Reaction of meso-tetraphenylsecochlorin bisaldehyde with hydroxylamine results in the formation of the known meso-tetraphenyl-2-nitroporphyrin and the novel meso-tetraphenylimidazolophorphyrin. The products are the result of two diverging pathways of the presumed intermediate monooxime monoaldehyde that are unusual and surprising, but fully rationalized. The structures of both products were con...

This laboratory first became interested in hydroxyguanidine as a result of our studies on the mechanism of action of transamidination enzymes. We have found that transamidinases from Streptomyces griseus (2), mammalian pancreas (3) and kidney (4), and chicken and frog liver (5) can catalyze a transfer of the terminal formamidine group of arginine to hydroxylamine, with the formation of hydroxyg...

The formation of chiral heterocycles via cycloisomerization reactions of allene derivatives has gained relevance due to their associated efficiency and atom-economy. The only drawback that keeps these reactions away from being routine synthetic strategies is the control in the regioselectivity (most often 5-endo vs. 6-endo). In this work, we computationally explore the experimental chemistry re...

The contents of this report are not to be used for advertising, publication , or promotional purposes. Citation of trade names does not constitute an official endorsement or approval of the use of such commercial products. The findings of this report are not to be construed as an official Department of the Army position, unless so designated by other authorized documents. Figure 1. Reduction pa...

While Lewis acids andmetal amides are among themost frequently usedmetal species, they are believed to be incompatible when combined. Here we describe a Lewis acid/metal amide hybrid, which contains electron-withdrawing groups and basic and bulky nitrogen functional groups in the same metal complex, as a novel catalyst. We have synthesized In(N(SiMe3)2)2Cl (In(HMDS)2Cl) and In(HMDS)2OTf as Lewi...

A wide range of N,O-bis-acylated hydroxylamine derivatives with chloro or arenesulfonyl leaving groups, and a related set of N-hydroxy-N-acylsulfonamides, have been synthesized and evaluated for nitroxyl (HNO) production. Mechanistic studies have revealed that the observed aqueous chemistry is more complicated than originally anticipated, and have been used to develop a new series of efficient ...

The ability of intestinal microorganisms to N-oxidize nitrogenous compounds to nitrite or nitrate was evaluated both in vivo and in vitro. Nitrate balance studies with germ-free and conventional rats indicated that the host and not the microbial flora is responsible for excess urinary nitrate. In vitro studies showed that most intestinal microorganisms are not able to N-oxidize nitrogenous comp...

Electrocatalytic behavior of TEMPO derivative SAMs on gold has been studied in the presence of benzyl alcohol. The results demonstrate that interfacial activity of the SAMs can be enhanced by diluting the TEMPO moiety with an alkyl passive matrix. The absolute catalytic activity exhibits a maximum for an intermediate value of the surface coverage of catalytic centers. The most significant featu...

The newly developed DNA-biosensor is a very promising tool for the investigation and study of the action of drugs specifically designed to interact with DNA. In this work the electrochemical reduction of nitroimidazole drugs was studied in the presence of DNA immobilized onto the surface of a glassy carbon electrode. This enabled preconcentration of the drug onto the electrode surface, which wa...