This paper is focused on the theoretical investigation of O-C Bond Dissociation Enthalpy (BDE) of methoxy OCH group in 15 meta- and 15 para-substituted anisoles in gas phase, non-polar environment, and water. Density Functional Theory (DFT) calculations were carried out using M06-2X functional and 6-311++G(d,p) basis set. Obtained BDEs were correlated with Brown and Okamoto σ and Hammett σ constants representing commonly used descriptors of electron-donating or electron-withdrawing substituent effect.
View Article and Find Full Text PDFInt J Environ Res Public Health
January 2023
Coumarins represent a broad class of compounds with pronounced pharmacological properties and therapeutic potential. The pursuit of the commercialization of these compounds requires the establishment of controlled and highly efficient degradation processes, such as advanced oxidation processes (AOPs). Application of this methodology necessitates a comprehensive understanding of the degradation mechanisms of these compounds.
View Article and Find Full Text PDFGuaiacol (2-methoxyphenol) is naturally occurring phenolic compound essential in various research areas. Oxidative transformation of guaiacol can lead to the formation of various products, including 1,3-benzodioxole or -quinone. Therefore, this study is focused on the investigation of the reaction enthalpies of experimentally observed guaiacol oxidation pathways in gas-phase, as well as in non-polar environment and aqueous solution.
View Article and Find Full Text PDFPhenolic acids represent naturally occurring antioxidants and play important role in free radicals scavenging. In this work, we have studied thermodynamics of the first step of primary antioxidant action for phenolic OH groups of benzoic and cinnamic acid derivatives, and their carboxylate anions. M06-2X/6-311++G(d,p) reaction enthalpies related to Hydrogen Atom Transfer (HAT), Single Electron Transfer - Proton Transfer (SET-PT), and Sequential Proton-Loss Electron-Transfer (SPLET) mechanisms were computed for model non-polar environment (benzene) and aqueous solution.
View Article and Find Full Text PDFDespite the intensive research on radical scavenging action of flavonoids, a systematic study of the thermochemistry for their mono-deprotonated species in aqueous solution is still missing. In this work, reaction enthalpies related to Sequential Proton-Loss Electron-Transfer (SPLET) mechanism were theoretically investigated for all mono-deprotonated forms of nine flavonoids: apigenin, luteolin, fisetin, kaempferol, quercetin, taxifolin, tricetin, tricin and cyanidin. Differences in reaction enthalpies of the first and the second deprotonation can be lower than 10 kJ mol, when two successive deprotonations occur in different aromatic rings of the molecule.
View Article and Find Full Text PDFRadical scavenging activity and subsequent oxidation resulting in quinone products represent one of the important features of phenols occurring in plants and other biological systems. However, corresponding thermochemistry data can be still considered scarce. For phenol and 25 para-substituted phenols, we investigate the thermodynamics of the individual reaction steps, including three subsequent hydrogen atom transfers, as well as hydroxyl HO radical addition, leading to final ortho-quinone formation.
View Article and Find Full Text PDFFor nine symmetric natural carotenoids, a comprehensive thermodynamics study of processes associated with their radical scavenging activity is proposed. We have investigated the hydrogen atom transfer (HAT) from the parent carotenoid, mono-radical species, radical cations and radical anions. Electron transfer and proton transfer reactions were also studied.
View Article and Find Full Text PDFThe role of antiradical moieties (catechol, guaiacyl and carboxyl group) and molecular conformation in antioxidative potency of dihydrocaffeic acid (DHCA) and dihydroferulic acid (DHFA) was investigated by density functional theory (DFT) method. The thermodynamic preference of different reaction paths of double (2H/2e) free radical scavenging mechanisms was estimated. Antiradical potency of DHCA and DHFA was compared with that exerted by their unsaturated analogs - caffeic acid (CA) and ferulic acid (FA).
View Article and Find Full Text PDFJ Can Chiropr Assoc
March 2017
In 2004, a 61-year-old male presented to a chiropractic clinic complaining of neck pain after hearing a 'crunch' when getting out of bed that morning. The initial history intake and physical examination identified no red flags or indications for the patient's pain, with the exception of traction being pain-provoking. Conventional radiographs were ordered, which identified a pathological burst fracture of the fourth cervical vertebra.
View Article and Find Full Text PDFJ Can Chiropr Assoc
March 2016
Objective: To report on a case of a pathological burst fracture in the cervical spine where typical core red flag tests failed to identify a significant lesion, and to remind chiropractors to be vigilant in the recognition of subtle signs and symptoms of disease processes.
Clinical Features: A 61-year-old man presented to a chiropractic clinic with neck pain that began earlier that morning. After a physical exam that was relatively unremarkable, imaging identified a burst fracture in the cervical spine.
In this paper, the study of melatonin and 60 meta- and ortho-substituted melatonins is presented. The reaction enthalpies related to the hydrogen atom transfer (HAT), single electron transfer - proton transfer (SET-PT) and sequential proton loss electron transfer (SPLET) have been calculated using DFT/B3LYP method in gas-phase and water. Results show that electron-withdrawing substituents increase the bond dissociation enthalpy (BDE), ionization potential (IP) and electron transfer enthalpy (ETE), while electron-donating ones cause a rise in the proton dissociation enthalpy (PDE) and proton affinity (PA).
View Article and Find Full Text PDFWe have performed Density Functional Theory B3LYP/6-311++G** calculations of reaction enthalpies of antioxidant action mechanisms for nine isoflavones. O-H bond dissociation enthalpies, ionization potentials, proton dissociation enthalpies, proton affinities and electron transfer enthalpies related to Hydrogen Atom Transfer (HAT), Single Electron Transfer-Proton Transfer (SET-PT) and Sequential Proton-Loss Electron-Transfer (SPLET) mechanisms were investigated in gas- and solution-phases. Studies on the radical scavenging ability of isoflavones, contrary to various flavonoids, are still scarce.
View Article and Find Full Text PDFIn this paper, 23 substituents with various electron-donating and electron-withdrawing characters were placed in available positions of trans-resveratrol in order to study their effect on the three O-H bond dissociation enthalpies (BDEs) via density functional theory (DFT) with Becke three-parameter exchange and Lee-Yang-Parr correlation (B3LYP). It has been found that the mutual positions of substituents and OH groups affect investigated BDEs substantially. Formation of strong intramolecular hydrogen bonds and suitable spin density distributions in several radicals result in low BDEs.
View Article and Find Full Text PDFIn this paper, quantum chemical calculations for various cyano derivatives of thiophene and terthiophenes at the density functional theory (DFT) and ab initio Møller-Plesset (MP2) levels of theory are presented. In the case of the studied terthiophenes, CN groups located in the central part of the molecule lead to a preference of cis-cis geometry over trans-trans conformation. For alpha-substituted dicyano terthiophene, the investigation of torsional dependences shows that the highest energy barrier occurs at the perpendicular orientation of the aromatic rings.
View Article and Find Full Text PDFThe reaction enthalpies related to the individual steps of two phenolic antioxidants action mechanisms, single electron transfer-proton transfer (SET-PT) and sequential proton loss electron transfer (SPLET), for 30 meta and para-substituted phenols (ArOH) were calculated using DFT/B3LYP method. These mechanisms represent the alternative ways to the extensively studied hydrogen atom transfer (HAT) mechanism. Except the comparison of calculated reaction enthalpies with available experimental and/or theoretical values, obtained enthalpies were correlated with Hammett constants.
View Article and Find Full Text PDFPedophilia is characterized by sexual attraction to prepubescent children. Despite the extensive literature documenting the pervasive and pernicious effects of childhood sexual abuse, there is surprisingly little psychiatric literature on pedophilia and its etiology remains enigmatic. In recent years, the psychiatric literature on the phenomenology, neurobiology, and treatment of impulsive-aggressive disorders has grown significantly.
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