4 resultados para 1st Total-synthesis
em Digital Commons at Florida International University
Resumo:
I. The target molecules are classified as 1-aryl 2-cyclopropyl substituted ethylene. In the ground state, these molecules have a number of conformers, which are in equilibrium through rotation about single bonds. Once excited, the conformers have fixed conformation and are no longer in equilibrium and can be distinguished by their UV-vis as well as fluorescence spectra. The synthetic strategy involves standard steps. Both 2-methylanthracene and 2-methylnaphthalene were brominated using N-bromosuccinimide to give the bromomethyl adduct, which then was reacted with triphenylphosphine to form the phosphonium salt. This was followed by the formation of the phosphorus ylide, which upon treatment with cyclopropanecarboxaldehyde gave the product.^ II. The degradation of three aliphatic haloethers: bis-(2-chloroethyl) ether, bis-(2-chloroisopropyl) ether, and bis-(2-chloroethoxy)methane and two aromatic haloethers: 4-chlorodiphenyl ether and 4-bromodiphenyl ether was studied. Product studies have been conducted on the titanium dioxide photocatalysis of these compounds including mass balance, monitoring and identifying intermediates to establish the reaction pathways to deduce a mechanism for their degradation. The extent of mineralization was determined from the measurement of halogen anion (Cl$\sp-$/Br$\sp-$) as well as total organic carbon. The relative rates of disappearance of the individual haloethers appear to be related to the hydrophobic character of the given compound. Reaction mechanisms involving hydroxyl radical are proposed to explain the observed results. ^
Resumo:
In broad terms — including a thief's use of existing credit card, bank, or other accounts — the number of identity fraud victims in the United States ranges 9-10 million per year, or roughly 4% of the US adult population. The average annual theft per stolen identity was estimated at $6,383 in 2006, up approximately 22% from $5,248 in 2003; an increase in estimated total theft from $53.2 billion in 2003 to $56.6 billion in 2006. About three million Americans each year fall victim to the worst kind of identity fraud: new account fraud. Names, Social Security numbers, dates of birth, and other data are acquired fraudulently from the issuing organization, or from the victim then these data are used to create fraudulent identity documents. In turn, these are presented to other organizations as evidence of identity, used to open new lines of credit, secure loans, “flip” property, or otherwise turn a profit in a victim's name. This is much more time consuming — and typically more costly — to repair than fraudulent use of existing accounts. ^ This research borrows from well-established theoretical backgrounds, in an effort to answer the question – what is it that makes identity documents credible? Most importantly, identification of the components of credibility draws upon personal construct psychology, the underpinning for the repertory grid technique, a form of structured interviewing that arrives at a description of the interviewee’s constructs on a given topic, such as credibility of identity documents. This represents substantial contribution to theory, being the first research to use the repertory grid technique to elicit from experts, their mental constructs used to evaluate credibility of different types of identity documents reviewed in the course of opening new accounts. The research identified twenty-one characteristics, different ones of which are present on different types of identity documents. Expert evaluations of these documents in different scenarios suggest that visual characteristics are most important for a physical document, while authenticated personal data are most important for a digital document. ^
Resumo:
Bacteria are known to release a large variety of small molecules known as autoinducers (AI) which effect quorum sensing (QS) initiation. The interruption of QS effects bacterial communication, growth and virulence. ^ Three novel classes of S-ribosylhomocysteine (SRH) analogues as potential inhibitors of S-ribosylhomocysteinase (LuxS enzyme) and AI-2 modulators of QS were developed. The synthesis of 2-deoxy-2-bromo-SRH analogues was attempted by coupling of the corresponding 2-bromo-2-deoxypentafuranosyl precursors with the homocysteinate anion. The displacement of the bromide from C2 rather than the expected substitution of the mesylate from C5 was observed. The synthesis of 4-C-alkyl/aryl-S-ribosylhomocysteine analogues involved the following steps: (i) conversion of the D-ribose to the ribitol-4-ulose; (ii) diastereoselective addition of various alkyl or aryl or vinyl Grignard reagents to 4-ketone intermediate; (iii) oxidation of the primary hydroxyl group at C1 followed by the intramolecular ring closure to the corresponding 4-C-alkyl/aryl-substituted ribono-1,4-lactones; (iv) displacement of the activated 5-hydroxyl group with the protected homocysteinate. Treatment of the 4-C-alkyl/aryl-substituted SRH analogues with lithium triethylborohydride effected reduction of the ribonolactone to the ribose (hemiacetal) and subsequent global deprotection with trifluoroacetic acid provided 4-C-alkyl/aryl-SRHs. ^ The 4-[thia]-SRH were prepared from the 1-deoxy-4-thioribose through the coupling of the &agr;-fluoro thioethers (thioribosyl fluorides) with homocysteinate anion. The 4-[thia]-SRH analogues showed concentration dependent effect on the growth on las (50% inhibitory effect at 200 µg/mL). The most active was 1-deoxy-4-[thia]-SRH analogue with sufur atom in the ring oxidized to sulfoxide decreasing las gene activity to approximately 35% without affecting rhl gene. Neither of the tested compounds had effect on bioluminescence nor on total growth of V. harveyi, but had however slight inhibition of the QS.^
Resumo:
In broad terms — including a thief's use of existing credit card, bank, or other accounts — the number of identity fraud victims in the United States ranges 9-10 million per year, or roughly 4% of the US adult population. The average annual theft per stolen identity was estimated at $6,383 in 2006, up approximately 22% from $5,248 in 2003; an increase in estimated total theft from $53.2 billion in 2003 to $56.6 billion in 2006. About three million Americans each year fall victim to the worst kind of identity fraud: new account fraud. Names, Social Security numbers, dates of birth, and other data are acquired fraudulently from the issuing organization, or from the victim then these data are used to create fraudulent identity documents. In turn, these are presented to other organizations as evidence of identity, used to open new lines of credit, secure loans, “flip” property, or otherwise turn a profit in a victim's name. This is much more time consuming — and typically more costly — to repair than fraudulent use of existing accounts. This research borrows from well-established theoretical backgrounds, in an effort to answer the question – what is it that makes identity documents credible? Most importantly, identification of the components of credibility draws upon personal construct psychology, the underpinning for the repertory grid technique, a form of structured interviewing that arrives at a description of the interviewee’s constructs on a given topic, such as credibility of identity documents. This represents substantial contribution to theory, being the first research to use the repertory grid technique to elicit from experts, their mental constructs used to evaluate credibility of different types of identity documents reviewed in the course of opening new accounts. The research identified twenty-one characteristics, different ones of which are present on different types of identity documents. Expert evaluations of these documents in different scenarios suggest that visual characteristics are most important for a physical document, while authenticated personal data are most important for a digital document.