Formation of Hexamethylenetetramine (HMT) from HCHO and NH3--Relevance to Prebiotic Chemistry and B3LYP Consideration.

Despite its importance in the prebiotic and biochemical fields, a complete theoretical study of the formation of hexamethylenetetramine (HMT) starting from its precursors ammonia and formaldehyde has not received due considerations in the literature with regard to the thermodynamic feasibility of many of the mechanistically proposed intermediates in its formation. Most of the studies in this area have been mostly concerned with the initial steps of the reaction between formaldehyde and ammonia, while poor attention is dedicated to successive steps. In this article, different results from published literature were critically considered and the most probable hypothesis regarding the mechanism of HMT formation is discussed on the basis of B3LYP calculations of free energies.

Reduction of formaldehyde concentrations in the air and cadaveric tissues by ammonium carbonate.

The reduction of formaldehyde by ammonium carbonate was examined in cadavers and in vitro. Formaldehyde concentrations in the air (10 cm above human cadavers) and in various cadaveric tissues were measured with or without perfusion of ammonium carbonate solution into formaldehyde-fixed cadavers. Air samples were monitored using Kitagawa gas detector tubes. For measurement of formaldehyde in tissues, muscles and organs were cut into small pieces and tissue fluids were separated out by centrifugation. These specimen fluids were diluted, supplemented with 3-methyl-2-benzothiazolinone hydrazone hydrochloride and quantified by spectrophotometry. In five cadavers without ammonium carbonate treatment, the formaldehyde concentrations in the air above the thorax and in various tissue fluids were 1.2-3.0 p.p.m. and 0.15-0.53%, respectively. Arterial reperfusion of saturated ammonium carbonate solution (1.0, 1.5 or 2.0 L) into five formaldehyde-fixed cadavers successfully reduced the formaldehyde levels, both in the air (0.5-1.0 p.p.m.) and in various tissue fluids (0.012-0.36%). In vitro experiments demonstrated that formaldehyde concentrations decreased, first rapidly and then gradually, with the addition of ammonium carbonate solution into fluids containing formaldehyde. It was confirmed that formaldehyde reacted with the ammonium carbonate and was thereby changed into harmless hexamethylenetetramine. The application of ammonium carbonate solution via intravascular perfusion and, if necessary, by infusion into the thoracic and peritoneal cavities, injection into muscles and spraying on denuded tissues can be anticipated to reduce formaldehyde to satisfactorily low levels in cadaveric tissues and, consequently, in the air, which may provide safe and odorless dissecting rooms.

Simulated cometary matter as a test for enantiomer separating chromatography for use on comet 46P/Wirtanen.

The Cometary Sampling and Composition Experiment on board of European Space Agency's cornerstone mission ROSETTA is designed to identify organic molecules in cometary matter in situ by a combined pyrolysis gas chromatographic and mass spectrometric technique. Its capillary columns coated with chiral stationary phases received considerable attention, because they are designed for separations of non-complex enantiomers to allow the determination of enantiomeric ratios of cometary chiral organic compounds and consequently to provide information about the origin of molecular parity violation in biomolecules. To get gas chromatographic access to organic compounds on the comet, where macromolecules and complex organic polymers of low volatility are expected to make up the main organic ingredients, the combination of two injection techniques will be applied. The pyrolysis technique performed by heating cometary samples stepwise to defined temperatures in specific ovens resulting in thermochemolysis reactions of polymers and a chemical derivatization technique, in which the reagent dimethylformamide dimethylacetal assists pyrolysis derivatization reactions in producing methyl esters of polar monomers. The combination of the reagent assisted pyrolysis gas chromatographic technique with enantiomer separating chromatography was tested with laboratory-produced simulated cometary matter.

[Antimicrobial action of ammonium salts of fused heterocycles containing ortho-nitrogen]. / Kondensuotu heterociklu amonio drusku su azoto atomu ortopadetyje bakteriostatinis poveikis.

By alkylation of hexamethylenetetramine with halogenated derivatives of ketones, ethers, esters or amides of acids, alkyl- and aralkyl halides the corresponding N-monoalkylated compounds of hexamethylenetetramine were obtained. The quaternization of pyridine nitrogen in 5,6-benzoquinoline, 8-hydroxyquinoline, quinoline, 1,10-phenanthroline molecules with alkyl- or aralkylhalides was carried out. The susceptibility of Gram-positive (Streptococcus agalactiae and Staphylococcus aureus) and Gram-negative (E. coli, Salmonella cholerae suis, Salmonella enteridis Gartneri) microorganisms to synthesized quaternary ammonium salts by disc difussion method has been detected. The bacteriostatic action of 0.5-1% solutions of all compounds was assessed in comparison with benzalkonium chloride. It was shown, that the most effectiveness against all strains is possessed by quaternary hexamethylenetetramine ammonium salts, and especially salts, containing 1-propynyl- or hydroxycarbamoylmethyl radicals. The action of these two compounds against Salmonella and Streptococcus was stronger than the action of benzalkonium chloride. Susceptibility of Pseudomonas aeruginosa to these compounds were detected. It was shown, that 1% solutions of chlorides of N-(1-propynyl) hexamethylenetetramonium and N-(hydroxycarbamoylmethyl) hexamethylenetetrammonium demonstrate the same bacteriostatic action against P. aeruginosa as well as benzalkonium chloride.