Chemistry Commons^™

A Raman Spectroscopic Study Of The Effects Of Hydrogen Bonding On 1,2,3-Triazole, Anna Craig

Honors Theses

The goal of this thesis is to analyze the effects of hydrogen bonding on liquid 1H- 1,2,3-triazole. Spectra of neat 1H-1,2,3-triazole are compared to simulated spectra and are found to differ greatly. The experimental spectrum, however, matches the simulated spectra of 1H-1,2,3-triazole dimers very well. This suggests that dimers play a large role in the liquid structure of 1H-1,2,3-triazole. Though tautomerism is thought to play a large role in the vibrational behavior of 1,2,3- triazole, the Raman spectra obtained here suggest that molecular dimers dominate the liquid state much more so than tautomerism. Even in aqueous solution, the simulated spectra …

Spectroscopic Study Of Charge Transfer Induced Blue Shifting Of Pyrimidine/Water Mixtures On Silver Substrate, Annie Katherine Mcclellan

Honors Theses

Surface enhanced Raman spectroscopy (SERS) is a chemical method gaining much popularity in recent years. With the use of a roughened metal surface or metal nanoparticles, surface plasmon resonances enhance the electromagnetic field allowing for increased Raman signal. Pyrimidine, having two lone pairs of electrons, is capable of charge transfer interactions contributing to a SERS chemical enhancement factor as well. It has recently been reported that hydrogen bonding with water results in the blue-shifting of certain normal modes of pyrimidine. By comparing experimental polarized Raman spectra with the results of electronic structure calculations, the origin of this blue-shifting was found …

Conical Intersection And Potential Energy Surface Features Of A Model Retinal Chromophore: Comparison Of Eom-Cc And Multireference Methods, Samer Gozem, Anna I. Krylov, Massimo Olivucci

Chemistry Faculty Publications

This work investigates the performance of equation-of-motion coupled-cluster (EOM-CC) methods for describing the changes in the potential energy surfaces of the penta-2,4-dieniminium cation, a reduced model of the retinal chromophore of visual pigments, due to dynamical electron correlation effects. The ground-state wave function of this model includes charge-transfer and diradical configurations whose weights vary along different displacements and are rapidly changing at the conical intersection between the ground and the first excited states, making the shape of the potential energy surface sensitive to a balanced description of nondynamical and dynamical correlation. Recently, variational (MRCISD) and perturbative (MRPT2) approaches for including …

Test Selection On Extended Finite State Machines With Provable Guarantees, Bo Guo, Mahadevan Subramaniam

Chemistry Faculty Publications

Building high confidence regression test suites to validate new system versions is a challenging problem. A model- based approach to build a regression test suite from a given test suite is described. The generated test suite includes every test that will traverse a change performed to produce the new version, and consists of only such tests to reduce the testing costs. Finite state machines extended with typed variables (EFSMs) are used to model systems and system changes are mapped to EFSM transition changes adding/deleting/replacing EFSM transitions and states. Tests are a sequence of input and expected output messages with concrete …

Lomustine Analogous Drug Structures For Intervention Of Brain And Spinal Cord Tumors: The Benefit Of In Silico Substructure Search And Analysis, Ronald Bartzatt

Chemistry Faculty Publications

Lomustine is a nitrosourea anticancer agent shown to be effective for treatment of childhood medulloblastoma. In silico substructure searches produced 17 novel nitrosourea agents analogous to lumustine and retaining activity for DNA alkylation and cytotoxic activity. The mean values for Log P, polar surface area, formula weight, number of oxygens & nitrogens, and rotatable bonds were 2.524, 62.89 Anstroms2, 232.8, 5, and 2, respectively. All 17 agents have formula weight less than 450 and Log P less than 5, two criteria preferred for blood-brain barrier penetration.These agents have a polar surface area less than 90 Angstroms2. Each show zero violations …

The Critical Role Of Mechanism-Based Models For Understanding And Predicting Liposomal Drug Loading, Binding And Release Kinetics, Sweta Modi

Theses and Dissertations--Pharmacy

Liposomal delivery systems hold considerable promise for improvement of cancer therapy provided that critical formulation design criteria can be met. The main objective of the current project was to enable quality by design in the formulation of liposomal delivery systems by developing comprehensive, mechanism-based mathematical models of drug loading, binding and release kinetics that take into account not only the therapeutic requirement but the physicochemical properties of the drug, the bilayer membrane, and the intraliposomal microenvironment.

Membrane binding of the drug affects both drug loading and release from liposomes. The influence of bilayer composition and phase structure on the partitioning …

Amalgamation Of Nucleosides And Amino Acids In Antibiotic Biosynthesis, Sandra H. Barnard

Theses and Dissertations--Pharmacy

The rapid increase in antibiotic resistance demands the identification of novel antibiotics with novel targets. One potential antibacterial target is the biosynthesis of peptidoglycan cell wall, which is both ubiquitous and necessary for bacterial survival. Both the caprazamycin-related compounds A-90289 and muraminomicin, as well as the capuramycin-related compounds A-503083 and A-102395 are potent inhibitors of the translocase I enzyme, one of the key enzymes required for cell wall biosynthesis. The caprazamycin-related compounds contain a core nonproteinogen b-hydroxy-a-amino acid referred to as 5’-C-glycyluridine (GlyU). Residing within the biosynthetic gene clusters of the aforementioned compounds is a shared open reading …

Reaction Between Polyol-Esters And Phosphate Esters In The Presence Of Metal Carbides, David W. Johnson, Carolyn Iacullo, John E. Hils

Chemistry Faculty Publications

The reaction of metal carbides with polyol esters found in aerospace lubricants and phosphate esters commonly used as additives was investigated. Carbides were of particular interest since modern materials under consideration at high temperature bearings have surfaces that are primarily metal carbides. Vanadium and chromium carbide were found to react with the ester and phosphate ester by a transesterification reaction, producing an alkyl phosphate which is less stable than the aromatic phosphate esters. In the process, the metal carbide is converted to the metal phosphate and metal polyphosphate, evidenced by the infrared and Raman spectra of the solid residue and …

Environmentally Persistent Free Radicals (Epfrs) In Pm₂.₅ : Their Contribution To Hydroxyl Radical Formation And Atmospheric Transformation, William Micheal Gehling, Jr.

LSU Doctoral Dissertations

Previous research demonstrated environmentally persistent free radicals (EPFRs) will form on particulate surfaces under combustion conditions (temperature range of 150-400 °C) from reactions of organic precursors with redox-active transition metals. With an understanding of how these EPFRs form, it is necessary to determine how they behave in a natural environment after emission. To better understand this, the nature of EPFRs in ambient PM2.5 under simulated atmospheric conditions was investigated. Ambient PM2.5 samples were collected at a roadside ambient monitoring site near heavy interstate traffic and major industrial activity. The EPFR concentration and general radical structure were determined with EPR spectroscopy. …

Experimental And Computational Studies Of Environmentally Persistent Free Radicals (Epfrs) Formation, Lucy W. Kiruri

LSU Doctoral Dissertations

The first part of the thesis investigates the use of theoretical quantum calculations for the study of EPFRs as the initial and fundamental step in the formation of polychlorinated dibenzo-p-dioxin and dibenzofuran. The computational model comprised of density functionals (B3LYP, PBE1PBE, and M06) and two types of basis set namely: LANL2DZ for all atoms and GEN (LANL2DZ for metals and aug-cc-pVDZ for non-metals). Full mechanisms of EPFRs formation over (CuO)1-8, and aluminum oxide clusters were studied. The most stable intermediates and products have been determined and compared to available experimental data. In case of (CuO)1-8 clusters, the small clusters are …

Microfluidics For The Analysis Of Integral Membrane Proteins: A Top-Down Approach, Katrina Nychole Battle

LSU Doctoral Dissertations

The development of fully automated and high-throughput systems for proteomics is now in demand because of the need to generate new protein-based disease biomarkers. Unfortunately, it is difficult to identify protein biomarkers that are low abundant when in the presence of highly abundant proteins, especially in complex biological samples like serum, cell lysates, and other biological fluids. Membrane proteins, which are in many cases of low abundance compared to cytosolic proteins, have various functions and can provide insight into the state of disease and serve as targets for new drugs making them attractive biomarker candidates. Traditionally, proteins are identified through …

Synthesis Of The Western Hemisphere Of Theonellamide C, Saroj Yadav

LSU Doctoral Dissertations

Theonellamides A-F were isolated from Theonella swinhoei by Fusetani and co-workers. Despite considerable synthetic effort to produce theonellamide F by the Shioiri group in the early 1990’s, the total synthesis of a theonellamide has yet to be reported. We report herein our efforts toward some of the required amino acid residues and construction of the western ring of theonellamide C. We describe the synthesis of an uncoded amino acid, (2S,4R)-ɣ-hydroxy-α-amino adipic acid (Ahad), a building block for theonellamide C. We initially investigated the Corey-Lygo method for the catalytic asymmetric generation of the Cα stereocenter. Unfortunately, the alkylation of glycine benzophenone …

Toward The Advancement Of Tetraphosphine Ligand Synthesis For Homogeneous Bimetallic Catalysis, Marc Anthony Peterson

LSU Doctoral Dissertations

A tetraphosphine ligand rac-et,ph-P4 (Et2PCH2CH2(Ph)PCH2P(Ph)CH2CH2PEt2) is used for the formation of a highly active and regioselective bimetallic hydroformylation catalyst. The proposed active catalytic species in acetone, [Rh2H2(µ-CO)2(rac-et,ph- P4)]2+, is formed in situ under H2/CO pressure. This is one of the most impressive examples of cooperativity in homogeneous catalysis. The fragmentation of this catalyst by CO has been investigated and confirmed by in situ NMR spectroscopic studies. A new tetraphosphine ligand rac-et,ph-P4-Ph (et,ph-P4-Ph = Et2P(o-C6H4)P(Ph)CH2(Ph)P(o-C6H4)PEt2) has been synthesized to combat this fragmentation problem. However, the inability to successfully separate the meso and racemic diastereomers led to the attempted alteration of the …

Polymer Microsystems For The Enrichment Of Circulating Tumor Cells And Their Clinical Demonstration, Joyce W. Kamande

LSU Doctoral Dissertations

Cancer research is centered on the discovery of new biomarkers that could unlock the obscurities behind the mechanisms that cause cancer or those associated with its spread (i.e., metastatic disease). Circulating tumor cells (CTCs) have emerged as attractive biomarkers for the management of many cancer-related diseases due primarily to the ease of securing them from a simple blood draw. However, their rarity (~1 CTC per mL of whole blood) makes enrichment analytically challenging. Microfluidic systems are viewed as exquisite platforms for the clinical analysis of CTCs due to their ability to be used in an automated fashion, minimizing sample loss …

Analysis Of Protein Aggregates And Synthetic Nanoparticles Using Capillary Electrophoresis With Light Scattering And Fluorescence Detection, Suresh Chandra Regmi

LSU Doctoral Dissertations

The goal of the research presented in this dissertation is to develop capillary electrophoresis (CE) based analysis techniques for the characterization of individual particles including amyloid beta (Aâ) peptide aggregates and to apply these methods to study the aggregation of Aâ peptides. Protein self-assembly into ordered aggregates is a common and important process in normal biological function, but this process is also involved in several diseases. Amyloid beta peptide aggregation is linked to Alzheimer’s disease. Thioflavin T (ThT) has been used as a fluorescent probe for the detection of Aâ aggregation. Based on previous observations of false positive fluorescent signals …

Synthesis, Spectroscopic Characterization, And Biological Screening Of Binuclear Transition Metal Complexes Of Bicompartmental Schiff Bases Containing Indole And Resorcinol Moieties, Mahendra Raj Karekal, Mruthyunjayaswamy Bennikallu Hire Mathada

Turkish Journal of Chemistry

A series of binucleating Cu(II), Ni(II), and Zn(II) complexes of bicompartmental ligands with ONO donors were prepared. The ligands were synthesized by the condensation of 5-substituted-3-phenyl-1H-indole-2-carboxyhydrazides and 4,6-diacetylresorcinol. The newly synthesized ligands and their complexes were characterized by elemental analysis and various spectral studies like IR, ^1H NMR, ESI-mass, UV-Vis, ESR, thermal studies, magnetic susceptibility, molar conductance, and powder-XRD data. All the complexes were binuclear and monomeric in nature. Cu(II) complexes have octahedral geometry, whereas Ni(II) and Zn(II) complexes have square planar and tetrahedral geometry, respectively. The redox property of the Cu(II) complex was investigated by electrochemical method using cyclic …

Air-Sea Dimethylsulfide (Dms) Gas Transfer In The North Atlantic: Evidence For Limited Interfacial Gas Exchange At High Wind Speed, T. G. Bell, Warren J. De Bruyn, S. D. Miller, B. Ward, K. Christensen, E. S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Shipboard measurements of eddy covariance dimethylsulfide (DMS) air-sea fluxes and seawater concentration were carried out in the North Atlantic bloom region in June/July 2011. Gas transfer coefficients (k(660)) show a linear dependence on mean horizontal wind speed at wind speeds up to 11 m s(-1). At higher wind speeds the relationship between k(660) and wind speed weakens. At high winds, measured DMS fluxes were lower than predicted based on the linear relationship between wind speed and interfacial stress extrapolated from low to intermediate wind speeds. In contrast, the transfer coefficient for sensible heat did not exhibit this effect. The apparent …

New Bimetallic Iridium Cluster Carbonyl Complexes, Mingwei Chen

Theses and Dissertations

Platinum group metal derived bimetallic clusters have been used as precursors to nanoscale catalysts which have been proven to be more effective than their monometallic counterparts. Iridium is a platinum group metal and its applications in catalysis continue to grow. To take advantages of synergies between mixed-metals, we modified iridium clusters with other metal ligands like tin, germanium, and group IB (gold, silver, copper) etc. and obtained a fairly large amount of new iridium derived bimetallic clusters which could be precursors to catalysts with superior properties than that available nowadays. The reaction of Ir4(CO)12 with Ph3SnOH in the presence of …

Synthesis And Modification Of Octafluoro[2.2]Paracyclophane (Parylene Af4), Craig Hicks, Brendan Duffy, Gráinne Hargaden

Articles

Parylenes are a class of organic compounds which have gained significant attention due to their application as coatings in areas such as medical devices and electronics. This review highlights the development of synthetic pathways to Octafluoro[2.2]Paracyclophane, commonly referred to as parylene AF4. Methods which have been used to functionalise AF4 are also presented.

Matrix-Assisted Laser Desorption Ionization Mass Spectrometry For Identificaiton Of Shrimp, Venkatesulu Salla

LSU Master's Theses

Matrix-assisted laser desorption ionization (MALDI) time of flight mass spectrometry was used to identify shrimp at the species level using commercial mass spectral fingerprint matching software (Bruker Biotyper). In the first step, a mass spectrum reference database was constructed from the analysis of six shrimp species that are commercially important in the United States: L. setiferus, F. azticus, S. brevirostris, P. robustus, P. dispar and P. platyceros. In the second step, the reference database was tested using 74 unknown shrimp samples from these six species. Correct identification was achieved for 72 of the 74 samples (97 percent): 72 samples were …

A Microfluidic Bacteria Culturing Device With Maldi Mass Spectrometry Detection, Pratap Reddy Machavaram Siva

LSU Master's Theses

A novel microfluidic device was developed for bacterial cell culturing using mass spectrometry as the detector. One of the challenges in proteomics is to achieve high sensitivity in the identification of proteins in complex samples with widely varying concentrations. The main limitations for proteomic studies are relatively slow and labor-intensive steps such as cell culturing and protein digestion of small sample quantities. Microfluidics is a promising approach to increase throughput and to reduce the time-consuming steps that are necessary for proteomics. When an analytical detection method is combined with microfluidics it can overcome limitations that are important in the analysis …

Instrument And Method Development For Single-Cell Classification Using Fluorescence Imaging Multivariate Optical Computing, Joseph Swanstrom

Theses and Dissertations

Multivariate optical computing (MOC) is an all-optical approach of predictive spectroscopy that utilizes multivariate calibration and spectral pattern recognition techniques while operating in a simple filter photometer instrument, removing the need for expensive instrumentation and post-processing of spectral data. This is accomplished with specially designed interference filters called multivariate optical elements (MOEs). MOC can provide analytical solutions for applications requiring low cost, rugged, and simple to operate instrumentation for use in remote and hazardous environments such as open ocean waters. These instrument specifications are central for developing a method for classifying phytoplankton in their natural environment. Phytoplankton are photosynthetic single …

Structural And Photoluminescent Characterization Of Substituted A3mo4f (A = Sr, Ba, Ca; M = Al, Ga, In, Si And Ge), Robert Lenwood Green

Theses and Dissertations

In this dissertation, the structure and photoluminescent properties of A3MO4F-type materials (A = Sr, Ba, Ca; M =Al, Ga, In, Si, Ge) are studied as potential phosphors for compact fluorescent lamps (CFLs) and phosphor converted light emitting diode (pc LED) lights. Chapter 1 outlines background information of the evolution of lighting technology as well as detailing the synthesis, structural characterization and photoluminescence measurements. Chapter 2 focuses on the changes that the Sr3AlO4F structure undergoes as a result of exposure to a 5% H2/95% Ar atmosphere. High-resolution neutron powder diffraction is used to probe for minute structural changes. Chapter 3 is …

Challenges And Rewards Of Single Crystal Flux Growth: Physical Properties Of Structurally Related Ln-Ru-Al Intermetallics, Gregory Morrison

LSU Doctoral Dissertations

The availability of single crystals is vital for understanding the intrinsic properties of crystalline materials. The flux growth method is a versatile technique which may be used to grow single crystals. However, their synthesis can often be challenging, especially when a competing phase is very robust. Herein, we study the growth competition between structurally related compounds in the Ln-Ru-Al phase space. We demonstrate the benefits of single crystals and suggest methods to grow competing phases. CeRu2Al10 has garnered interest due to its higher ordering temperate than expected from de Gennes scaling and its metal-to-insulator transition at the same temperature. Here, …

Electrochemical Properties Of 1,3-Disubstituted Methyl Methoxy Phenyl-5-Phenylformazans And Comparison With Spectral Properties, Habi̇be Tezcan, Güler Ekmekci̇, Mehmet Levent Aksu

Turkish Journal of Chemistry

In this study, electrochemical behaviors of formazans were investigated. The compounds contained CH_3 and OCH_3 groups at the o-, m-, and p-positions of the 1-phenyl ring and an OCH_3 group at the p-position of the 3-phenyl ring. Their electrochemical behaviors, such as the number of electrons transferred, diffusion coefficients, and heterogeneous rate constants, were studied by cyclic voltammetry, ultramicrodisk electrode, and chronoamperometry. Possible mechanisms were proposed based upon the data obtained. There was a correlation between the absorption and electrochemical properties. A linear correlation was obtained between \lambda_{\max} and E_{red2} and Hammett substituent coefficients with E_{red2} and k_s values.

Synthesis, Characterization, And Antimicrobial Activity Of Some New Phosphorus Macrocyclic Compounds Containing Pyrazole Rings, Tarik El-Sayed Ali, Salah Abdel-Aziz Abdel-Ghaffar, Kamilia Mohamed El-Mahdy, Somaia Mohamed Abdel-Karim

Turkish Journal of Chemistry

A simple synthetic method is reported for the preparation of some new phosphorus macrocycles in which the pyrazole rings are appended to a phosphorus atom. The methodology is based on the cyclocondensation reaction of bis(4-formylpyrazolyl) phosphine oxide(1a, 1b) with nitrogen nucleophiles that contain active terminal amino groups. The antimicrobial activities of the synthesized compounds were assayed.

Synthesis And Cytotoxic Activity Of Some 2-(2,3-Dioxo-2,3-Dihydro-1h-Indol-1-Yl)Acetamide Derivatives, Özlem Akgül, Ayşe Hande Tari̇koğullari, Fadi̇me Aydin Köse, Petek Ballar Kirmizibayrak, Mehmet Varol Pabuççuoğlu

Turkish Journal of Chemistry

Isatin, 1H-indoline-2,3-dione, an endogenous compound, is also a synthetically versatile molecule that possesses a diversity of biological activities including anticonvulsant, antibacterial, antifungal, antiviral, anticancer, and cytotoxic properties. Based on the promising cytotoxic activity studies on N-substituted isatin derivatives, a series of 18 derivatives of 2-(2,3-dioxo-2,3-dihydro- 1H-indol-1-yl)-N-phenylacetamide were designed, synthesized, and characterized according to their analytical and spectral data. All of the compounds were evaluated for their cytotoxic activity against MCF7, A549, HeLa, and HEK293 cell lines by real time cell analyzer. Etoposide was used as a standard compound. Briefly, ortho substitutions gave better results compared to meta and para substitutions …

Electrochemistry Of 2,6-Diaminopurine On Multiwall Carbon Nanotube Modified Glassy Carbon Electrode, Ebru Mavi̇oğlu Ayan, Şükri̇ye Karabi̇beroğlu, Zekerya Dursun

Turkish Journal of Chemistry

The electrochemical oxidation of 2,6-diaminopurine (2,6-DAP) was studied in pH 7.4 phosphate buffer solution on multiwall carbon nanotube modified glassy carbon electrode (MWCNT/GCE) over a temperature range of 20 to 50 °C using cyclic voltammetry. 2,6-DAP oxidation on MWCNT/GCE showed a well-defined and irreversible oxidation peak at about 0.72 V vs. Ag/AgCl at pH 7.4. The oxidation potential of 2,6-DAP linearly varied with pH over the range of 3.0 to 10.0 with a slope of --0.0547 V/pH, implying that 2 protons were accompanied by 2 electrons transferred in the electrochemical reaction. The activation energy, Ea, of oxidation reaction was found …

A Two-Component Protocol For Synthesis Of 3-(2-(Substituted Phenylamino)Thiazol-4-Yl)-2h-Chromen-2-Ones, Aamer Saeed, Mubeen Arif, Madiha Irfan, Michael Bolte

Turkish Journal of Chemistry

An efficient 2-component synthesis of a series of 3-(2-(substituted phenylamino)thiazol-4-yl)-2H-chromen-2-ones (3a--j) was achieved by the reaction of 3-(2-thiocyanatoacetyl)-2H-chromen-2-one (1) with a variety of suitably substituted anilines in 1:1 molar ratio in ethanol. The structures of the products were established by elemental analyses, and UV-vis, FTIR, ^1H and ^{13}C NMR, and mass spectroscopy. 3-(2-(4-Methylphenylamino)thiazol-4-yl)-2H-chromen-2-one (3j) was further characterized by single crystal X-ray diffraction study. This compound, C_{19}H_{14}N_2OS, crystallizes in the orthorhombic space group Pna21, with Z = 4, and unit cell parameters a = 13.0785(11), b = 25.746(2), c = 4.7235(3) Å, \alpha = \beta = \gamma = 90°.

A Phthalocyanine--Fluorescein Conjugate, İlker Ün, Yunus Zorlu, Hani̇fe İbi̇şoğlu, Fabienne Dumoulin, Vefa Ahsen

Turkish Journal of Chemistry

A phthalocyanine--fluorescein conjugate was designed and prepared. Its photophysical properties (electronic absorption and fluorescence) were determined and compared with those of an analogous derivative functionalized by a simple triazole without chromophore. It is likely to be used as a theranostic agent in photodynamic therapy.