution (pH 7.40) as the supporting electrolyte, alkyl phenols gave a well-defined oxidation peak at about 700 mV vs. Ag/AgCl. The detection limits established for each alkyl phenol were: 0.25 \muM for 4-octylphenol, 0.42 \muM for 4-nonylphenol, …

Molecular Docking And Qsar Study On Imidazole Derivatives As 14 /Alpha -Demethylase Inhibitors, Asghar Davood, Maryam Iman

Turkish Journal of Chemistry

14\alpha-Demethylase (CYP51) inhibitors have been widely used in the treatment of fungal infections. In this study, a series of imidazole derivatives with CYP51 inhibitory activity were subjected to a molecular docking study followed by quantitative structure-activity relationship (QSAR) analyses in search of the ideal physicochemical characteristics of potential CYP51 inhibitors. Desired imidazoles were built using the HyperChem program, and conformational studies were performed through a semiempirical method followed by the PM3 method. Docking study was performed using the AutoDock program on all of the compounds. Different QSAR descriptors were calculated using DRAGON, AutoDock, and HyperChem. Multilinear regression was used as …

Enaminonitriles In Heterocyclic Synthesis: Synthesis And Biological Evaluation Of Novel Indeno[2,1-B]Thiophene Derivatives, Ahmed A. Fadda, Abd El Galil M. Khalil, Eman H. Tawfik

Turkish Journal of Chemistry

No abstract provided.

Synthesis, Characterization, And Swelling Behaviors Of A Ph-Responsive Cmc-G-Poly(Aa-Co-Amps) Superabsorbent Hydrogel, Yizhe Wang, Xiaoning Shi, Wenbo Wang, Aiqin Wang

Turkish Journal of Chemistry

New superabsorbent hydrogels were synthesized through free radical graft copolymerization of partially neutralized acrylic acid (AA) and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) onto carboxymethyl cellulose (CMC) backbones. The structure and morphology of the synthesized superabsorbent hydrogels were characterized by Fourier transform infrared spectroscopy and scanning electron microscope. The effect of the molar ratio of AMPS to AA, the APS concentration, and the CMC content on swelling ratio was optimized. The swelling properties in various pH solutions and saline solutions as well as the swelling kinetics were also evaluated. Results showed that the introduction of AMPS enhanced the swelling capacity, swelling rate, and …

Spectrophotometric Determination Of 3-Hydroxy-3-Methylglutaryl Coenzyme-A Reductase Inhibitors In Pharmaceutical Preparations, Gamze Ergi̇n, Sena Çağlar, Armağan Önal, Sidika Ertürk Toker

Turkish Journal of Chemistry

Simple and accurate spectrophotometric methods are presented for the determination of five 3-hydroxy-3-methylglutaryl coenzyme-A (HMG-CoA) reductase inhibitors (statins), namely atorvastatin, fluvastatin, pitavastatin, rosuvastatin, and simvastatin, in pharmaceutical preparations. The methods are based on the reaction of drugs as n-electron donor with 7,7,8,8-tetracyanoquinodimethane as \pi-acceptors to give highly colored complex species. All variables were studied in order to optimize the reaction conditions. Beer's law was obeyed in the concentration ranges 4--20 \mu g mL^{-1}, 4--12 \mu g mL^{-1}, 0.8--2.4 \mu g mL^{-1}, 4--14 \mu g mL^{-1}, and 2.5--20 \mu g mL^{-1} for atorvastatin, fluvastatin, pitavastatin, rosuvastatin, and simvastatin, respectively. The proposed …

Removal Of Cr(Iii) And Cu(Ii) Using Oly(2-Chloroaniline)/Polyvinylidenefluoride Composite Cation-Exchange Membranes By Donnan Dialysis, Esengül Kir, Sabri̇ye Perçi̇n Özkorucuklu, Tuğba Sardohan Köseoğlu, Esi̇n Karamizrak

Turkish Journal of Chemistry

P2ClAn/PVDF composite membranes were prepared utilizing cation-exchange groups in the PVDF (polyvinylidenefluoride) membrane matrix by casting method. The poly(2-chloroaniline) (P2ClAn) was chemically synthesized with different dopant anions such as o-aminobenzene sulfonic acid (ABS) and sodium dodecyl sulfate (SDS). P2ClAn/PVDF membranes were extensively characterized for their surface morphology, thickness, ion-exchange capacity, SEM, AFM, and FTIR-ATR measurements. The SEM, AFM and FTIR-ATR pictures, comparing the original PVDF membrane support sheet to P2ClAn/PVDF composite membranes, indicate that the morphologies of the membranes are different. The membrane potential measurements were performed in various electrolyte solutions in order to observe the selectivity and stability of …

Antimicrobial Activity And Chemical Composition Of The Essential Oils Of Mosses (Hylocomium Splendens (Hedw.) Schimp. And Leucodon Sciuroides (Hedw.) Schwägr.) Growing In Turkey, Tayyi̇be Beyza Cansu, Büşra Yayli, Turan Özdemi̇r, Nevzat Batan, Şengül Alpay Karaoğlu, Nuretti̇n Yayli

Turkish Journal of Chemistry

In the present work, the volatiles of mosses [Hylocomium splendens (Hedw.) Schimp. (Hylocomiaceae) and Leucodon sciuroides (Hedw.) Schwägr. (Leucodontaceae)] have been investigated by GC-FID and GC/MS. Fifty-eight compounds in the oil of H. splendens, representing 75.4%, and 41 compounds in the oil of L. sciuroides, representing 87.6%, were identified. The major components were found to be \beta-pinene (11.6%) and \alpha-pinene (8.9%) in the oil of H. splendens, and nonanal (26.8%) and heptanal (13.7%) in the oil of L. sciuroides. The essential oil of H. splendens was rich in monoterpenes (30.8%), and aldehydes (49.9%) were the major constituents in the oil …

New Synthetic Methodology For Construction Of The 3,4-Dihydroquinolin-2-One Skeleton, Çağatay Dengi̇z, Meti̇n Balci

Turkish Journal of Chemistry

We hereby report a new method for preparation of 3,4-dihydroquinolin-2(2H)-one starting from the methyl 2-(2-carboxyethyl)benzoic acid. The acid functionality, adjacent to the methylene, was regiospecifically converted to the desired methyl ester and the remaining acid functionality was transferred into acyl azide. Curtius rearrangement of acyl azide followed by trapping with aniline and alcohols provided the corresponding urea and urethane derivatives. Hydrolysis of methyl ester groups gave the acids. Ring closure in the presence of thionyl chloride resulted in the formation of the 3,4-dihydroquinolin-2(2H)-one skeleton.

A One-Pot Strategy For Regioselective Synthesis Of 6-Aryl-3-Oxo-2,3-Dihydropyridazine-4-Carbohydrazides, Mehdi Rimaz, Hossein Mousavi

Turkish Journal of Chemistry

A simple and efficient method for the synthesis of 6-aryl-3-oxo-2,3-dihydropyridazine-4-carbohydrazide derivatives was developed. The synthesis was achieved via one-pot multicomponent reaction of arylglyoxals, dialkylmalonates, and hydrazine hydrate in pyridine at room temperature. This procedure features high regioselectivity, generally good to excellent yields, the use of easily available starting materials, and operational simplicity. This chemistry provides an efficient and promising synthetic strategy for diversity-oriented construction of the 6-arylpyridazinone skeleton.

An Efficient Ligand-Free Method For The Transfer Hydrogenation Of Ketones And Aldehydes Catalyzed By Different Complexes, Sedat Yaşar, Suzan Çeki̇rdek, Ni̇lay Akkuş Taş, Semi̇ha Yildirim, İsmai̇l Özdemi̇r

Turkish Journal of Chemistry

A very efficient ligand-free method was developed for the transfer hydrogenation of ketones and aldehydes catalyzed by different metal complexes. With this catalytic system, the catalytic performance and catalytic stability of different Ir, Ru, and Pd complexes were more favorable than those of the previously reported systems for transfer hydrogenation. This ligand-free catalytic system showed good stability and excellent activity even with lower catalyst concentrations for the ketones and aldehydes tested.

Synthesis And Characterization Of New Chromogenic Substrates For Exoglycosidases: \Alpha-Glucosidase, \Alpha-Mannosidase, And \Beta-Galactosidase, Dumitru Petru Iga, Richard Schmidt, Silvia Iga, Corina Loredana Hotoleanu, Florentina Duica, Alina Nicolescu, Silvia Stefania Gitman

Turkish Journal of Chemistry

Glycosides of 4-nitrocatechol (1,2-dihydroxy 4-nitrobenzene) with \alpha-D-glucopyranose and \alpha-D-mannopyranose were synthesized by the glycosylation of phenol with peracetylated sugars in the presence of BF_3\cdot OBu_2. The glycoside of 4-nitrocatechol with \beta-D-galactopyranose was prepared by the glycosylation of this phenol as sodium phenoxide with tetra-O-benzoyl-\alpha-D- galactopyranosyl bromide. The structure of the reaction products was confirmed by ^1 H and ^{13}C NMR spectra and by chemical analysis. The latter consisted of acidic hydrolysis, followed by ethyl ether extraction and colorimetric determination of 4-nitrocatechol in the ether phase and application of the anthrone method for the sugar in the water phase. The synthetic …

Potentiometric Determination Of Some Food Additives And Their Binding To A Polycationic Species Using Polyion Sensors, Nedi̇me Dürüst, Ali̇ Kayansalan

Turkish Journal of Chemistry

Polycation-sensitive membrane electrodes based on dinonylnaphthalene sulfonate (DNNS) were examined for the determination of some polyanions, namely xanthan (Xanth), alginate (Alg), carboxymethyl cellulose (CMC), and carrageenan (Carr). The potentiometric titrations of polyanionic analytes yielded sharp end points and correlative stoichiometries. After the determinations were successfully performed in saline, these polyanions were also determined in some food products consumed in Bolu (Turkey). In addition, the titration data were used to estimate the interactions between titrant and polyanionic analytes. The equilibrium constants, K_{eq}, and the number of titrant binding sites (n) per mole of analyte polyanion were calculated using Scatchard plots. The …

Application Of Experimental Design On Determination Of Aluminum Content In Saline Samples By Adsorptive Cathodic Stripping Voltammetry, Si̇nan Yilmaz, Betül Öztürk, Durmuş Özdemi̇r, Ahmet Emi̇n Eroğlu, Fatma Ni̇l Ertaş

Turkish Journal of Chemistry

Adsorptive cathodic stripping voltammetric determination of aluminum at ng mL^{-1} levels in salt samples based on the metal complexation with Calcon (1-(2-hydroxynaphthylazo)-2 naphthol-4-sulfonic acid) and the subsequent adsorptive deposition onto a hanging mercury drop electrode was studied. Central composite design was used as a design method. Several chemical and instrumental parameters (pH, ligand concentration, deposition time, deposition potential, and complexing time) were involved in the experimental design. Analytical parameters such as repeatability, linearity, and accuracy were also investigated and the detection limit was found as 0.32 ng mL^{-1}.