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The identification of the allylic nitrite and nitro derivatives of methyl linoleate and methyl linolenate by negative chemical ionization mass spectroscopy.

The autoxidation of polyunsaturated fatty acids is initiated both in vivo and in vitro by nitrogen dioxide. The mechanism of the initiation process is believed to involve both addition reactions and hydrogen atom abstraction reactions, with hydrogen abstraction predominating at low levels of nitrogen dioxide. Therefore low levels of nitrogen dioxide should react with polyunsaturated fatty acids to give allylic derivatives; in an anaerobic system these derivations should be allylic nitro and nitrite compounds. Using negative methane chemical ionization mass spectrometry and other analytical techniques, we have identified these allylic nitrite and nitro compounds from the reactions of low levels of nitrogen dioxide with methyl linoleate and methyl linolenate in the absence of oxygen.

Chromatography, High Pressure Liquid↗

ESR and electrochemical study of 5-nitroindazole derivatives with antiprotozoal activity.

The electrochemistry of 3-alkoxy- and 3-hydroxy-1-[omega-(dialkylamino)alkyl]-5-nitroindazole derivatives were characterized using cyclic voltammetry in DMSO. The nitro reduction process was studied and this was affected by the acid moieties present in these compounds. A nitro anion self-protonation process was observed. This phenomenon was studied by cyclic voltammetry in presence of increasing amount of NaOH. The reactivity of the nitro anion radical of these derivatives with glutathione was also studied by cyclic voltammetry. The oxidizing effect of glutathione is supported by the parallel decrease of the anodic peak current and increase of the cathodic peak in the cyclic voltammograms, corresponding to the wave of the nitro anion radical from uncharged species with the addition of glutathione. Nitro anion radicals obtained by electrolytic reduction of these derivatives were measured and analyzed in DMSO using electron spin resonance spectroscopy.

Anions↗

Assessment of sister chromatid exchange in spermatogonia and intestinal epithelium in Chinese hamsters.

The induction of sister chromatid exchange (SCE) has been proposed as a predictive test for the identification of mutagens/carcinogens. The in vivo application of this test was investigated by examining the chemical induction of SCE in spermatogonia, intestinal epithelium and bone marrow cells from Chinese hamsters. Sister chromatid differentiation (SCD) was achieved in differentiating spermatogonial cells of male Chinese hamsters by the abdominal subcutaneous (sc) implantation of an agar-coated bromodeoxyuridine (BrdUrd) tablet. A number of genotoxins were administered intraperitoneally (ip) and the induction of SCE in spermatogonia and bone marrow was compared. A significant increase in SCE frequency in spermatogonia occurred following treatment with mitomycin C (MMC), cyclophosphamide (CP), or N,N',N"-triethylenethiophosphoramide (ThioTEPA). Treatment with busulfan, hycanthone (HC), or triethylenemelamine (TEM) failed to induce SCE in vivo in spermatogonia, but these compounds did induce SCE in bone marrow. Differences in cell cycle kinetics were considered to be the major factor involved in the differential induction of SCE in spermatogonia and bone marrow. The induction of SCE in intestinal epithelium was investigated as a system for the identification of genotoxins that may result from the metabolism of xenobiotics by the gastrointestinal flora. Nitro-aromatic compounds were administered orally to Chinese hamsters. Nitro-aromatic compounds were chosen for this study since the mutagenic activity of these compounds is thought to result from their metabolism by bacterial nitroreductase. Metronidazole (MN) and 2-nitro-p-phenylenediamine (2NPPD) induced a dose-related increase in SCE formation in intestinal epithelium but not in bone marrow. Treatment with 3-nitro-o-phenylenediamine (3NOPD) or 4-nitro-o-phenylenediamine (4NOPD) did not induce the formation of SCE in either intestinal epithelium or bone marrow. These findings indicate that studies in axenic animals will be required to elucidate the contribution of the enteric flora to the metabolic activation of some genotoxins.

Animals↗

3-nitroadipate, a metabolic intermediate for mineralization of 2, 4-dinitrophenol by a new strain of a Rhodococcus species.

The bacterial strain RB1 has been isolated by enrichment cultivation with 2,4-dinitrophenol as the sole nitrogen, carbon, and energy source and characterized, on the basis of 16S rRNA gene sequence comparison, as a Rhodococcus species closely related to Rhodococcus opacus. Rhodococcus sp. strain RB1 degrades 2,4-dinitrophenol, releasing the two nitro groups from the compound as nitrite. The release of nitro groups from 2,4-dinitrophenol occurs in two steps. First, the 2-nitro group is removed as nitrite, with the production of an aliphatic nitro compound identified by 1H nuclear magnetic resonance and mass spectrometry as 3-nitroadipate. Then, this metabolic derivative is further metabolized, releasing its nitro group as nitrite. Full nitrite assimilation upon reduction to ammonia requires that an additional carbon source be supplied to the medium.

2,4-Dinitrophenol↗

Detection of nitroaromatic and cyclic nitramine compounds by cyclodextrin assisted capillary electrophoresis quadrupole ion trap mass spectrometry.

An Agilent 3DCE capillary electrophoresis system using sulfobutylether-beta-cyclodextrin (SB-beta-CD)-ammonium acetate separation buffer pH 6.9 was coupled to a Bruker Esquire 3000+ quadrupole ion trap mass detector via a commercially available electrospray ionization interface with acetonitrile sheath flow. The CE-MS system was applied in negative ionization mode for the resolution and detection of nitroaromatic and polar cyclic or caged nitramine energetic materials including TNT [2,4,6-trinitrotoluene, formula mass (FW) 227.13], TNB (1,3,5-trinitrobenzene, FW 213.12), RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine, FW 222.26) HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine, FW 296.16), and CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane, FW 438.19). The CE-MS system conformed to the high-performance liquid chromatography with ultraviolet absorbance detection (HPLC-UV) and HPLC-MS reference methods for the identification of energetic contaminants and their degradation products in soil and marine sediment samples.

Aza Compounds↗

Theoretical prediction of condensed phase heat of formation of nitramines, nitrate esters, nitroaliphatics and related energetic compounds.

An empirical approach is presented for calculation heats of formation of nitramines, nitrate esters, nitroaliphatics and related energetic compounds which contain at least one of the functional groups including N-NO(2), C-ONO(2) or nonaromatic C-NO(2). This approach is based on elemental composition and various structural and functional group parameters of C(a)H(b)N(c)O(d) energetic compounds. Heat of formation for 78 nitrocompounds including nitramines, nitrate esters, nitroaliphatics and the data obtained is compared with experimental data. Root mean square (rms) of deviation for 19 well known of mentioned energetic compounds are also compared with complex quantum mechanical computations which show 23.8 and 21.3 kJ/mol for new and quantum mechanical methods, respectively. Predicted condensed phase heats of formation for remainder 59 energetic molecules with complex molecular structures have a rms deviation from experiment of 42.3 kJ/mol.

Aniline Compounds↗

Approximate prediction of melting point of nitramines, nitrate esters, nitrate salts and nitroaliphatics energetic compounds.

A simple new procedure is introduced to predict melting point of selected class of energetic compounds containing nitramines, nitrate esters, nitrate salts and nitroaliphatics energetic compounds. The number of nitrogen and oxygen as well as the number of nitramine group and the contribution of some specific functional groups would be needed in the new method. Energetic compounds should contain at least one of the functional groups including N-NO(2), C-ONO(2) or nonaromatic C-NO(2). Calculated melting point for 33 nitramines, nitrate esters, nitrate salt and nitroaliphatics are compared with experimental data. Predicted melting points have average deviation of 5.4% for these energetic compounds.

Aniline Compounds↗

Palladium-catalyzed direct N-arylation of nucleosides, nucleotides, and oligonucleotides for efficient preparation of dG-N2 adducts with carcinogenic amino-/nitroarenes.

A method for direct palladium-catalyzed N-arylation reaction of nucleobases was developed for the convenient synthesis of DNA adducts with carcinogenic compounds. Using xantphos as the phosphine ligand and tetraethylammonium fluoride as the base in DMSO, several o-iodonitroarenes could be efficiently coupled with 2'-deoxyguanosine, 2'-deoxyadenosine, and 2'-deoxycytidine. The presence of a 3'-phosphate group in the deoxyribose moiety was found to be compatible with this N-arylation reaction; further, oligonucleotides could serve as substrates. The facile nitroreduction of the coupling compounds (12) yielded 2'-deoxyguanosin-N2-ylarylamine adducts, which are known to be biologically important. Compound 12 was easily converted to phosphoramidite derivatives, allowing the preparation of site-specific modified oligonucleotides with arylamine after the nitroreduction.

Carcinogens↗

First production-level bioremediation of explosives-contaminated soil in the United States.

Umatilla Army Depot Activity (UMDA) near Hermiston, Oregon was the location of the first production-level bioremediation of explosives-contaminated soil in the U.S. Soil from munitions washout lagoons contained high concentrations of TNT (2,4,6-Trinitrotoluene) and RDX (Hexahydro-1,3,5-trinitro-1,3,5- triazine) as well as HMX (Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine). In addition to these primary contaminants, laboratory tests were performed for Tetryl (Methyl-2,4,6-trinitrophenylnitramine), 4-Am-DNT (4-Amino-2,6-dinitrotoluene), 2-Am-DNT (2-Amino-4,6-dinitrotoluene), 2,4 DNT (2,4-Dinitrotoluene), 2,6 DNT (2,6-Dinitrotoluene), 1,3,5-TNB (1,3,5-Trinitrobenzene), 1,3,-DNB (1,3-Dinitrobenzene) and NB (Nitrobenzene) during the pilot-scale treatability tests. The clean-up goal established by the Record of Decision (ROD) was 30 mg/kg each for TNT and RDX. Degradation progress was monitored using immunoassay field screening Methods SW 846,4050 and 4051. Confirmational analysis consisted of EPA Method 8330. Treatment time on a 2,700 cubic yard batch (810 cubic yards of soil) was 10-12 days. A composting technique developed by the Army Environmental Center and implemented by Bioremediation Service, Inc., Portland, Oregon was used at the site. Agricultural waste products (or amendments including cow manure, chicken manure, potato waste, sawdust and alfalfa) were blended with the contaminated soil during treatment. Specialized soil turning equipment mixed the compost for optimum biological action and homogeneity. Homogeneity of the compost mix ensured rapid degradation of all contaminants. Physical and chemical properties were closely monitored to ensure that thermophilic bacteria played a dominant role in the degradation process. Nearly 5,000 cubic yards of soil have been successfully treated, and more than 70% of all analyses indicate non-detectable levels of both TNT and RDX. The U.S. Army Corps of Engineers estimates that over $2.6 million is being saved using bioremediation at Umatilla.

Azocines↗

Levels of synthetic musk compounds in municipal wastewater for potential estimation of biota exposure in receiving waters.

We analyzed water samples from the confluence of three municipal sewage treatment effluent streams, surface water, and whole carp (Cyprinus carpio) for synthetic musks for a period of 7-12 months. The lipid content of each fish was determined and compared with the concentration of musks in the whole fish tissue. Enhanced methods were used for water sampling and musk extraction. The data presented here provide insight as to the relationship between concentrations of synthetic musks in the municipal effluent and associated biota. This study confirmed the presence of polycyclic and nitro musk compounds in sewage effluent, Lake Mead water, and carp. The concentrations were found to be considerably lower than previous studies conducted in other countries. This study also provides data for polycyclic and nitro musk compounds, as well as some of the nitro musk metabolites in sewage treatment plant effluent, lake water, and carp.

Animals↗

Development of a polar-embedded stationary phase with unique properties.

This paper describes a new polar-embedded stationary phase that contains an internal sulfonamide functional group coupled with an ether linkage. The synthesis involves functionalization of spherical silica particles with ligands prepared in a multi-step synthesis. The resulting material contains 16.5% carbon, corresponding to a ligand coverage of 2.4mumol/m(2). Chromatographic evaluations indicates that the new stationary phase exhibits lower polarity than any other polar-embedded packings investigated, with additional features such as low silanol activity, excellent compatibility with 100% aqueous mobile phases, higher shape selectivity for polycyclic aromatic hydrocarbons, and strong affinity to nitro-containing compounds.

Chromatography, High Pressure Liquid↗