A thermochemistry and kinetic study on the thermal decomposition of ethoxyquinoline and ethoxyisoquinoline

The file attached to this record is the author's final peer reviewed version. The Publisher's final version can be found by following the DOI link.Quantum chemical calculations were used to study the production of ethylene and keto/enol tautomers from ethoxyquinoline (2‐EQ) and ethoxyisoquinoline (1‐EisoQ and 3‐EisoQ) in the gas phase and ethanol at the MP2/6‐311++G(2d,2p)//BMK/6‐31+G(d,p) level. The obtained data indicate that the elimination of ethylene from 1‐EisoQ and 2‐EQ is slightly more favorable than from 3‐EisoQ. Formation of quinolone and isoquinolone (2‐EQO, 1‐EisoQO, and 3‐EisoQO) is kinetically favored compared to their enols. Decomposition of 2‐EQ and 1‐EisoQ to ethylene and keto forms is thermodynamically and kinetically preferable more stable than the corresponding enols. However, the hydroxy form of 3‐EisoQ is more stable than its keto tautomer in the gas phase and ethanol. The enol tautomers cost less energy when formed from their keto forms rather than from the parent ethoxyquinolone and ethoxyisoquinoline

Atmospheric Oxidation of Methyl Propanoate by the OH radical

The file attached to this record is the author's final peer reviewed version.Atmospheric oxidation of methyl propanoate (MP) by the OH radical has been performed using density functional theory (BMK, BBIK) and ab initio (MP2, CBS-QB3) calculations. The thermodynamic and kinetic parameters are calculated. Three channels have been discussed. These reactions occur through low energy barriers of 3.2–4.3 kcal/mol. The energy barriers increase in the order α < μ < β at CBS–QB3. However, BMK shows slightly different order. Rate constants and branching ratios reveal that the H-abstraction from Cα is as the dominant reaction over the whole temperature range of 200–300 K, with a competition from Cβ channel at lower temperature. The BB1K data reproduce the available experimental rate constant

Theoretical and experimental studies on anticancer drug mitoxantrone

The file attached to this record is the author's final peer reviewed version. The Publisher's final version can be found by following the DOI link.Mitoxantrone (MX) is an important antineoplastic drug used for treatment of different types of cancer with lower side effects. The purpose of this study is to shade more light on the mechanism of interaction between MX and biological molecules. This study would result in drug design and development. Molecular structure was computed at the B3LYP/6-31 + G(d) level. All possible intramolecular hydrogen bonding interactions were considered and calculated at the same level. Five conformers of MX were located and computed to lie in the energy range 0.000–48.495 kcal/mol. Molecular reactivity of MX towards biological systems was explored using condensed molecular descriptors, Fukui functions of electrophilic, nucleophilic and free radical attack. Molecular docking studies for the inhibition of CDK2 and DNA binding were carried out to explore the anticancer potency of MX. The role of charge transfer binding in the interaction of MX with biological molecules was investigated via studying the ability of MX to act as a charge transfer acceptor with known donors using NMR spectroscopy. Charge transfer complex formation was confirmed by proton chemical shift and stability constants were measured from the NMR chemical shift data. Stability constants of MX with donors, phenylene diamine, hexamethyl benzene and pyrene are 4.178, 2.527 and 1.240 M-1 respectively

Computational Studies on the Thermodynamic and Kinetic Parameters of Oxidation of 2-Methoxyethanol Biofuel via H-Atom Abstraction by Methyl Radical

In this work, a theoretical investigation of thermochemistry and kinetics of the oxidation of bifunctional 2-Methoxyethanol (2ME) biofuel using methyl radical was introduced. Potential-energy surface for various channels for the oxidation of 2ME was studied at density function theory (M06-2X) and ab initio CBS-QB3 levels of theory. H-atom abstraction reactions, which are essential processes occurring in the initial stages of the combustion or oxidation of organic compounds, from different sites of 2ME were examined. A similar study was conducted for the isoelectronic n-butanol to highlight the consequences of replacing the ϒ CH2 group by an oxygen atom on the thermodynamic and kinetic parameters of the oxidation processes. Rate coefficients were calculated from the transition state theory. Our calculations show that energy barriers for n-butanol oxidation increase in the order of α ‹ O ‹ ϒ ‹ β ‹ ξ, which are consistent with previous data. However, for 2ME the energy barriers increase in the order α ‹ β ‹ ξ ‹ O. At elevated temperatures, a slightly high total abstraction rate is observed for the bifunctional 2ME (4 abstraction positions) over n-butanol (5 abstraction positions). © 2019, The Author(s).Scopu

Design, Synthesis and Biological Evaluation of Pyrido[23-d] pyrimidine derivatives as potential anticancer agents

The file attached to this record is the author's final peer reviewed version. The Publisher's final version can be found by following the DOI link.Background: CDK2 shows a fundamental role as a controller of cell growing, which makes it as one of the goals of anticancer inhibitors. The current study participated in design (docking and binding energy), which used to select the promising proposed compounds, synthesis of novel diverse 14 pyrido[2,3-d]pyrimidine derivatives and biological studies of the prepared compounds as promising anticancer agents aiming CDK2. All the fresh generated compounds were scanned for their anticancer activity versus MCF-7 and CaCO2 and 14 compounds were found to be active. Compounds 6c and 8d displayed expressive activity with IC50 values 7.4 and 5.5 on MCF-7 respectively. The created compounds were submitted to enzyme inspection (CDK2 TK) for assigning their inhibitory activity. The initial results showed that compound 8d, which demonstrates potent inhibitory activity towards tumor development and powerful inhibitions of CDK2 TK enzyme (89% inhibition) could be utilized as a lead candidate. Method: The products were characterized by IR, 1H NMR, 13CNMR and MS. Results and Conclusion: Preliminary bioassays indicated that most of the compounds exhibited very good antitumor activity and powerful inhibitions of CDK2 TK enzyme