RESUMO
"Heptil" (unsymmetrical dimethylhydrazine-UDMH) is extensively employed worldwide as a propellant for rocket engines. However, UDMH constantly loses its properties as a result of its continuous and uncontrolled absorption of moisture, which cannot be rectified. This situation threatens its long-term usability. UDMH is an exceedingly toxic compound (Hazard Class 1), which complicates its transportation and disposal. Incineration is currently the only method used for its disposal, but this process generates oxidation by-products that are even more toxic than the original UDMH. A more benign approach involves its immediate reaction with a formalin solution to form 1,1-dimethyl-2-methylene hydrazone (MDH), which is significantly less toxic by an order of magnitude. MDH can then be polymerized under acidic conditions, and the resulting product can be burned, yielding substantial amounts of nitrogen oxides. This review seeks to shift the focus of MDH from incineration towards its application in the synthesis of relatively non-toxic and readily available analogs of various pharmaceutical substances. We aim to bring the attention of the international chemical community to the distinctive properties of MDH, as well as other hydrazones (such as glyoxal, acrolein, crotonal, and meta-crolyl), wherein each structural fragment can initiate unique transformations that have potential applications in molecular design, pharmaceutical research, and medicinal chemistry.
Assuntos
Acroleína , Glioxal , Dimetilidrazinas/química , Formaldeído , Técnicas de Química SintéticaRESUMO
When released to the environment, the rocket fuel unsymmetrical dimethylhydrazine (UDMH) undergoes oxidative transformations, resulting in the formation of an extremely large number of nitrogen-containing transformation products, including isomeric compounds which are difficult to discriminate by common chromatography techniques. In the present work, supercritical fluid chromatography-tandem mass spectrometry (SFC-MS/MS) was proposed for resolving the problem of fast separation and simultaneous quantification of 1-formyl-2,2-dimethylhydrazine (FADMH) as one of the major UDMH transformation products, and its isomers-1,1-dimethylurea (UDMU) and 1,2-dimethylurea (SDMU). 2-Ethylpyridine stationary phase provided baseline separation of analytes in 1.5 min without the distortion of the chromatographic peaks. Optimization of SFC separation and MS/MS detection conditions allowed for the development of rapid, sensitive, and "green" method for the simultaneous determination of FADMH, UDMU, and SDMU in environmental samples with LOQs of 1-10 µg L-1 and linear range covering three orders of magnitude. The method was validated and successfully tested on the real extracts of peaty and sandy soils polluted with rocket fuel and UDMH oxidation products. It was shown that both UDMU and SDMU are formed in noticeable amounts during UDMH oxidation. Despite relatively low toxicity, UDMU can be considered one of the major UDMH transformation products and a potential marker of soil pollution with toxic rocket fuel.
Assuntos
Cromatografia com Fluido Supercrítico , Cromatografia com Fluido Supercrítico/métodos , Dimetilidrazinas/análise , Dimetilidrazinas/química , Solo/química , Espectrometria de Massas em Tandem/métodosRESUMO
1,1-Dimethylhydrazine (UDMH) and its by-products were considered carcinogenic toxins and represent a serious health hazard to the population once present in water under natural conditions without treatment. The conventional degradation method suffers from incomplete removal of intermediate products (especially N-nitrosodimethylamine (NDMA)), the powdery catalysis being difficult to recover and results in high energy consumption. In this study, a series of Bi2O3/TiO2/Al2O3 (BTA) photocatalysts have been successfully synthesized by a simple dry mixing method with powder material followed by their immobilization. It was evaluated by the photocatalytic degradation of UDMH present in wastewater, which can be recovered by rapid filtration and utilizes only solar energy. The catalyst exhibited markedly enhanced photocatalytic activity for the degradation of UDMH wastewater compared with conventional TiO2/Al2O3 (TA) catalysts under UV, visible and solar irradiation. Besides, the intermediate NDMA was gradually completely degraded. The photocatalysts were extensively characterized using scanning electron microscopy, energy dispersive spectrometry, specific surface area (BET), X-ray diffraction, X-ray photoelectron spectroscopy, UV-visible diffuse reflectance spectroscopy and photo-electrochemical I-t curves evaluation. The results revealed that all the BTA composites exhibited high stability and stronger absorbance in visible light. In addition, the BTA exhibited a reversible photochromic property that can effectively expand the range of light absorption and enhance the photocatalytic activity. The reversible photochromic properties of BTA explained in the proposed mechanism model are expected to be useful for detecting and sensing UDMH or other organic contaminants.
Assuntos
Óxido de Alumínio/química , Bismuto/química , Dimetilidrazinas/isolamento & purificação , Titânio/química , Poluentes Químicos da Água/isolamento & purificação , Catálise , Dimetilidrazinas/química , Dimetilnitrosamina/química , Dimetilnitrosamina/isolamento & purificação , Fotólise , Propriedades de Superfície , Poluentes Químicos da Água/química , Purificação da Água/métodosRESUMO
Existing methods for cleanup of wastewaters and soils polluted with the extremely toxic rocket fuel unsymmetrical dimethylhydrazine (UDMH) are mainly based on the treatment with various oxidative reagents. Until now, the assessment of their effectiveness was based on the residual content of UDMH and did not take into account the possibility of the formation of a large number of potentially dangerous nitrogen-containing transformation products (TPs). In this study, using the recently developed approach based on high-resolution Orbitrap mass spectrometry, the comprehensive characterization of UDMH TPs formed by the action of air oxygen and different oxidants (Fenton's reagent, KMnO4, HOCl, H2O2 in the presence of Cu2+ and [Fe (EDTA)]- catalysts) typically used to detoxify spill sites was performed. The range of the identified molecular formulas of TPs comprised 303 compounds of various classes. Among them, there is a number of major products not previously described in the literature. It was established that none of the investigated oxidative reagents ensures complete conversion of rocket fuel to safe compounds. The hydrogen peroxide based reagents, particularly H2O2 + Na [Fe (EDTA)] system currently used in Kazakhstan, give the greatest number of TPs, for many of which a toxicity was not characterized so far. The majority of the compounds found in model solutions was detected in extracts of soil from the crash site of the Proton carrier rocket, which was subjected to the on-site reagent treatment. During successive treatments, along with the decrease in the number of detectable UDMH TPs, their ratios change in favor of amines.
Assuntos
Dimetilidrazinas/química , Espectrometria de Massas/métodos , Oxidantes/química , Solo/química , Água/química , Dimetilidrazinas/análiseRESUMO
The precise cellular function of peroxynitrite (ONOO-) in biosystems remains elusive, primarily owing to being short of ultrasensitive techniques for monitoring its intracellular distribution. In this work, a novel rhodamine B cyclic 1,2-dimethylhydrazine fluorescent chemodosimeter RDMH-PN for highly specific and ultrasensitive monitoring of basal ONOO- in biosystems was rationally designed. The fluorescence titration experiments demonstrated that RDMH-PN was capable of quantitatively detecting 0-100 nM ONOO- (limit of detection = 0.68 nM). In addition, RDMH-PN has outstanding performances of ultrafast measurement, naked-eye detection, and preeminent selectivity toward ONOO- to accurately detect intracellular basal ONOO-. Finally, it has been confirmed that RDMH-PN could not only map the intracellular basal ONOO- level by inhibition tests but also trace the fluctuations of endogenous and exogenous ONOO- levels with diverse stimulations in live cells and zebrafish.
Assuntos
Dimetilidrazinas/química , Corantes Fluorescentes/química , Ácido Peroxinitroso/análise , Espectrometria de Fluorescência/métodos , Peixe-Zebra/metabolismo , Animais , Macrófagos/química , Macrófagos/citologia , Macrófagos/metabolismo , Camundongos , Ácido Peroxinitroso/biossíntese , Células RAW 264.7 , Rodaminas/química , Espectrometria de Fluorescência/instrumentaçãoRESUMO
Unsymmetrical dimethylhydrazine (UDMH) is a rocket propellant for carrier rockets and missiles. UDMH is environmentally hostile compound, which easily forms a variety of toxic products of oxidative transformation. The liquidation of unused UDMH from retired launch sites is performed by the complete burning of UDMH-containing wastes. Due cyclicity of the burning equipment the UDMH-containing wastes are subject of prolonged storage in contact with atmospheric oxygen and thus contains a complicated mixture of UDMH degradation products. High performance liquid chromatography (HPLC), high resolution mass spectrometry (HRMS) and NMR were used for the isolation on characterization of new highly polar and potentially toxic UDMH transformation products in the mixture. Two series of unreported isomers with high ionization cross section in electrospray ionization were isolated by repeated preparative HPLC. The structures of the isomers were established by tandem HRMS and NMR. The cytotoxicity of the isolated compounds has been preliminarily studied and found to be similar to UDMH or higher.
Assuntos
Dimetilidrazinas/química , Triazóis/química , Cromatografia Líquida de Alta Pressão , Dimetilidrazinas/toxicidade , Isomerismo , Espectrometria de Massas , Oxirredução , Oxigênio/químicaRESUMO
1,1-Dimethylhydrazine is used as a fuel for carrier rockets in the majority of countries implementing space exploration programs. Being highly reactive, 1,1-dimethylhydrazine easily undergoes oxidative transformation with the formation of a number of toxic, mutagenic, and teratogenic compounds. The use of high-resolution mass spectrometry for the study of the reaction of 1,1-dimethylhydrazine oxidation with hydrogen peroxide in aqueous solution allowed us to find hundreds of nitrogen-containing products of the CHN and CHNO classes, formed via radical processes. The vast majority of the compounds have not been previously considered as possible products of the transformation of rocket fuel. We have shown that the oxidation of 1,1-dimethylhydrazine proceeds in two stages, with the formation of a great number of complex unstable intermediates that contain up to ten nitrogen atoms. These intermediates are subsequently converted into final reaction products with a concomitant decrease in the average molecular weight. The intermediates and final products of the oxidative transformation of 1,1-dimethylhydrazine were characterised on the basis of their elemental composition using van Krevelen diagrams and possible compounds corresponding to the most intense peaks in the mass spectra were proposed. The data obtained are indicative of the presence of the following classes of heterocyclic nitrogen-containing compounds among the oxidation products: imines, piperidines, pyrrolidines, dihydropyrazoles, dihydroimidazoles, triazoles, aminotriazines, and tetrazines. The results obtained open up possibilities for the targeted search and identification of new toxic products of the degradation of rocket fuel and, as a result, a more adequate assessment of the ecological consequences of space-rocket activity.
Assuntos
Dimetilidrazinas/análise , Dimetilidrazinas/química , Peróxido de Hidrogênio/química , Espectrometria de Massas/métodos , Oxidantes/química , OxirreduçãoRESUMO
The role of Cu(II) in the reduction of N-nitrosodimethylamine (NDMA) with zero-valent metals was investigated by determining the effects of Cu(II) on the removal, kinetics, products, and mechanism. NDMA removal was enhanced, and all reactions followed a pseudo-first-order kinetic model except for the Fe and Fe/0.1 mM Cu(II) systems. The iron mass-normalized pseudo-first-order rate constants (kMFe) increased with the Cu(II) concentration. The zinc mass-normalized pseudo-first-order rate constants (kMZn) were identical to those with the Cu(II) concentrations from 0.1 mM to 1.0 mM and were higher with 2.0 mM Cu(II). The types of products detected were unchanged. Some unknown products were also found. NDMA was reduced to 1,1-dimethylhydrazine (unsymmetrical dimethylhydrazine, UDMH). Then, UDMH was reduced into dimethylamine (DMA) by the Fe/Cu(II) and Zn/Cu(II) systems. Catalytic hydrogenation was proposed as the reduction mechanism. Several copper species, such as Cu(OH)2 in the Fe/Cu(II) system and Cu2O and Cu(OH)2 in the Zn/Cu(II) system enhanced NDMA reduction. Differences between the Fe/Cu(II) and Zn/Cu(II) systems were caused by the reduction potentials and surface conditions of the different metals and the copper species in the various systems.
Assuntos
Cobre/química , Dimetilnitrosamina/química , Ferro/química , Poluentes Químicos da Água/química , Zinco/química , Dimetilaminas/química , Dimetilidrazinas/química , Cinética , Oxirredução , Purificação da ÁguaRESUMO
The vanadium(V) dimethylhydrazido compounds were structurally characterized to elucidate the effect of the alkoxide ligands in the coordination environment of vanadium(V) hydrazido center. The single-crystal X-ray structure determination of the vanadium(V) dimethylhydrazido compound with isopropoxide ligands revealed a dimeric structure with the V(1)-N(1) distance of 1.680(5)Å, in which each vanadium atom is coordinated in a distorted trigonal-bipyramidal geometry (τ5=0.81) with the hydrazido and bridging isopropoxide ligands in the apical positions. On the contrary, nearly tetrahedral arrangement around the vanadium metal center (τ4=0.06) with the V(1)-N(1) distance of 1.660(2)Å was observed in the vanadium(V) dimethylhydrazido compound with tert-butoxide ligands. The introduction of the 2,2',2â³-nitrilotriethoxide ligand led to a pseudo-trigonal-bipyramidal geometry (τ5=0.92) at the vanadium center with the V(1)-N(1) distance of 1.691(5)Å, wherein vanadium atom is pulled out of the plane formed by the nitrilotriethoxide oxygen atoms in the direction of the hydrazido nitrogen. The coordination from the apical ligand in the vanadium(V) dimethylhydrazido compound was found to result in the longer V(1)-N(1) distance.
Assuntos
Complexos de Coordenação/química , Complexos de Coordenação/síntese química , Dimetilidrazinas/química , Vanádio/química , Cristalografia por Raios X , Estrutura MolecularRESUMO
There was performed an assessment of genotoxic effects of rocket fuel component--unsymmetrical dimethylhydrazine (UDMH, heptyl)--on forming germ cells of male mice. Immunocytochemically there was studied the structure of meiotic nuclei at different times after the intraperitoneal administration of UDMH to male mice. There were revealed following types of disturbances of the structure of synaptonemal complexes (SCs) of meiotic chromosomes: single and multiple fragments of SCs associations of autosomes with a sex bivalent, atypical structure of the SCs with a frequency higher than the reference level. In addition, there were found the premature desinapsis of sex bivalents, the disorder offormation of the genital corpuscle and ring SCs. Established disorders in SCs of spermatocytes, analyzed at 38th day after the 10-days intoxication of animal by the component of rocket fuel, attest to the risk of permanent persistence of chromosomal abnormalities occurring in the pool of stem cells.
Assuntos
Aberrações Cromossômicas/induzido quimicamente , Dimetilidrazinas , Gasolina/toxicidade , Espermatócitos , Complexo Sinaptonêmico , Animais , Antiespermatogênicos/administração & dosagem , Antiespermatogênicos/química , Antiespermatogênicos/toxicidade , Dimetilidrazinas/administração & dosagem , Dimetilidrazinas/química , Dimetilidrazinas/toxicidade , Imuno-Histoquímica/métodos , Infecções Intra-Abdominais , Masculino , Camundongos , Modelos Animais , Maturação do Esperma/efeitos dos fármacos , Espermatócitos/efeitos dos fármacos , Espermatócitos/fisiologia , Complexo Sinaptonêmico/efeitos dos fármacos , Complexo Sinaptonêmico/genéticaRESUMO
Continuous generation of hydrogen peroxide catalyzed by low concentrations of 1,1-dimethylhydrazine (heptyl)--a rocket fuel component--in air saturated water was shown by the method of enhanced chemiluminescence in the system of luminol-p-iodophenol-peroxidase. The concentration dependence and the influence of heat and light on the formation of hydrogen peroxide in the water under the influence of dimethylhydrazine at concentrations considerably lower than maximum allowable concentrations were studied, and the physical-chemical mechanism of this process was considered. It is supposed that dimethylhydrazine at ultra-low concentrations is associated with air nanobubbles and represents a long-lived complex performing catalysis of hydrogen peroxide formation under the influence of heat and light. We put forward the new concept of.toxicity of dimethylhydrazine at very low concentrations due to violation of homeostasis of reactive oxygen species formation in aqueous solutions entering the body of humans and animals.
Assuntos
Poluentes Ocupacionais do Ar/química , Dimetilidrazinas/química , Peróxido de Hidrogênio/síntese química , Oxigênio/química , Água/química , Animais , Catálise , Temperatura Alta , Humanos , Peróxido de Hidrogênio/análise , Iodobenzenos/química , Luz , Medições Luminescentes , Luminol/química , Peroxidase/química , Espécies Reativas de Oxigênio/químicaRESUMO
N-Nitrosodimethylamine (NDMA) is an emerging disinfection byproduct, and we show that use of chlorine dioxide (ClO2) has the potential to increase NDMA formation in waters containing precursors with hydrazine moieties. NDMA formation was measured after oxidation of 13 amines by monochloramine and ClO2 and pretreatment with ClO2 followed by postmonochloramination. Daminozide, a plant growth regulator, was found to yield 5.01 ± 0.96% NDMA upon reaction with ClO2, although no NDMA was recorded during chloramination. The reaction rate was estimated to be â¼0.0085 s(-1), and on the basis of our identification by mass spectrometry of the intermediates, the reaction likely proceeds via the hydrolytic release of unsymmetrical dimethylhydrazine (UDMH), with the hydrazine structure a key intermediate in NDMA formation. The presence of UDMH was confirmed by gas chromatography-mass spectrometry analysis. For 10 of the 13 compounds, ClO2 preoxidation reduced NDMA yields compared with monochloramination alone, which is explained by our measured release of dimethylamine. This work shows potential preoxidation strategies to control NDMA formation may not impact all organic precursors uniformly, so differences might be source specific depending upon the occurrence of different precursors in source waters. For example, daminozide is a plant regulator, so drinking water that is heavily influenced by upstream agricultural runoff could be at risk.
Assuntos
Compostos Clorados/química , Dimetilnitrosamina/química , Óxidos/química , Purificação da Água/métodos , Aminas/química , Cloraminas/química , Dimetilaminas/análise , Dimetilaminas/química , Dimetilidrazinas/análise , Dimetilidrazinas/química , Desinfecção/métodos , Água Potável/química , Cromatografia Gasosa-Espectrometria de Massas , OxirreduçãoRESUMO
(-)-Hinokinin (1) is a dibenzylbutyrolactone lignan obtained by the partial synthesis of (-)-cubebin. This study reports the antigenotoxic and anticarcinogenic potential of 1 by the comet and aberrant crypt focus assays in the peripheral blood and colon of 4-5-week-old Wistar rats, respectively. The rats were exposed to 1,2-dimethylhydrazine (40 mg/kg) and were treated by gavage with doses of 10, 20, and 40 mg/kg of 1. The results showed that the dose of 40 mg/kg was neither genotoxic nor carcinogenic. In the comet assay, all 1 doses displayed antigenotoxic effects. In addition, this compound (20 and 40 mg/kg) exhibited an anticarcinogenic effect in the aberrant crypt focus assay.
Assuntos
1,2-Dimetilidrazina/farmacologia , 4-Butirolactona/análogos & derivados , Dioxóis/farmacologia , Lignanas/farmacologia , 4-Butirolactona/química , 4-Butirolactona/farmacologia , Animais , Anticarcinógenos/farmacologia , Benzodioxóis , Carcinógenos/farmacologia , Colo/efeitos dos fármacos , Ensaio Cometa , Dano ao DNA/efeitos dos fármacos , Dimetilidrazinas/química , Dioxóis/química , Lignanas/química , Masculino , Estrutura Molecular , Piper/química , Ratos , Ratos Wistar , EstereoisomerismoRESUMO
The reaction of the oxidovanadium(V) complexes with N,N-dimethylhydrazine was demonstrated to afford the corresponding vanadium(V) dimethylhydrazido complexes. The substituent at the 3-position of the tris(2-hydroxyphenyl)amine ligand was found to influence the electronic environment of the vanadium center. The crystal structure of the non-substituted vanadium(V) dimethylhydrazido complex exhibited a distorted trigonal bipyramidal geometry with phenolate oxygen atoms in equatorial positions and the near-linear V(1)-N(2)-N(3) angle. The vanadium(V) diphenylhydrazido complexes could be obtained by the reaction of the oxidovanadium(V) complexes with N,N-diphenylhydrazine. A distorted trigonal bipyramidal geometry with phenolate oxygen atoms in equatorial positions was also observed in the crystal structure of the non-substituted vanadium(V) diphenylhydrazido complex.
Assuntos
Aminas/química , Dimetilidrazinas/química , Compostos Organometálicos/química , Vanádio/química , Cristalografia por Raios X , Ligantes , Modelos Moleculares , Estrutura Molecular , Compostos Organometálicos/síntese químicaRESUMO
A precise understanding of the mechanism-based inactivation of cytochrome P450 enzymes (P450s) at the quantum mechanical level should allow more reliable predictions of drug-drug interactions than those currently available. Hydrazines are among the molecules that act as mechanism-based inactivators to terminate the function of P450s, which are essential heme enzymes responsible for drug metabolism in the human body. Despite its importance, the mechanism explaining how a metabolic intermediate (MI) is formed from hydrazine is not fully understood. We used density functional theory (DFT) calculations to compare four possible mechanisms underlying the reaction between 1,1-dimethylhydrazine (or unsymmetrical dimethylhydrazine, UDMH) and the reactive compound I (Cpdâ I) intermediate of P450. Our DFT calculations provided a clear view on how an aminonitrene-type MI is formed from UDMH. In the most favorable pathway, hydrogen is spontaneously abstracted from the N2 atom of UDMH by Cpdâ I, followed by a second hydrogen abstraction from the N2 atom by Cpdâ II. Nitrogen oxidation of nitrogen atoms and hydrogen abstraction from the C-H bond of the methyl group were found to be less favorable than the hydrogen abstraction from the N-H bond. We also found that the reaction of protonated UDMH with Cpdâ I is rather sluggish. The aminonitrene-type MI binds to the ferric heme more strongly than a water molecule. This is consistent with the notion that the catalytic cycle of P450 is impeded when such an MI is produced through the P450-catalyzed reaction.
Assuntos
Sistema Enzimático do Citocromo P-450/química , Sistema Enzimático do Citocromo P-450/metabolismo , Dimetilidrazinas/química , Heme/química , Heme/metabolismo , Nitrogênio/química , Catálise , Hidrogênio , Ligação de Hidrogênio , Oxirredução , Teoria Quântica , Água/químicaRESUMO
In our research, three fall places of first stages of Proton rockets have been studied for the presence and distribution of transformation products of 1,1-dimethylhydrazine (1,1-DMH). Results of identification of transformation products of 1,1-DMH in real soil samples polluted due to rocket fuel spills allowed to detect 18 earlier unknown metabolites of 1,1-DMH being formed only under field conditions. According to the results of quantitative analyses, maximum concentrations of 1-methyl-1H-1,2,4-triazole made up 57.3, 44.9 and 13.3 mg kg(-1), of 1-ethyl-1H-1,2,4-triazole - 5.45, 3.66 and 0.66 mg kg(-1), of 1,3-dimethyl-1H-1,2,4-triazole - 24.0, 17.8 and 4.9 mg kg(-1) in fall places 1, 2 and 3, respectively. 4-Methyl-4H-1,2,4-triazole was detected only in fall places 2 and 3 where its maximum concentrations made up 4.2 and 0.66 mg kg(-1), respectively. The pollution of soils with transformation products of 1,1-DMH was only detected in epicenters of fall places having a diameter of 8 to10 m where rocket boosters landed. The results of a detailed study of distribution of 1,1-DMH transformation products along the soil profile indicate that transformation products can migrate down to the depth of 120 cm, The highest concentrations of 1,1-DMH transformation products were detected, as a rule, at the depth 20 to 60 cm. However, this index can vary depending on the compound, humidity and physical properties of soil, landscape features and other conditions. In the surface layer, as a rule, only semi-volatile products of transformation were detected which was caused by fast evaporation and biodegradation of volatile metabolites.
Assuntos
Dimetilidrazinas/análise , Poluentes do Solo/análise , Dimetilidrazinas/química , Monitoramento Ambiental , Cromatografia Gasosa-Espectrometria de Massas , Cazaquistão , Poluentes do Solo/química , Microextração em Fase SólidaRESUMO
A Cu(I) complex, LCu(CH(3)CN), was prepared and characterized, where L(-) is a sterically unencumbered ß-diketiminate ligand, the deprotonated version of 4-(2,2-dimethylhydrazino)dimethylhydrazone-3-penten-2-one (LH). Analysis of FTIR spectra of the products of the reaction of LCu(CH(3)CN) with CO indicate that L(-) is strongly electron donating, and support an equilibrium in solution between monomeric and dimeric forms with terminal and bridging CO ligands, respectively. Low temperature oxygenation of LCu(CH(3)CN) generated a bis(µ-oxo)tricopper complex with a S = 1 [Cu(3)O(2)](3+) core that was identified on the basis of UV-vis (λ(max) (ε, M(-1) cm(-1) per Cu) = 328 (10700), 420 (1500), 590 (835) nm) and X-band electron paramagnetic resonance (EPR) spectroscopy (Δm(s) = 2 transition at 1500 G), electrospray ionization (ESI) mass spectrometry, and spectrophotometric titration (0.35(2) equiv of O(2) per copper atom), magnetic susceptibility (µ(eff) = 2.8(1) BM), and H(2)O(2) detection experiments (no H(2)O(2) evolved upon acidification). Unlike other reported variants supported by neutral N-donor ligands, L(3)Cu(3)O(2) is not reduced by ferrocene, does not abstract H-atoms from phenols or 1,2-dihydroanthracene, oxidizes PPh(3) to Ph(3)PâO, and generates carbonate species upon exposure to CO(2). This unique reactivity for a [Cu(3)O(2)](3+) complex may be traced to the anionic charge and strong electron donating characteristics of L(-).
Assuntos
Cobre/química , Dimetilidrazinas/química , Temperatura Baixa , Espectroscopia de Ressonância de Spin Eletrônica , Ligantes , Espectrometria de Massas por Ionização por ElectrosprayRESUMO
The often observed scarcity of physical-chemical and well as toxicological data hampers the assessment of potentially hazardous chemicals released to the environment. In such cases Quantitative Structure-Activity Relationships/Quantitative Structure-Property Relationships (QSAR/QSPR) constitute an obvious alternative for rapidly, effectively and inexpensively generatng missing experimental values. However, typically further treatment of the data appears necessary, e.g., to elucidate the possible relations between the single compounds as well as implications and associations between the various parameters used for the combined characterization of the compounds under investigation. In the present paper the application of QSAR/QSPR in combination with Partial Order Ranking (POR) methodologies will be reviewed and new aspects using Formal Concept Analysis (FCA) will be introduced. Where POR constitutes an attractive method for, e.g., prioritizing a series of chemical substances based on a simultaneous inclusion of a range of parameters, FCA gives important information on the implications associations between the parameters. The combined approach thus constitutes an attractive method to a preliminary assessment of the impact on environmental and human health by primary pollutants or possibly by a primary pollutant well as a possible suite of transformation subsequent products that may be both persistent in and bioaccumulating and toxic. The present review focus on the environmental - and human health impact by residuals of the rocket fuel 1,1-dimethylhydrazine (heptyl) and its transformation products as an illustrative example.
Assuntos
Relação Quantitativa Estrutura-Atividade , Animais , Biodegradação Ambiental , Daphnia/efeitos dos fármacos , Dimetilidrazinas/química , Dimetilidrazinas/farmacocinética , Dimetilidrazinas/toxicidade , Ecotoxicologia , Poluentes Ambientais/química , Poluentes Ambientais/farmacocinética , Poluentes Ambientais/toxicidade , Meia-Vida , Humanos , Medição de Risco , Solo/química , Água/químicaRESUMO
Very few animal studies have used 1,1-dimethyl hydrazine (unsymmetrical dimethyl hydrazine - UDMH) as a carcinogen. This study was designed to investigate the carcinogenicity of UDMH in the gastrointestinal tract in a rat model. We wanted to observe if there were any changes in tissue zinc levels and tissue copper zinc superoxide dismutase (CuZnSOD) enzyme activity during the carcinogenic process, and to compare these values with those of control rats in the medium- and long-term. Six-week-old Wistar rats were given a subcutaneous injection of UDMH (30mg/kg body wt) twice a week for 20 weeks, and sacrificed after 5 and 9 months of treatment. Tissue zinc levels showed a significant decrease (p<0.05) in the large intestine at 9 months, whereas in the stomach and small intestine there were no significant changes at 5 and 9 months. Tissue CuZnSOD enzyme activity in the stomach, small intestine and large intestine showed no significant decrease at 5 and 9 months as compared to controls. Histologically, the large intestine was normal at 9 months. This study suggests that UDMH administered at the above dosage was not carcinogenic in this model.