Screening Stability, Thermochemistry, and Chemical Kinetics of 3-Hydroxybutanoic Acid as a Bifunctional Biodiesel Additive.

The thermo-kinetic aspects of 3-hydroxybutyric acid (3-HBA) pyrolysis in the gas phase were investigated using density functional theory (DFT), specifically the M06-2X theoretical level in conjunction with the cc-pVTZ basis set. The obtained data were compared with benchmark CBS-QB3 results. The degradation mechanism was divided into 16 pathways, comprising 6 complex fissions and 10 barrierless reactions. Energy profiles were calculated and supplemented with computations of rate coefficients and branching ratios over the temperature range of 600-1700 K at a pressure of 1 bar using transition state theory (TST) and Rice-Ramsperger-Kassel-Marcus (RRKM) methods. Thermodynamics results indicated the presence of six stable conformers within a 4 kcal mol-1 energy range. The estimated chemical kinetics results suggested that TST and RRKM approaches are comparable, providing confidence in our calculations. The branching ratio analysis reveals that the dehydration reaction pathway leading to the formation of H2O and CH3CH═CHCO2H dominates entirely at T ≤ 650 K. At these temperatures, there is a minor contribution from the simple homolytic bond fission reaction, yielding related radicals [CH3•CHOH + •CH2CO2H]. However, at T ≥ 700 K, this reaction becomes the primary decomposition route. At T = 1700 K, there is a minor involvement of a reaction pathway resulting in the formation of CH3CH(OH)•CH2 + •CHO(OH) with an approximate contribution of 16%, and a reaction leading to [•CH3 + •CH2OHCH2CO2H] with around 9%.

Computational analysis of substituent effects on proton affinity and gas-phase basicity of TEMPO derivatives and their hydrogen bonding interactions with water molecules.

The study investigates the molecular structure of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and its derivatives in the gas phase using B3LYP and M06-2X functional methods. Intermolecular interactions are analyzed using natural bond orbital (NBO) and atoms in molecules (AIM) techniques. NO2-substituted TEMPO displays high reactivity, less stability, and softer properties. The study reveals that the stability of TEMPO derivatives is mainly influenced by LP(e) → σ∗ electronic delocalization effects, with the highest stabilization observed on the oxygen atom of the nitroxide moiety. This work also considers electron density, atomic charges, and energetic and thermodynamic properties of the studied NO radicals, and their relative stability. The proton affinity and gas-phase basicity of the studied compounds were computed at T = 298 K for O-protonation and N-protonation, respectively. The studied DFT method calculations show that O-protonation is more stable than N-protonation, with an energy difference of 16.64-20.77 kcal/mol (22.80-25.68 kcal/mol) at the B3LYP (M06-2X) method. The AIM analysis reveals that the N-O…H interaction in H2O complexes has the most favorable hydrogen bond energy computed at bond critical points (3, - 1), and the planar configurations of TEMPO derivatives exhibit the highest EHB values. This indicates stronger hydrogen bonding interactions between the N-O group and water molecules.

Chemical Investigation on the Mechanism and Kinetics of the Atmospheric Degradation Reaction of Trichlorofluoroethene by OH⋠and Its Subsequent Fate in the Presence of O2 /NOx.

The M06-2X/6-311++G(d,p) level of theory was used to examine the degradation of Trichlorofluoroethene (TCFE) initiated by OH⋅ radicals. Additionally, the coupled-cluster single-double with triple perturbative [CCSD(T)] method was employed to refine the single-point energies using the complete basis set extrapolation approach. The results indicated that OH-addition is the dominant pathway. OH⋅ adds to both the C1 and C2 carbons, resulting in the formation of the C(OH)Cl2 -⋅CClF and ⋅CCl2 -C(OH)ClF species. The associated barrier heights were determined to be 1.11 and -0.99 kcal mol-1 , respectively. Furthermore, the energetic and thermodynamic parameters show that pathway 1 exhibits greater exothermicity and exergonicity compared to pathway 2, with differences of 8.11 and 8.21 kcal mol-1 , correspondingly. The primary pathway involves OH addition to the C2 position, with a rate constant of 6.2×10-13 cm3 molecule-1 sec-1 at 298 K. This analysis served to estimate the atmospheric lifetime, along with the photochemical ozone creation potential (POCP) and ozone depletion potential (ODP). It yielded an atmospheric lifetime of 8.49 days, an ODP of 4.8×10-4 , and a POCP value of 2.99, respectively. Radiative forcing efficiencies were also estimated at the M06-2X/6-311++G(d,p) level. Global warming potentials (GWPs) were calculated for 20, 100, and 500 years, resulting in values of 9.61, 2.61, and 0.74, respectively. TCFE is not expected to make a significant contribution to the radiative forcing of climate change. The results obtained from the time-dependent density functional theory (TDDFT) indicated that TCFE and its energized adducts are unable to photolysis under sunlight in the UV and visible spectrum. Secondary reactions involve the [TCFE-OH-O2 ]⋅ peroxy radical, leading subsequently to the [TCFE-OH-O]⋅ alkoxy radical. It was found that the alkoxy radical resulting from the peroxy radical can lead to the formation of phosgene (COCl2 ) and carbonyl chloride fluoride (CClFO), with phosgene being the primary product.

Understanding the kinetics and atmospheric degradation mechanism of chlorotrifluoroethylene (CF2CFCl) initiated by OH radicals.

The atmospheric degradation of chlorotrifluoroethylene (CTFE) by OH˙ was investigated using density functional theory (DFT). The potential energy surfaces were also defined in terms of single-point energies derived from the linked cluster CCSD(T) theory. With an energy barrier of -2.62 to -0.99 kcal mol-1 using the M06-2x method, the negative temperature dependence was determined. The OH˙ attack on Cα and Cß atoms (labeled pathways R1 and R2, respectively) shows that reaction R2 is 4.22 and 4.42 kcal mol-1, respectively, more exothermic and exergonic than reaction R1. The main pathway should be the addition of OH˙ to the ß-carbon, resulting in ˙CClF-CF2OH species. At 298 K, the calculated rate constant was 9.87 × 10-13 cm3 molecule-1 s-1. The TST and RRKM calculations of rate constants and branching ratios were performed at P = 1 bar and in the fall-off pressure regime over the temperature range of 250-400 K. The formation of HF and ˙CClF-CFO species via the 1,2-HF loss process is the most predominant pathway both kinetically and thermodynamically. With increasing temperature and decreasing pressure, the regioselectivity of unimolecular processes of energized adducts [CTFE-OH]˙ gradually decreases. Pressures greater than 10-4 bar are often adequate for assuring saturation of the estimated unimolecular rates when compared to the RRKM rates (in high-pressure limit). Subsequent reactions involve the addition of O2 to the [CTFE-OH]˙ adducts at the α-position of the OH group. The [CTFE-OH-O2]˙ peroxy radical primarily reacts with NO and then directly decomposes into NO2 and oxy radicals. "Carbonic chloride fluoride", "carbonyl fluoride", and "2,2-difluoro-2-hydroxyacetyl fluoride" are predicted to be stable products in an oxidative atmosphere.

Atmospheric degradation mechanism of anthracene initiated by OH•: A DFT prediction.

Density functional theory (DFT) calculations at the M06-2X/def2-TZVP level have been employed to investigate the atmospheric oxidation mechanism of anthracene (ANT) initiated by HO•. Direct hydrogen atom abstraction from the ANT using HO• takes place hardly at ambient conditions while addition of HO• to the C1, C2, and C4 sites are thermodynamically and kinetically more advantageous. The addition reactions are controlled by the aromaticity and the kinetic trends were justified by resonance stabilization energies. The rate constants were calculated by using the Rice-Ramsperger-Kassel-Marcus (RRKM) and canonical transition state theory (CTST) methods in conjugation with zero curvature tunneling (ZCT). The overall RRKM-bimolecular rate constant at ambient conditions is 6.72 × 10-12 cm3 molecule-1 s-1, is negatively dependent on the temperature and can be expressed as k250-3501bar=3.92×10-14exp(1534.9T). Contribution of the AD-C4 path in the overall reaction is about 70-80%, implying that the dependence of overall rate constant on pressure can be ignored. The kinetic data exhibit that the ANT is degraded during its long-range transport in the atmosphere and cannot be classified as persistent organic pollutants.

Computational studies on thermo-kinetics aspects of pyrolysis of isopropyl acetate and its methyl, bromide and hydroxyl derivatives.

The gas-phase decomposition kinetics of isopropyl acetate (IPA) and its methyl, bromide and hydroxyl derivatives into the corresponding acid and propene were investigated using density functional theory (DFT) with the ωB97XD and M06-2x functionals, as well as the benchmark CBS-QB3 composite method. Transition state theory (TST) and RRKM theory calculations of rate constants under atmospheric pressure and in the fall-off regime were used to supplement the measured energy profiles. The results show that the formation of propene and bromoacetic acid is the most dominant pathway at the CBS-QB3 composite method, both kinetically and thermodynamically. There was a good agreement with experimental results. Pressures greater than 0.01 bar, corresponding to larger barrier heights are insufficient to ensure saturation of the measured rate coefficient when compared to the RRKM kinetic rates. Natural bond orbitals (NBO) charges, bond orders, bond indices, and synchronicity parameters all point to the considered pathways taking place via a homogenous, first-order concerted, as well as an asynchronous mechanism involving a non-planar cyclic six-membered transition state. The calculated data exhibit that the elongation of the Cα-O bond length and subsequent polarization of the Cα +δ…O-δ bond is the rate-determining step of the considered reactions in the cyclic transition state, which appears to be involved in this type of reaction.

Novel 1, 2, 4-Triazoles as Antifungal Agents.

The development of innovative antifungal agents is essential. Some fungicidal agents are no longer effective due to resistance development, various side effects, and high toxicity. Therefore, the synthesis and development of some new antifungal agents are necessary. 1,2,4-Triazole is one of the most essential pharmacophore systems between five-membered heterocycles. The structure-activity relationship (SAR) of this nitrogen-containing heterocyclic compound showed potential antifungal activity. The 1,2,4-triazole core is present as the nucleus in a variety of antifungal drug categories. The most potent and broad activity of triazoles have confirmed them as pharmacologically significant moieties. The goal of this review is to highlight recent developments in the synthesis and SAR study of 1,2,4-triazole as a potential fungicidal compound. In this study, we provide the results of a biological activity evaluation using various structures and figures. Literature investigation showed that 1, 2, 4-triazole derivatives reveal the extensive span of antifungal activity. This review will assist researchers in the development of new potential antifungal drug candidates with high effectiveness and selectivity.

DFT study on tautomerism and natural bond orbital analysis of 4-substituted 1,2,4-triazole and its derivatives: solvation and substituent effects.

Density functional theory investigations at the DFT-B3LYP/6-311++G** theoretical level employed to determine the tautomerism, substituent effects of 4-substituted 4-amino-5-methyl-2,4-dihydro-3H-1,2,4-triazole-3-thione, and its derivatives (4-R-H, 4-R-CH3, 4-R-F, 4-R-NO2) in the selected solvent (acetone, acetonitrile, and dichloromethane) and gas phases using the polarizable continuum method (PCM) model. The substituted 1,2,4-triazoles have two main different tautomers namely N2-H and S7-H. For considered derivatives, thione forms are more energetically stable and dominant form in the studied solvent and gas phases. In addition, geometrical parameters, charges on atoms, dipole moments, energetic properties, and the nucleus-independent chemical shifts (NICS) are investigated. It has been seen that these molecular features of the studied compound and its derivatives are mostly solvent dependent. For electron-releasing and -withdrawing derivatives in the solution and gas phases, 2-H forms are the more stable and dominant form. The relative stability of the C4-substituted 1,2,4-triazole tautomerism is influenced by the possibility for intramolecular interactions between substituent and electron-donor or electron-acceptor centers of the triazole ring.

Kinetic and mechanistic insight into the OH-initiated atmospheric oxidation of 2,3,7,8-tetrachlorodibenzo-p-dioxin via OH-addition and hydrogen abstraction pathways: A theoretical investigation.

The 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) is the most toxic polychlorinated dibenzo-p-dioxin. The OH-initiated oxidation of TCDD has been studied using the density functional, canonical transition state, and canonical Rice-Ramsperger-Kassel-Marcus theories. The kinetic data were corrected for quantum tunneling by the Wigner and Eckart models. All OH addition and hydrogen atom abstraction channels were thermodynamically exergonic. The kinetic and thermodynamic data analysis at the reliable level MPWB1K/MG3S//M06-2X/MG3S indicate that the addition of OH to the carbon atom adjacent to the oxygen atom in dioxin ring leads to the formation of predominant adduct. The calculated bimolecular rate constant for the formation of predominant adduct was ~5.97-6.75 × 10-13 cm3 molecule-1 s-1, its branching ratio was ~0.955, and the overall rate constant for the OH-initiated oxidation of TCDD was ~6.25-7.08 × 10-13 cm3 molecule-1 s-1. The atmospheric lifetime of TCDD determined by OH was ~8.17-9.26 days indicating the TCDD can be categorized as medium lifetime organic pollutant.

Atmospheric oxidation reactions of imidazole initiated by hydroxyl radicals: kinetics and mechanism of reactions and atmospheric implications.

The atmospheric oxidation mechanism of imidazole initiated by hydroxyl radicals is investigated via OH-addition and H-abstraction pathways by quantum chemistry calculations at the M06-2X/aug-cc-pVTZ level of theory coupled with reaction kinetics calculations using statistical Rice-Ramsperger-Kassel-Marcus (RRKM) theory and transition state theory (TST). It was found that OH addition proceeds more rapidly than H-abstraction by several orders of magnitude. Moreover, H-abstraction reactions with submerged barriers exhibit positive temperature dependence. Effects of reaction temperature and pressure on the reaction between imidazole and OH radicals are studied by means of RRKM calculations. Effective rate coefficients involve two-step mechanisms. According to the experiment, the obtained branching ratios show that the kinetically most efficient process corresponds to OH addition onto a carbon atom which is adjacent to a nitrogen atom having a lower energy barrier. These ratios also reveal that the regioselectivity of the oxidation reaction decreases with increasing temperatures and decreasing pressures. Because of negative activation energies, pressures larger than 100 bar are required to reach the high pressure limit. The atmospheric lifetime of imidazole in the presence of OH radicals is estimated to be ∼4.74 days, based on the calculated overall kinetic rate constant of 1.22 × 10-12 cm3 molecule-1 s-1 at a pressure of 1 bar and nearly ambient temperature. NBO analysis demonstrates that the calculated energy barriers are dictated by charge transfer effects and aromaticity changes because of the delocalization of nitrogen lone pairs to empty π* orbitals.

Following the Molecular Mechanism of Decarbonylation of Unsaturated Cyclic Ketones Using Bonding Evolution Theory Coupled with NCI Analysis.

The synergetic use of bonding evolution theory (BET) and noncovalent interaction (NCI) analysis allows to obtain new insight into the bond breaking/forming processes and electron redistribution along the reaction path to understand the molecular mechanism of a reaction and recognize regions of strong and weak electron pairing. This viewpoint has been considered for cheletropic extrusion of CO from unsaturated cyclic ketones cyclohepta-3,5-dien-1-one CHD, cyclopent-3-en-1-one CPE, and bicyclo[2.2.1]hept-2-en-7-one BCH by using hybrid functional MPWB1K in conjugation with aug-cc-pVTZ basis set. Decarbonylation of CHD, CPE, and BCH are nonpolar cyclo-elimination reactions that are characterized by the sequence of turning points (TPs) as CHD, 1-11-C[CC]C†C†FFFTSC†C†C†-0:HT + CO; CPE, 1-8-CC[C†C†F†][FF][FF]FTS[C†C†]-0:BD + CO; and BCH, 1-8-CC[C†C†]F[FF]FTS[C†C†]-0:CD + CO. Breaking of C-C bond between the terminal carbon atoms of diene/triene framework and carbon atom of CO fragment starts at a distance of ca. 1.9-2.0 Å in the vicinity of the transition structure where the transition states are not reached yet. NCI analysis explains that the noncovalent interactions between two fragments appeared after the breaking of C-C bonds.

Theoretical study of the oxidation mechanisms of thiophene initiated by hydroxyl radicals.

The mechanisms for the oxidation of thiophene by OH radicals under inert conditions (Ar) have been studied using density functional theory in conjunction with various exchange-correlation functionals. These results were compared with benchmark CBS-QB3 theoretical results. Kinetic rate constants were estimated by means of variational transition state theory (VTST) and the statistical Rice-Ramsperger-Kassel-Marcus (RRKM) theory. Effective rate constants were calculated via a steady-state analysis based upon a two-step model reaction mechanism. In line with experimental results, the computed branching ratios indicate that the most kinetically efficient process involves OH addition to a carbon atom adjacent to the sulfur atom. Due to the presence of negative activation energies, pressures larger than 10(4) bar are required to reach the high-pressure limit. Nucleus-independent chemical shift indices and natural bond orbital analysis show that the computed activation energies are dictated by changes in aromaticity and charge-transfer effects due to the delocalization of lone pairs from sulfur to empty π(*) orbitals. Graphical Abstract CBS-QB3 energy profiles for the reaction pathways 1-3 characterizing the oxidation of thiophene by hydroxyl radicals into the related products.

Theoretical study of the oxidation mechanisms of naphthalene initiated by hydroxyl radicals: the OH-addition pathway.

The oxidation mechanisms of naphthalene by OH radicals under inert (He) conditions have been studied using density functional theory along with various exchange-correlation functionals. Comparison has been made with benchmark CBS-QB3 theoretical results. Kinetic rate constants were correspondingly estimated by means of transition state theory and statistical Rice-Ramsperger-Kassel-Marcus (RRKM) theory. Comparison with experiment confirms that, on the OH-addition reaction pathway leading to 1-naphthol, the first bimolecular reaction step has an effective negative activation energy around -1.5 kcal mol(-1), whereas this step is characterized by an activation energy around 1 kcal mol(-1) on the OH-addition reaction pathway leading to 2-naphthol. Effective rate constants have been calculated according to a steady state analysis upon a two-step model reaction mechanism. In line with experiment, the correspondingly obtained branching ratios indicate that, at temperatures lower than 410 K, the most abundant product resulting from the oxidation of naphthalene by OH radicals must be 1-naphthol. The regioselectivity of the OH(•)-addition onto naphthalene decreases with increasing temperatures and decreasing pressures. Because of slightly positive or even negative activation energies, the RRKM calculations demonstrate that the transition state approximation breaks down at ambient pressure (1 bar) for the first bimolecular reaction steps. Overwhelmingly high pressures, larger than 10(5) bar, would be required for restoring to some extent (within ∼5% accuracy) the validity of this approximation for all the reaction channels that are involved in the OH-addition pathway. Analysis of the computed structures, bond orders, and free energy profiles demonstrate that all reaction steps involved in the oxidation of naphthalene by OH radicals satisfy Leffler-Hammond's principle. Nucleus independent chemical shift indices and natural bond orbital analysis also show that the computed activation and reaction energies are largely dictated by alterations of aromaticity, and, to a lesser extent, by anomeric and hyperconjugative effects.

Theoretical study of the oxidation mechanisms of naphthalene initiated by hydroxyl radicals: the H abstraction pathway.

Reaction mechanisms for the initial stages of naphthalene oxidation at high temperatures (T ≥ 600 K) have been studied theoretically using density functional theory along with various exchange-correlation functionals, as well as the benchmark CBS-QB3 quantum chemical approach. These stages correspond to the removal of hydrogen atoms by hydroxyl radical and the formation thereby of 1- and 2-naphthyl radicals. Bimolecular kinetic rate constants were estimated by means of transition state theory. The excellent agreement with the available experimental kinetic rate constants demonstrates that a two-step reaction scheme prevails. Comparison with results obtained with density functional theory in conjunction with various exchange-correlation functionals also shows that DFT remains unsuited for quantitative insights into kinetic rate constants. Analysis of the computed structures, bond orders, and free energy profiles demonstrates that the reaction steps involved in the removal of hydrogen atoms by OH radicals satisfy Hammond's principle. Computations of branching ratios also show that these reactions do not exhibit a particularly pronounced site-selectivity.