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- Chemiluminescence (2)
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Articles 1 - 9 of 9
Full-Text Articles in Physical Sciences and Mathematics
Quantification Of Nanomolar Superoxide In Aqueous Solution : Flow Injection Analysis Using The Chemiluminescent Reagent Mcla., Nathan Boland
Quantification Of Nanomolar Superoxide In Aqueous Solution : Flow Injection Analysis Using The Chemiluminescent Reagent Mcla., Nathan Boland
Honors Theses
A flow injection system using the chemiluminescent reagent 2-methyl-6-(4methoxyphenyl)- 3,7-dihydroimidazo[1,2-a]pyrazin-3-one (MCLA) was used to quantify aqueous concentrations of superoxide. Stock solutions of superoxide were produced by photolysis of a solution of 2-propanol and benzophenone. The concentration of superoxide was quantified in the stock solutions by direct measurement of the absorbance at 240 nm. Quantified additions of superoxide to the flow injection analysis system reacted with MCLA at pH 5.1 demonstrated a detection limit of 0.074 nM superoxide. Selective superoxide detection was confirmed by pH-dependent decay of superoxide, which was in excellent agreement with published rates.
Metal Ion Stabilization Of G-Tetrads Containing 6-Thioguanosine, Julia Drees
Metal Ion Stabilization Of G-Tetrads Containing 6-Thioguanosine, Julia Drees
Honors Theses
As alternative structures to the double helix, G-tetrads are thought to occur in DNA with many repeating deoxyguanosines (dG). These tetrads have one dG on each corner of a plane and can stack into tetraplexes that can be aptamers and may be found in telomeres. G-tetrads are destabilized by incorporation of 6-thiodeoxyguanosine (?sdG). Addition of metal ions that bind sulfur may stabilize these ?sdG-tetrads. We have carried out a survey of metal ion titrations into ?sG. Stable ?sG:MD? complexes were found for Hg2? (2:1), Cd2? (4:1), Ag2? (0.7:1) and Pt2? (thought to be 2:1). UV/Visible spectrophotometry indicates that G-tetrads containing …
Photochemical Generation And Intramolecular Chemistry Of 2-Hydroxy-2-Methylpropylidene, Robin Farlow
Photochemical Generation And Intramolecular Chemistry Of 2-Hydroxy-2-Methylpropylidene, Robin Farlow
Honors Theses
2-(1a,9b-Dihydro-lH-cyclopropa[l]phenanthren-1-yl)-propan-2-ol was synthesized by two different but related synthetic routes and characterized by melting point, IR GC/MS, CHN, and NMR spectroscopy. Photolysis of the alcohol in benzene d-6 led to the formation of 2-butanone, 1-methylcyclopropanol, and 2,2-dimethyloxirane in a 26:10:1 ratio via 2-hydroxy-2methylpropylidene, a novel ?-hydroxycarbene. These products are a consequence of intramolecular insertions of the carbene into C-C, C-H, and O-H bonds. Molecular orbital calculations performed at the Becke-3LYP/6-31G(d) level indicate that the singlet form of this carbene is more thermodynamically stable than the triplet. Furthermore, the transition states to the three products from the singlet species were modeled …
Study Of The Effects Of Co2(G) On The Fe(Ii)-Luminol Chemiluminescence System: Application To Ultra-Trace Analysis Of Fe(Ii), Sara Beth Lovitz
Study Of The Effects Of Co2(G) On The Fe(Ii)-Luminol Chemiluminescence System: Application To Ultra-Trace Analysis Of Fe(Ii), Sara Beth Lovitz
Honors Theses
The Fe(II)-catalyzed oxidation of luminol has been a well-accepted chemiluminescence method for the trace and ultra-trace analysis of Fe(II) and Fe(III) in natural waters. Investigation into this chemiluminescence system has shown that COlg) is essential to Fe-catalyzed luminol chemiluminescence. In absence of CO2(g) there is no chemiluminescent signal. These reactions worked well in the past because CO2 is present in most laboratory H20 supplies. Intentional saturation of CO2 results in a 5-fold increase for this conventional system. We propose a mechanism for CO 2(g) enhancement that includes formation of a CO2-superoxide intermediate, which serves as the oxidant of luminol to …
Isolation And Characterization Of Chromium- And Cobalt-Binding Peptides, Michael J. Jose
Isolation And Characterization Of Chromium- And Cobalt-Binding Peptides, Michael J. Jose
Honors Theses
Metal substitution has been proposed as an aid in the characterization of the structure of Low-Molecular-Weight Chromium-binding substance (LMWCr), which appears to be the biologically active chromium species. Preparations of bovine liver were diced and suspended in an isolation solution containing either a cobalt or a chromium salt. Peptide samples from these preparations were isolated by precipitation and centrifugation and purified by liquid chromatography. Several methods were used to analyze these samples, which may contain LMWCr or the cobalt-substituted form (LMWCo), in order to determine their purity, molecular weight (MW), and metal-to-peptide ratio. Methods used to determine MW included sodium …
Probing The Capabilities Of Copper Complexes With Nitrogen And Sulfur Containing Macrocyclic Ligands As Aziridination Catalysts, Jonathan Natkin
Probing The Capabilities Of Copper Complexes With Nitrogen And Sulfur Containing Macrocyclic Ligands As Aziridination Catalysts, Jonathan Natkin
Honors Theses
Aziridines are three-membered rings containing one nitrogen atom. They are useful as synthetic intermediates in many organic reactions. Much work has been devoted to synthesizing their analogs, cyclopropanes and epoxides, but little work has been done on the aziridination reaction. This study endeavored to probe the efficiencies of novel copper aziridination catalysts with N3 and S3 macrocyclic ligands compared to an NS2 analog for the reaction with the nitrene precursor (N-(paratosylsulfonyl) imino)phenyliodinane, PhINTs, and the olefin styrene. The nitrogen containing catalyst complex gave higher yields than the sulfur containing catalyst complex. Both ligands were found to decrease the yield of …
Synthetic Approach To Hexaoxa[6]Peristylanes. A Novel Ddq-Induced Oxidative Rearrangement, Douglas Arthur Otte
Synthetic Approach To Hexaoxa[6]Peristylanes. A Novel Ddq-Induced Oxidative Rearrangement, Douglas Arthur Otte
Honors Theses
The structural beauty and interesting bonding properties of polycyclic cage compounds have been a source of fascination to many chemists. In this work, progress toward the synthesis of large oxabowl systems, such as hexaoxa[6]peristylane and its derivative dipbenylhexaoxa[6)peristylane, is described. Thus, the adduct obtained from the cycloaddition of maleic anhydride and cyc!ooctatetraene is converted into key dicarbonyl intermediates. Subsequently, the ozonolysis of these intermediates is carried out in order to generate hexaoxa(6)peristylane as well as diphenylhexaoxa[6]peristylane. Molecular modeling studies, performed at the semi-empirical level, are also described.
Exploratory Chemistry In Route To Aromatic Natural Products, Nicholas P. Bizier
Exploratory Chemistry In Route To Aromatic Natural Products, Nicholas P. Bizier
Honors Theses
The focus of this research was the synthesis of two natural products, 1-methyl-s-(1,2,2-trimethy1cyclopentyl)-benzene (formally cuparene), and 3-(1,2dimethylcyclopenty1)-5-methylbenzene-l,2-diol (formally herbertene diol). Cuparene possesses anti-fungal and anti-arthritic properties. This molecule has been the target of a number of syntheses. Herbertene diol, a natural product itself, represents one retrosynthetic step back from mastigophorane; a compound isolated form the liverwort Mastigophora diaclolades. Mastigophorane has been shown to have neural network forming capabilities and has warranted complete synthetic efforts. Through the same chemistry involve in the formation of cuparene, we sought a route to herbertene diol in two steps. We report a successful route to …
Photochemical Degradation Of 2,4-D And Atrazine In Well-Defined Media, Asher D. Ghertner
Photochemical Degradation Of 2,4-D And Atrazine In Well-Defined Media, Asher D. Ghertner
Honors Theses
Atrazine and 2,4-D are common herbicides used for crop, lawn, and rangeland management. Photochemical degradation has been proposed as one safe and efficient remediation strategy for both 2,4-D and Atrazine. In the presence of iron(llI) and hydrogen peroxide these herbicides decay by both thermal and light induced oxidation. Past studies have focused primarily on sun light as an energy source. This work provides a mechanistic description of herbicide degradation incorporating intermediate degradation products produced in the dark and under well-defined light conditions.