Chemistry Commons^™

Mutational Analysis Of The Stability Of The H2a And H2b Histone Monomers, Matthew R. Stump, Lisa M. Gloss

Faculty Publications - Department of Biological & Molecular Science

The eukaryotic histone heterodimer H2A–H2B folds through an obligatory dimeric intermediate that forms in a nearly diffusion-limited association reaction in the stopped-flow dead time. It is unclear whether there is partial folding of the isolated monomers before association. To address the possible contributions of structure in the monomers to the rapid association, we characterized H2A and H2B monomers in the absence of their heterodimeric partner. By far-UV circular dichroism, the H2A and H2B monomers are 15% and 31% helical, respectively—significantly less than observed in X-ray crystal structures. Acrylamide quenching of the intrinsic Tyr fluorescence was indicative of tertiary structure. The …

Stereochemical And Regiochemical Trends In The Selective Spectrophotometric Detection Of Biological Molecules, Shan Jiang

LSU Doctoral Dissertations

Useful mechanistic studies to date concerning sugar detection by arylboronic acid chemosensors have mainly involved the elucidation of equilibrium constants and the role of boron-nitrogen interactions in signal transduction. However, several discreet sugarboronate complexes exist in solution. This is due to the complex equilibria between isomeric species of even the simplest monosaccharides. Relatively few reports have been devoted to a systematic study of the structures of each of the corresponding individual sugar-boronate complexes. We have investigated some of the precise regio- and stereochemical features of the various equilibrating sugar isomers that induce selective signal transduction. As a result of this …

Laser Induced Fluorescence Spectroscopy Of Molecular Bromine: Observations Of Emission To High Vibrational Levels In The Ground (X) State, David Jonathan Postell

Browse all Theses and Dissertations

The Laser Induced Fluorescence spectrum of the B - X system of molecular bromine was recorded using a Red and Near Infrared sensitive PMT coupled to a scanning monochromator. A 543 nm HeNe laser was used to excite three resonances. Assignment of those resonances was made. A line narrowed Nd:YAG laser was used to excite eight fluorescence progressions, six from the (79,81) bromine isotopomer and one each from the (79,79) bromine and (81,81) bromine isotopomers. Analysis of the visible bands helped determine the resonances excited by the Nd:YAG laser. Fluorescence in the near infrared region, 9500 - 14000 angstroms, was …

Probing The Association Behavior Of Hydrophobic Organic Compounds With Dissolved Humic Materials, Hadi M. Marwani

LSU Doctoral Dissertations

The association mechanism between hydrophobic organic compounds (HOC) and dissolved humic materials (DHM) has continued to be one of the interesting areas in environmental applications. The goal of the research reported in this dissertation is to investigate the association behavior of HOC with DHM. The first part of this research involves steady-state fluorescence measurements of these multi-component systems to study the effect of DHM content on the association mechanism of HOC, in particular using pyrene as a model. Results showed that steady-state fluorescence alone may not provide enough information about the quenching mechanism of pyrene with DHM. Lifetime based fluorescence …

Detection Of Proteins By Two-Photon Excitation Of Native Fluorescence, Li Li

Theses and Dissertations

Proteins are of primary importance to the structure and function of all living cells. Study of proteins relies on the ability to separate a complex mixture so that individual proteins can be more easily processed by other techniques. Since protein samples often exist at low concentration in a small volume, the trend in chemical analysis is toward micro total analysis systems (µTAS) or lab-on-a-chip devices. Among µTAS separation methods, the relatively new electric field gradient focusing (EFGF) technique has shown potential. It focuses and separates analytes based on their electrophoretic migration in an opposing hydrodynamic flow. The detection principles that …

Charge-Mediated Recognition Of N-Terminal Tryptophan In Aqueous Solution By A Synthetic Host, Meghan E. Bush, Nicole D. Bouley, Adam R. Urbach

Chemistry Faculty Research

The molecular recognition of peptides and proteins in aqueous solution by designed molecules remains an elusive goal with broad implications for basic biochemical research and for sensors and separations technologies. This paper describes the recognition of N-terminal tryptophan in aqueous solution by the synthetic host cucurbit[8]uril (Q8). Q8 is known to form 1:1:1 heteroternary complexes with methyl viologen (MV) and a second aromatic guest. Here, the complexes of Q8·MV with (i) the four natural aromatic α-amino acids, (ii) four singly charged tryptophan derivatives, and (iii) four tryptophan-containing tripeptides were characterized by isothermal titration calorimetry, mass spectrometry, and UV−visible, fluorescence, and …

A Bilayer Self-Assembled Membrane Electrode For Fluorescence And Its Electrochemical Characterization, Xiang-Ying Sun, Bin Liu, Yun-Bao Jiang

Journal of Electrochemistry

The bilayer membrane was assemblied on Au electrode by the electrostatic interaction between the fluorescence regent 1-naphthylamine diacetate acid (NADA) and DL-Cysteine. The SAMs electrode NADA/Cys/Au can be used as fluorescence and electrochemical sensor for metal ions. This paper states the electrochemical characterization of NADA/Cys/Au and SAMs' application in continous determination for Cu²⁺ and Ni²⁺.

Investigation Of Model Cell Membrane Disruption Via Fluorescence And Light Scattering Techniques, Imara Charles

Seton Hall University Dissertations and Theses (ETDs)

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Synthesis, Characterization, And Application Of Water-Soluble Chiral Calix[4]Arene Derivatives In Spectroscopy And Capillary Electrokinetic Chromatography, Kim Hamilton

LSU Doctoral Dissertations

This dissertation is an account of the synthesis, characterization, and application of novel water-soluble chiral calixarenes in spectroscopy and capillary electrophoresis. It is divided into four sections. The first part describes the synthesis and nuclear magnetic resonance (NMR) characterization of four p-t-butylcalix[4]arenes bearing L-amino acid moieties on their lower rims (CX4-AA). The structure and conformation of the derivatives have been determined using one- and two-dimensional NMR techniques. Proton and carbon-13 spectra show that the derivatives are tetra-substituted and adopt a cone conformation. The preparation and characterization of silica-bonded calixarene stationary phases for capillary electrochromatography is also reported in Chapter 2. …

Solid-Phase Dna Sequencing Reactions Performed In Micro-Capillary Reactors And Solid-Phase Reversible Immobilization In Microfluidic Chips For Purification Of Dye-Labeled Dna Sequencing Fragments, Yichuan Xu

LSU Doctoral Dissertations

The research presented in this dissertation involves micro-capillary reactors for solid phase DNA sequencing, the identification of dye terminator sequencing fragments with time-resolved methods, and purification of dye-labeled DNA fragments using solid- phase reversible immobilization in microfluidic chips. Solid-phase micro-reactors have been prepared for DNA sequencing applications using slab gel electrophoresis. A PCR product was immobilized to the interior wall of a fused-silica capillary tube via a biotin-streptavidin linkage. Solid-phase sequencing was carried out in micro-capillary reactors using a four-lane, single color dye primer chemistry strategy. The read length was found to be 589 bases. The complementary DNA fragments generated …

Analysis Of Near-Infrared Dye-Labeled Sanger Sequencing Fragments With Gel Electrophoresis Using The Time-Resolved Flourescence Lifetime Indentification Methods, Suzanne Jeanel Lassiter

LSU Doctoral Dissertations

The research presented in this dissertation involves the identification of sequencing fragments with time-resolved methods. For this application, near-infrared heavy-atom tricarbocyanine dyes were developed in our laboratory, which can be excited with a single laser and emission collected using a single detection channel. The dyes have four spectroscopically unique, but relatively short lifetimes that can be altered by the intramolecular heavy-atom they contain. The work described here involves the optimization of dye-primer chemistry for preparing Sanger sequencing reactions for longer reads and the optimization of the separation matrix for capillary gel electrophoresis that produces favorable statistical analysis of the aforementioned …

Aneuploidy Frequencies In Semen Fractions From Ten Oligoasthenoteratozoospermic Patients Donating Sperm For Intracytoplasmic Sperm Injection, Jerome Pfeffer, Myung-Geol Pang, Stanton F. Hoegerman, Christopher J. Osgood, M. W. Stacey, Jacob Mayer, Sergio Oehninger, William G. Kearns

Biological Sciences Faculty Publications

Objective: To determine aneuploidy frequencies in pellet and swim-up semen fractions from 10 infertile men with severe oligoasthenoteratozoospermia (OAT) who were donating sperm for intracytoplasmic sperm injection and to determine whether the swim-up isolation method would successfully separate aneuploid from haploid sperm.

Design: Prospective study.

Setting: Infertility clinic and molecular genetics laboratory.

Patient(s): Ten patients with severe OAT.

Intervention(s): Cytogenetic analyses by fluorescence in situ hybridization to determine aneuploidy frequencies for chromosomes 1, 13, 18, 21, X, and Y in sperm from swim-up and pellet fractions.

Main Outcome Measure(s): Gametic aneuploidy was scored in sperm fractions separated by the swim-up …

The Association Of Nadph With The Guanine Nucleotide Exchange Factor From Rabbit Reticulocytes: A Role Of Pyridine Dinucleotides In Eukaryotic Polypeptide Chain Initiation, Jaydev N. Dholakia, Timothy C. Muesser, Charles L. Woodley, Lawrence J. Parkhurst, Albert J. Wahba

Department of Chemistry: Faculty Publications

The guanine nucleotide exchange factor (GEF) was purified to apparent homogeneity from postribosomal supernatants of rabbit reticulocytes by chromatography on DEAE-celiulose and phosphocellulose, fractionation by glycerol gradients, and chromatography on Mono S and Mono Q (Pharmacia). At the Mono S step GEF is isolated as a complex with the eukaryotic polypeptide chain initiation factor 2 (eIF-2) and is separated from this factor by column chromatography on Mono Q. An emission spectrum characteristic of a reduced pyridine dinucleotide was observed when GEF was subjected to fluorescence analysis. By both coupled enzymatic analysis and chromatography on reverse-phase or Mono Q columns, the …

Pressure Dependence Of Fluorescent And Photolytic Interferences In Ho Detection By Laser-Excited Fluorescence, Thomas M. Hard, Robert J. O'Brien, T. B. Cook

Chemistry Faculty Publications and Presentations

In the measurement of HO concentrations by laser-excited fluorescence, expansion of the sampled air offers a way to reduce fluorescent and photolytic interference by other species. The decrease in [HO] upon expansion is balanced by an increase in HO fluorescence yield over a wide range of pressures. Background air fluorescence is reduced if the responsible species have fluorescence yields higher than those of HO. Preliminary experiments indicate that most of the fluorescence observed in laboratory air is due to such species. Upon expansion, the suppression of fluorescent interference can be no greater than the reduction in pressure, whereas the suppression …

The Kinetics Of Solvent Reorientation In Hydroxylated Solvents From The Exciting-Wavelength Dependence Of Chromophore Emission Spectra, John Milton, Robert M. Purkey, William C. Galley

WM Keck Science Faculty Papers

The disappearance of the exciting-wavelength dependence of the phosphorescence spectra of polar, aromatic chromophores in supercooled glycol–water mixtures is utilized to monitor the kinetics of solvent reorientation. Reorientation times in the nanosecond to second range are obtained for (3:2 v/v) glycerol–water and (1:1 v/v) ethylene glycol–water at 140–240 °K. The results suggest that the process is one involving a cluster of solvent molecules and in which the chromophore plays a relatively passive role. Steady-state data and direct measurements of phosphorescence shifts as a function of time indicate that the solvent reorientation process is nonexponential in nature. The decay function derived …