Computational study of NTO (5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one) tautomeric properties in aqueous solution

Golius, Anastasiia; Gorb, Leonid; Scott, Andrea Michalkova; Hill, Frances C.; Leszczyński, Jerzy

doi:10.1007/s11224-014-0526-z

Cited by 12 publications

(10 citation statements)

References 23 publications

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“…The deprotonation route with the lowest Gibbs free energy was assumed as the most likely one. This procedure is in line with previous strategies successfully used to identify the deprotonation routes of poliprotic species. − …”

Section: Computational Detailssupporting

confidence: 78%

Comprehensive Investigation of the Antioxidant and Pro-oxidant Effects of Phenolic Compounds: A Double-Edged Sword in the Context of Oxidative Stress?

et al. 2018

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Oxidative stress (OS) is a health-threatening process that is involved, at least partially, in the development of several diseases. Although antioxidants can be used as a chemical defense against OS, they might also exhibit pro-oxidant effects, depending on environmental conditions. In this work, such a dual behavior was investigated for phenolic compounds (PhCs) within the framework of the density functional theory and based on kinetic data. Multiple reaction mechanisms were considered in both cases. The presence of redox metals, the pH, and the possibility that PhCs might be transformed into benzoquinones were identified as key aspects in the antioxidant versus pro-oxidant effects of these compounds. The main virtues of PhCs as antioxidants are their radical trapping activity, their regeneration under physiological conditions, and their behavior as OH-inactivating ligands. The main risks of PhCs as pro-oxidants are predicted to be the role of phenolate ions in the reduction of metal ions, which can promote Fenton-like reactions, and the formation of benzoquinones that might cause protein arylation at cysteine sites. Although the benefits seem to overcome the hazards, to properly design chemical strategies against OS using PhCs, it is highly recommended to carefully explore their duality in this context.

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Section: Computational Detailssupporting

confidence: 78%

Comprehensive Investigation of the Antioxidant and Pro-oxidant Effects of Phenolic Compounds: A Double-Edged Sword in the Context of Oxidative Stress?

et al. 2018

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“…That with the lowest energy cost was identified as the most likely one. Similar computational strategies have been previously used to successfully elucidate deprotonation routes of chemical compounds with multiple acid sites …”

Section: Computational Detailsmentioning

confidence: 99%

Role of purines on the copper‐catalyzed oxidative damage in biological systems: Protection versus promotion

Castañeda‐Arriaga

Pérez-González

Álvarez-Idaboy

et al. 2017

Int J of Quantum Chemistry

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Oxidative damage to biomolecules is a serious health-threatening issue, which leads to the development of several diseases. Oxidative conditions are frequently catalyzed by metal ions. In this study, the role of purines in the copper-catalyzed oxidative stress was investigated using the density functional theory. The obtained results indicate that purines can have a dual behavior, acting as both protectors and promoters of oxidative stress. Their protection role arises from their known radical scavenging activity, as well as their ability to chelate Cu(II) leading to complexes that areto some extent-harder to reduce than free Cu(II). Conversely, their pro-oxidant role is a consequence of their reductant behavior, when deprotonated. Thus, the purines' anions can reduce Cu (II) to Cu(I), making the latter available to be involved in Fenton-like reactions. Consequently, mixtures of purines and Cu(II), at pHs where the fraction of deprotonated purines is rather significant, would yield • OH radicals. In turn, these very reactive radicals would damage biological targets such as lipids, proteins, and DNA.antioxidants, kinetics, pro-oxidants, rate constants, reaction mechanism 1 | I N TR ODU C TI ON Oxidative damage (OD) to biological targets such as lipids, proteins, and DNA is a serious health-threatening phenomenon. It has been held responsible, at least in part, for the onset and development of several diseases including cancer [1][2][3] ; rheumatoid arthritis [4][5][6] ; neurodegenerative disorders such as Parkinson's and Alzheimer's diseases, depression, multiple sclerosis, and memory loss [7][8][9][10][11][12][13] ; cardiovascular diseases such as atherosclerosis, ischemia, hypertension, cardiac hypertrophy, heart failure, and cardiomyopathy [14][15][16][17] ; as well as renal [18][19][20] and pulmonary failure. [21][22][23] OD arises as a consequence of a chemical imbalance between the production and consumption of oxidants, known as oxidative stress (OS). [24] One of the most damaging oxidants in biological systems is the hydroxyl radical ( • OH). It can be produced, in the presence of metal ions such as Fe(II) or Cu(I), by Fenton or Fenton-like reactions (M q 1 H 2 O 2 ! M q11 1OH -1 • OH). However, the most stable and abundant forms of these two metals, under physiological conditions, are Fe(III) and Cu(II). Thus, • OH production would actually involve the metal-catalyzed Haber-Weiss recombination (HWR). It comprises two chemical steps. The first one is the reduction of the metal ions (M q11 1 O •2 2 ! M q 1 3 O 2 ) and the second one is the Fenton reaction. Consequently, redox active metal ions are of particular interest for the chemistry of living systems. These ions cannot only bind to DNA, but they can also promote OD to DNA by mediating the production of oxygen reactive species (ROS). [25] In fact metal-mediated OD to DNA has become an important topic in metal toxicity and carcinogenesis. [26][27][28][29]

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“…As follows from the Gibbs energy pro le presented in Figure 6, the rst step, in this case, is a transfer of the closes NH proton in the direction of the nitro-group oxygen. Since the mobility of this hydrogen is greater than in the case of hydrogen mobility from the CH 3 -group (it is more acidic (Golius et al 2015) the observable reaction barriers are smaller than the one that relates to TNT transformation. Similar to TNT, the reaction is characterized by high exothermicity effects.…”

Section: Pathways Of Nto Decompositionmentioning

confidence: 91%

Decomposition of 2,4,6-Trinitrotoluene (TNT) and 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one (NTO) by Fe13O13 Nano-particle: Density Functional Theory Study

Gorb

Ilchenko

Leszczyński

2022

Preprint

Self Cite

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To obtain more insight into the mechanisms of the decomposition of energetic compounds, we performed a computational study of the interaction of Fe13O13 nano-particle with two energetic molecules (2,4,6-Trinitrotoluene - TNT and 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one - NTO). The density functional theory using M06-2X, B3LYP and BLYP density functionals has been applied. It has been found that the reactivity of these molecules strongly depends on the place of adsorption (so-called top and bottom planes of Fe13O13). Namely, only the interaction with the bottom plane results in the thermodynamic characteristics of the decomposition which provide a medium reaction rate of the studied processes. Several pathways for such a decomposition have been found. One of them is the inter-complex oxygen transfer of nitro-group oxygen to Fe13O13. This pathway results in the formation of adsorbed nitroso compounds. Second pathway describes more complex decomposition which includes the transfer of nitro-group oxygen accompanied by hydrogen transfer. In all cases, the interaction of energetic molecules with Fe13O13 nano-particle takes place along with barrier-less electron transfer from Fe13O13 to TNT or NTO species.

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Computational study of NTO (5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one) tautomeric properties in aqueous solution

Cited by 12 publications

References 23 publications

Comprehensive Investigation of the Antioxidant and Pro-oxidant Effects of Phenolic Compounds: A Double-Edged Sword in the Context of Oxidative Stress?

Comprehensive Investigation of the Antioxidant and Pro-oxidant Effects of Phenolic Compounds: A Double-Edged Sword in the Context of Oxidative Stress?

Role of purines on the copper‐catalyzed oxidative damage in biological systems: Protection versus promotion

Decomposition of 2,4,6-Trinitrotoluene (TNT) and 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one (NTO) by Fe13O13 Nano-particle: Density Functional Theory Study

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