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Acta Crystallographica. Section E,... Jun 2011In the title compound, C(16)H(14)Br(2)N(2)O(2), the dihedral angle between the mean planes of the two benzene rings is 33.4 (2)°. The hydrazine group is twisted...
In the title compound, C(16)H(14)Br(2)N(2)O(2), the dihedral angle between the mean planes of the two benzene rings is 33.4 (2)°. The hydrazine group is twisted slightly, with C-N-N-C and C-C-N-N torsion angles of 167.5 (4) and 177.2 (4)/174.2 (4)°, respectively.
PubMed: 21754769
DOI: 10.1107/S1600536811016904 -
Chemical Reviews Jun 2020The metallobiochemistry underlying the formation of the inorganic N-N-bond-containing molecules nitrous oxide (NO), dinitrogen (N), and hydrazine (NH) is essential to... (Review)
Review
The metallobiochemistry underlying the formation of the inorganic N-N-bond-containing molecules nitrous oxide (NO), dinitrogen (N), and hydrazine (NH) is essential to the lifestyles of diverse organisms. Similar reactions hold promise as means to use N-based fuels as alternative carbon-free energy sources. This review discusses research efforts to understand the mechanisms underlying biological N-N bond formation in primary metabolism and how the associated reactions are tied to energy transduction and organismal survival. These efforts comprise studies of both natural and engineered metalloenzymes as well as synthetic model complexes.
Topics: Hydrazines; Metalloproteins; Models, Molecular; Nitrogen; Nitrous Oxide
PubMed: 32108471
DOI: 10.1021/acs.chemrev.9b00629 -
ACS Central Science Jul 2022We report a postsynthetic strategy and its implementation to make covalent organic frameworks (COFs) with irreversible hydrazide linkages. This involved the synthesis of...
We report a postsynthetic strategy and its implementation to make covalent organic frameworks (COFs) with irreversible hydrazide linkages. This involved the synthesis of three 2D and 3D hydrazine-linked frameworks and their partial oxidation. The linkage synthesis and functional group transformation-hydrazine and hydrazide-were evidenced by N multi-CP-MAS NMR. In addition, the isothermal water uptake profiles of these frameworks were studied, leading to the discovery of one hydrazine-hydrazide-linked COF suitable for water harvesting from air in arid conditions. This COF displayed characteristic S-shaped water sorption profiles, a steep pore-filling step below 18% relative humidity at 25 °C, and a total uptake capacity of 0.45 g g. We found that even small changes made on the molecular level can lead to major differences in the water isotherm profiles, therefore pointing to the utility of water sorption analysis as a complementary analytical tool to study linkage transformations.
PubMed: 35912353
DOI: 10.1021/acscentsci.2c00398 -
Environmental and Molecular Mutagenesis Aug 2022Hydrazine is a rodent carcinogen and is classified as a probable human carcinogen by IARC. Though hydrazine is positive in both in vitro and in vivo DNA strand break...
Hydrazine is a rodent carcinogen and is classified as a probable human carcinogen by IARC. Though hydrazine is positive in both in vitro and in vivo DNA strand break (comet) assays, hydrazine was reported to be negative in an in vitro mutation Muta Mouse lung epithelial cell (FE1) test, as well as in a regulatory-compliant, in vivo Big Blue mouse mutation test. In this article, mechanistic studies explored the cellular response to hydrazine. When tested in a regulatory-compliant mouse lymphoma assay, hydrazine yielded unusual, weakly positive results. This prompted an investigation into the transcriptional response to hydrazine in FE1 cells via RNA sequencing. Amongst the changes identified was a dose-dependent increase in G2/M DNA damage checkpoint activation associated genes. Flow cytometric experiments in FE1 cells revealed that hydrazine exposure led to S-phase cell cycle arrest. Clonogenic assays in a variety of cell lines harboring key DNA repair protein deficiencies indicated that hydrazine could sensitize cells lacking homology dependent repair proteins (Brca2 and Fancg). Lastly, hprt assays with hydrazine were conducted to determine whether a lack of DNA repair could lead to mutagenicity. However, no robust, dose-dependent induction of mutations was noted. The transcriptional and cell cycle response to hydrazine, coupled with functional investigations of DNA repair-deficient cell lines support the inconsistencies noted in the genetic toxicology regulatory battery. In summary, while hydrazine may be genotoxic, transcriptional and functional processes involved in cell cycle regulation and DNA repair appear to play a nuanced role in mediating the mutagenic potential.
Topics: Humans; Mice; Animals; Transcriptome; DNA Repair; DNA Damage; Mutagens; Cell Line; Carcinogens; Hydrazines
PubMed: 36176055
DOI: 10.1002/em.22508 -
Water Research Oct 2020Hydroxylamine is a key intermediate in several biological reactions of the global nitrogen cycle. However, the role of hydroxylamine in anammox is still not fully...
Hydroxylamine is a key intermediate in several biological reactions of the global nitrogen cycle. However, the role of hydroxylamine in anammox is still not fully understood. In this work, the impact of hydroxylamine (also in combination with other substrates) on the metabolism of a planktonic enrichment culture of the anammox species Ca. Kuenenia stuttgartiensis was studied. Anammox bacteria were observed to produce ammonium both from hydroxylamine and hydrazine, and hydroxylamine was consumed simultaneously with nitrite. Hydrazine accumulation - signature for the presence of anammox bacteria - strongly depended on the available substrates, being higher with ammonium and lower with nitrite. Furthermore, the results presented here indicate that hydrazine accumulation is not the result of the inhibition of hydrazine dehydrogenase, as commonly assumed, but the product of hydroxylamine disproportionation. All kinetic parameters for the identified reactions were estimated by mathematical modelling. Moreover, the simultaneous consumption and growth on ammonium, nitrite and hydroxylamine of anammox bacteria was demonstrated, this was accompanied by a reduction in the nitrate production. Ultimately, this study advances the fundamental understanding of the metabolic versatility of anammox bacteria, and highlights the potential role played by metabolic intermediates (i.e. hydroxylamine, hydrazine) in shaping natural and engineered microbial communities.
Topics: Anaerobiosis; Bacteria; Hydroxylamine; Hydroxylamines; Nitrites; Oxidation-Reduction
PubMed: 32739592
DOI: 10.1016/j.watres.2020.116188 -
Acta Crystallographica. Section E,... May 2011The title compound, C(13)H(12)N(4)OS·0.5C(3)H(7)NO, contains four hydrazine mol-ecules and two solvent mol-ecules in the asymmetric unit. The dihedral angles between...
The title compound, C(13)H(12)N(4)OS·0.5C(3)H(7)NO, contains four hydrazine mol-ecules and two solvent mol-ecules in the asymmetric unit. The dihedral angles between the pyridine and phenyl rings in the hydrazine mol-ecules are 67.51 (16), 68.28 (16), 81.36 (15) and 83.32 (15)°. In the crystal, the mol-ecules are linked by N-H⋯N, N-H⋯O and N-H⋯S hydrogen bonds.
PubMed: 21754403
DOI: 10.1107/S1600536811011950 -
FEMS Microbiology Reviews May 2013Anaerobic ammonium-oxidizing (anammox) bacteria primarily grow by the oxidation of ammonium coupled to nitrite reduction, using CO2 as the sole carbon source. Although... (Review)
Review
Anaerobic ammonium-oxidizing (anammox) bacteria primarily grow by the oxidation of ammonium coupled to nitrite reduction, using CO2 as the sole carbon source. Although they were neglected for a long time, anammox bacteria are encountered in an enormous species (micro)diversity in virtually any anoxic environment that contains fixed nitrogen. It has even been estimated that about 50% of all nitrogen gas released into the atmosphere is made by these 'impossible' bacteria. Anammox catabolism most likely resides in a special cell organelle, the anammoxosome, which is surrounded by highly unusual ladder-like (ladderane) lipids. Ammonium oxidation and nitrite reduction proceed in a cyclic electron flow through two intermediates, hydrazine and nitric oxide, resulting in the generation of proton-motive force for ATP synthesis. Reduction reactions associated with CO2 fixation drain electrons from this cycle, and they are replenished by the oxidation of nitrite to nitrate. Besides ammonium or nitrite, anammox bacteria use a broad range of organic and inorganic compounds as electron donors. An analysis of the metabolic opportunities even suggests alternative chemolithotrophic lifestyles that are independent of these compounds. We note that current concepts are still largely hypothetical and put forward the most intriguing questions that need experimental answers.
Topics: Adenosine Triphosphate; Bacteria, Anaerobic; Carbon Dioxide; Energy Metabolism; Environmental Microbiology; Hydrazines; Nitric Oxide; Nitrites; Oxidation-Reduction; Quaternary Ammonium Compounds
PubMed: 23210799
DOI: 10.1111/1574-6976.12014 -
Applied and Environmental Microbiology Apr 2022Ammonia-oxidizing archaea (AOA) and bacteria (AOB) perform key steps in the global nitrogen cycle, the oxidation of ammonia to nitrite. While the ammonia oxidation...
Ammonia-oxidizing archaea (AOA) and bacteria (AOB) perform key steps in the global nitrogen cycle, the oxidation of ammonia to nitrite. While the ammonia oxidation pathway is well characterized in AOB, many knowledge gaps remain about the metabolism of AOA. Hydroxylamine is an intermediate in both AOB and AOA, but homologues of hydroxylamine dehydrogenase (HAO), catalyzing bacterial hydroxylamine oxidation, are absent in AOA. Hydrazine is a substrate for bacterial HAO, while phenylhydrazine is a suicide inhibitor of HAO. Here, we examine the effect of hydrazines in AOA to gain insights into the archaeal ammonia oxidation pathway. We show that hydrazine is both a substrate and an inhibitor for AOA and that phenylhydrazine irreversibly inhibits archaeal hydroxylamine oxidation. Both hydrazine and phenylhydrazine interfered with ammonia and hydroxylamine oxidation in AOA. Furthermore, the AOA " Nitrosocosmicus franklandus" C13 oxidized hydrazine into dinitrogen (N), coupling this reaction to ATP production and O uptake. This study expands the known substrates of AOA and suggests that despite differences in enzymology, the ammonia oxidation pathways of AOB and AOA are functionally surprisingly similar. These results demonstrate that hydrazines are valuable tools for studying the archaeal ammonia oxidation pathway. Ammonia-oxidizing archaea (AOA) are among the most numerous living organisms on Earth, and they play a pivotal role in the global biogeochemical nitrogen cycle. Despite this, little is known about the physiology and metabolism of AOA. We demonstrate in this study that hydrazines are inhibitors of AOA. Furthermore, we demonstrate that the model soil AOA " Nitrosocosmicus franklandus" C13 oxidizes hydrazine to dinitrogen gas, and this reaction yields ATP. This provides an important advance in our understanding of the metabolism of AOA and expands the short list of energy-yielding compounds that AOA can use. This study also provides evidence that hydrazines can be useful tools for studying the metabolism of AOA, as they have been for the bacterial ammonia oxidizers.
Topics: Adenosine Triphosphate; Ammonia; Archaea; Bacteria; Humans; Hydrazines; Hydroxylamines; Nitrification; Phenylhydrazines; Soil Microbiology
PubMed: 35384704
DOI: 10.1128/aem.02470-21 -
Acta Crystallographica. Section E,... Nov 2011The title compound, C(14)H(11)N(5)O(6), was obtained from the condensation reaction of 2,4-dinitro-phenyl-hydrazine and 2-nitro-acetophenone. The mol-ecule displays an E...
The title compound, C(14)H(11)N(5)O(6), was obtained from the condensation reaction of 2,4-dinitro-phenyl-hydrazine and 2-nitro-acetophenone. The mol-ecule displays an E conformation about the C=N double bond and an intra-molecular N-H⋯O hydrogen bond generates an S(6) ring motif. The dihedral angle between the benzene rings is 7.84 (6)°. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds and π-π stacking inter-actions [centroid-centroid distance = 3.6447 (8) Å] into a three-dimensional network.
PubMed: 22220090
DOI: 10.1107/S1600536811042620