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Articles 1 - 9 of 9
Full-Text Articles in Physical Sciences and Mathematics
Towards The Total Synthesis Of Thioviridamide: Thiyl Radical Approach To The Beta-Thioenamide Linkage Formation, Jung-Hoon Kang
Towards The Total Synthesis Of Thioviridamide: Thiyl Radical Approach To The Beta-Thioenamide Linkage Formation, Jung-Hoon Kang
Theses and Dissertations
We developed an approach to the β-thioenamide linkage contained in the S-(2-aminovinyl)cysteine (avCys) residue of thioviridamide.1,2 Kinetic and thermodynamic control of radical additions of thiols to ynamides were studied for the formation of β-thioenamide linkage. Thiyl radicals are electrophilic and ynamides are electron-rich alkynes. This complementary polarity of the radical and acceptor increases the likelihood of a successful radical addition reaction. Because little is known about these types of compounds (β-thioenamides), we were unsure what kinds of yields and stereoselectivities (cis vs. trans) to expect. The adduct stability is another issue to consider. Fortunately, under typical radical addition conditions, the …
Photocycloaddition Of Allenes, Crystal Ward
Photocycloaddition Of Allenes, Crystal Ward
Theses and Dissertations
For the past ten years the Fleming research group has been involved in the research of allene compounds. We have explored the synthesis of allenes as well as several reactions involving allenes, such as oxidation and nitrene addition. Recently, we have explored the synthesis and photochemistry of allenic alcohols tethered to silicon. There are literature examples using allenes in synthesis, but very few examples exist using allenes in photochemical cycloaddition reactions. We have found that a diisopropylallenyloxy(cinnamyloxy)silane derivative undergoes [2+2] photochemical cycloaddition to produce a cyclobutylsilane product when irradiated for 60-75 minutes.
I. Thermodynamics And Magnetism Of Cu2ocl2 Ii. Repairs To Microcalorimeter The "2"S Are Subscripts, And The Second 2 Is Preceded By A Lower Case L, Not A One, Thomas J. Parry
Theses and Dissertations
Adiabatic calorimetry provides accurate and precise specific heat (Cp) data. From this data, thermodynamic functions may be calculated. Cu2OCl2, melanothallite, became of interest as part of a study of a particular thermochemical cycle. The experimental specific heat data and the calculated thermodynamic functions are reported here. Free energies of formation, calculated from the thermodynamic functions, suggest the particular cycle of interest with this compound as an intermediate is not feasible; uncertainty as to the accuracy of CuO and CuCl2 data used in the calculations indicate further study may be necessary. Upon collection of the specific heat data, an antiferromagnetic transition …
A Radical Conjugate Addition Approach To The Total Synthesis Of Celogentin C, Steven G. Capps
A Radical Conjugate Addition Approach To The Total Synthesis Of Celogentin C, Steven G. Capps
Theses and Dissertations
The synthesis of five chiral DBFOX (dibenzofuran-oxazoline) ligands with either aryl or benzyl substituents will be presented. The requisite amino alcohols were obtained with high enantioselectivity either commercially (DBFOX/Bn), via Sharpless asymmetric aminohydroxylation (DBFOX/Nap, DBFOX/t-BuPh, DBFOX/Pip), or via phase-transfer catalyzed asymmetric alkylation (DBFOX/MeNap). These ligands, complexed with Mg(NTf2)2, were used as Lewis acid promoters of enantioselective radical conjugate additions to α/β-unsaturated nitro-amides/esters. A summary of these results is presented and discussed. These findings led us to believe that our initial binding model between metal, ligand, and substrate was flawed. Thus, we figured that if we started with a functionality known …
Regulators Of G-Protein Signaling, Rgs13 And Rgs16, Are Associated With Cxcl12-Mediated Cd4+ T Cell Migration, Lijin Xia
Theses and Dissertations
Chemokines are important chemical signals that guide lymphocyte movement within the immune system and promote the organization and functions of germinal centers (GCs) in the secondary lymphoid tissues. Previous studies have shown that GC T cells exhibit high expression of chemokine receptor 4, CXCR4, but that these cells are unable to migrate to the ligand for this receptor, the chemokine CXCL12. This “migratory paralysis” to CXCL12 was found to be correlated with the expression of two Regulators of G-protein Signaling, RGS13 and RGS16 in the GC T cells. The objective of my research was to determine whether RGS13 and RGS16 …
Spectroscopic Study Of Compressible Mobile Phase And Stationary Phase Behavior In Chromatography, Lawrence R. Baker
Spectroscopic Study Of Compressible Mobile Phase And Stationary Phase Behavior In Chromatography, Lawrence R. Baker
Theses and Dissertations
Raman spectroscopy, laser-induced fluorescence, and sum-frequency generation (SFG) spectroscopy are used to investigate the behavior of compressible mobile phases and stationary phases under a variety of chromatographic conditions. Efforts to understand and optimize separations employing compressible mobile phases have been limited by a lack of understanding of the mobile phase density gradient. Mobile phase compressibility leads to gradients in linear velocity and solute retention and affects separation speed and efficiency, especially in packed columns. This work describes on-column density measurement of CO2, a common carrier fluid for SFC and SGC, in packed capillary columns using Raman microspectroscopy. On-column detection by …
Genetic Analysis Of The Role Of Smpb In Establishing The Reading Frame On Tmrna, Talina Christensen Watts
Genetic Analysis Of The Role Of Smpb In Establishing The Reading Frame On Tmrna, Talina Christensen Watts
Theses and Dissertations
Ribosomes translate the genetic information encoded by mRNA into proteins. Defective mRNAs can cause stalling of translating ribosomes. The molecule tmRNA (transfer-messenger RNA) rescues stalled ribosomes in eubacteria. Together with its protein partner SmpB, tmRNA mimics a tRNA by entering the ribosomal A site and linking an alanine residue to the growing polypeptide chain. The ribosome then abandons the defective mRNA template and resumes translation on tmRNA, adding ten more amino acids to the nascent polypeptide. As a result of tmRNA action, stalled ribosomes are released and recycled, the defective mRNA is destroyed, and the aborted protein product is tagged …
Ion Permeation Through Membrane Channels: Molecular Dynamics Simulations Studies, Morad Mustafa
Ion Permeation Through Membrane Channels: Molecular Dynamics Simulations Studies, Morad Mustafa
Theses and Dissertations
Molecular dynamics simulation was used to study ion permeation through different membrane proteins embedded in a lipid bilayer (DMPC) with different saline solutions. The potential of mean force (PMF) for ion transport was obtained by umbrella sampling simulations. A revised MacKerell force field for tryptophan residues was studied using gramicidin A (gA) channel as a test model. The revised force field contribution to the Na+ PMF was consonant with the prediction from the experimental results, but in stark contrast to the prediction of the CHARMM force field, version 22, for the tryptophan side-chain. A new grid-based correction map algorithm by …
Statistical Approach To The Characterization And Recognition Of Human Gaits, Derrick M. Chelliah
Statistical Approach To The Characterization And Recognition Of Human Gaits, Derrick M. Chelliah
Theses and Dissertations
This thesis addresses the final portion of a complete process for human gait recognition. The thesis takes as input information that has been generated from videotaping walking individuals and converting their gaits into numerical data that measures the locations of various points on the body through time. Beginning with this data, this thesis uses a variety of mathematical and statistical methods to create identifying signatures for each individual and identify them on the basis of that signature. The end goal is to achieve under controlled laboratory conditions human gait recognition, an identification method which does not require contact or cooperation …