Chemistry Commons^™

The 14N Quadrupole Coupling In Hexamethylene Triperoxide Diamine (Hmtd), John Persons, Gerard S. Harbison

Gerard Harbison Publications

Using high-field NMR, we have determined the magnitude of the nuclear quadrupole interaction in hexamethylene triperoxide diamine (HMTD), the explosive allegedly used in the London bombings of July 2005. The experimental quadrupolar coupling constant, 5.334 MHz, is in good agreement with quantum chemical calculations. The predicted single zero-field transition frequency should lie in a relatively empty part of the 14N nuclear quadrupole resonance (NQR) spectrum; the spin relaxation rate is reasonably fast.

Mechanism Of Rate-Limiting Motions In Enzyme Function, Eric D. Watt, Hiroko Shimada, Evgueni Kovriguine, J. Patrick Loria

Chemistry Faculty Research and Publications

The ability to use conformational flexibility is a hallmark of enzyme function. Here we show that protein motions and catalytic activity in a RNase are coupled and display identical solvent isotope effects. Solution NMR relaxation experiments identify a cluster of residues, some distant from the active site, that are integral to this motion. These studies implicate a single residue, histidine-48, as the key modulator in coupling protein motion with enzyme function. Mutation of H48 to alanine results in loss of protein motion in the isotope-sensitive region of the enzyme. In addition, k _cat decreases for this mutant and the kinetic …

Functionalization Of Resorcinarenes And Study Of Antimicrobial Activity, Kirankirti Muppalla

USF Tampa Graduate Theses and Dissertations

Cavitands are very important class of compounds in supramolecular chemistry. These molecules contain rigid enforced cavity,and have attracted considerable attention in supramolecular chemistry as building blocks for the construction of carcerands, hemicarcerands, and other host guests complexes. Nearly 40 years ago, Niederl and Vogel laid foundation for the study of such type of condensation reactions. In our laboratory we are involved in synthesis of resorcinarenes with readily available substrates such as resorcinol and aldehydes to form a cyclic tetramer.

Herein, I present detailed studies about the functionalization of the synthesized tetramers and their antimicrobial activity. Octahydroxy resorcinarenes were synthesized and …

The Extent Of Perturbation Of Skin Models By Transdermal Penetration Enhancers Investigated By 31p Nmr And Fluorescence Spectroscopy, Charmita Patricia Burch

Chemistry Dissertations

The molecular basis of the potent transdermal enhancement activity of a series of iminosulfuranes, structure provided where X = H, Cl, Br, and I, is being investigated skin models. It has been shown (J. Lipid Res. 46(2005), 2192-2201.) that correlations exist between the activity of the aforementioned transdermal penetration enhancers (TPE) and the extent to which these agents bind to DMPC vesicles and perturb the gel to liquid crystal phase transition measured by calorimetry. The degree to which the perturbation of these compounds extends into the bilayer interior in contrast to surface activity is unclear. To gain insight into this …

Slow Turning Reveals Enormous Quadrupolar Interactions (Streaqi), John Persons, Gerard S. Harbison

Gerard Harbison Publications

We introduce a new solid-state NMR method, which uses very slow sample rotation to visualize NMR spectra whose width exceeds feasible spectrometer bandwidths. It is based on the idea that if we reorient a tensor by a known angle about a known axis, the shifts in the NMR frequencies observed across the spectral width allow us to reconstruct the entire tensor. Called STREAQI (Slow Turning Reveals Enormous Anisotropic Quadrupolar Interactions), this method allows us to probe NMR nuclei that are intractable to current methods. To prove the concept and demonstrate its promise we have implemented the method for several 79Br …

Solution Conformations Of Three Small Cluster Oligosaccharide Mimetics (Scom) From D-Glucosamine, D-Altrosamine, And (-)-Quinic Acid, Q. L. Nguyen, L. Olmstead, S. Bains, Andreas H. Franz

College of the Pacific Faculty Articles

Three small cluster oligosaccharide mimetics were synthesized, and their CDCl3 solution conformations were determined with NMR experiments. In this paper, we confirmed conformational similarities in rings A and B in all three compounds, and we provide the overall solution geometries. In all cases, an unusual cyclohexane twist-boat conformation with longrange 4 J-(W)-coupling was observed. The origin of the bias towards the twist-boat was attributed primarily to the fused ring system between the cyclohexane ring and the dioxacyclopentane (acetal) including hydrogen bonding. Temperature-annealed molecular dynamics simulations complemented the NMR experiments and supported the overall assignment.

Structure And Thermodynamics Of A Conserved U2 Snrna Domain From Yeast And Human, Dipali G. Sashital, Vincenzo Venditti, Courtney G. Angers, Gabriel Cornilescu, Samuel E. Butcher

Vincenzo Venditti

The spliceosome is a dynamic ribonucleoprotein complex responsible for the removal of intron sequences from pre-messenger RNA. The highly conserved 5′ end of the U2 small nuclear RNA (snRNA) makes key base-pairing interactions with the intron branch point sequence and U6 snRNA. U2 stem I, a stem–loop located in the 5′ region of U2, has been implicated in spliceosome assembly and may modulate the folding of the U2 and U6 snRNAs in the spliceosome active site. Here we present the NMR structures of U2 stem I from human and Saccharomyces cerevisiae. These sequences represent the two major classes of U2 …

Synthesis And Characterisation Of Tetra-Tetrazole Macrocycles, Andrew Bond, Adrienne Fleming, Fintan Kelleher, John Mcginley, Vipa Prajapati, Signe Skovsgaard

Articles

The syntheses of tetra-tetrazole macrocycles, containing two bis-tetrazole units linked by a variety of alkyl chain lengths from four to eight carbons, are described. The crystal structures of three of these derivatives are reported, and the molecular conformation in the solid state is compared to that of one previously reported tetra-tetrazole macrocycle and to other bis- and tris(tetrazole)benzene structures. The macrocycle conformation is influenced by the length of the alkyl chain linker, the relative orientation of the tetrazole rings on the benzene ring, and by intermolecular interactions. In the macrocycles based on 1,2-bis(tetrazole)benzene, the adjacent tetrazole rings on the benzene …

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 …

Tailoring Branching For Poly (Arylene Ether)S Via Reactivity Ratio Controlled Polymerizations, Amanda Ike

Browse all Theses and Dissertations

The ability to control physical and mechanical properties of polymer systems has become an important aspect of polymer science. In order to tailor the branching in polymer systems, an understanding into the reactivity of the electrophilic sites in the monomer is important. Kinetic methods have been explored in order to determine the reactivity of monomers in preparing poly(arylene ether)s and to predict the degree of branching that will occur in a polymer of this kind. The reactivity of AB2 sulfones and phosphine oxides was explored, along with the reactivity of ABB'B'' sulfones. NMR spectroscopy was used as a probe into …

Preparation, Spectroscopy, Antimicrobial Assay, And X-Ray Structure Of Dimethyl Bis-(4-Methylpiperidine Dithiocarbamato-S,S`)-Tin(Iv), Zia-Ur Rehman, Saira Shahzadi, Saqib Ali, Guo-Xin Jin

Turkish Journal of Chemistry

Dimethyl bis(4-methylpiperidine dithiocarbamato-S,S')-tin(IV) was synthesized and characterized by elemental analysis, IR and mass spectrometry, multinuclear NMR (^1H- and ^{13}C-NMR), and X-ray single crystal analysis. IR data showed that the ligand acts as a bidentate in the solid state. X-ray data showed the unsymmetrical nature of the ligand towards coordination to tin. It crystallized in the monoclinic P2_1/n space group. Its geometry is distorted octahedral. Antimicrobial activity data shows that the complex exhibits significantly more activity than the free ligand.