Novel Pyridinium Based Ionic Liquid Promoter for Aqueous Knoevenagel Condensation: Green and Efficient Synthesis of New Derivatives with Their Anticancer Evaluation

Herein, a distinctive dihydroxy ionic liquid ([Py-2OH]OAc) was straightforwardly assembled from the sonication of pyridine with 2-chloropropane-1,3-diol by employing sodium acetate as an ion exchanger. The efficiency of the ([Py-2OH]OAc as a promoter for the sono-synthesis of a novel library of condensed products through DABCO-catalyzed Knoevenagel condensation process of adequate active cyclic methylenes and ninhydrin was next investigated using ultimate greener conditions. All of the reactions studied went cleanly and smoothly, and the resulting Knoevenagel condensation compounds were recovered in high yields without detecting the aldol intermediates in the end products. Compared to traditional strategies, the suggested approach has numerous advantages including mild reaction conditions with no by-products, eco-friendly solvent, outstanding performance in many green metrics, and usability in gram-scale synthesis. The reusability of the ionic liquid was also studied, with an overall retrieved yield of around 97% for seven consecutive runs without any substantial reduction in the performance. The novel obtained compounds were further assessed for their in vitro antitumor potential toward three human tumor cell lines: Colo-205 (colon cancer), MCF-7 (breast cancer), and A549 (lung cancer) by employing the MTT assay, and the findings were evaluated with the reference Doxorubicin. The results demonstrated that the majority of the developed products had potent activities at very low doses. Compounds comprising rhodanine (5) or chromane (12) moieties exhibited the most promising cytotoxic effects toward three cell lines, particularly rhodanine carboxylic acid derivative (5c), showing superior cytotoxic effects against the investigated cell lines compared to the reference drug. Furthermore, automated docking simulation studies were also performed to support the results obtained.     

A new strategy for the synthesis of 2-mercaptobenzazole derivatives by green chemistry metrics

Abstract

A green and efficient method has been developed for the synthesis of 2-mercaptobenzazole derivatives via the reaction of commercially available aniline derivatives with low-cost and nontoxic potassium thiocyanate in water. The reactions proceeded smoothly under catalyst- and ligand-free conditions to give the corresponding products in good to excellent yields. The versatility, low cost, and environmental friendliness, in combination with high yields and easy work-up makes the procedure noteworthy.     

The strengthening effect of a hydrogen or lithium bond on the Z···N aerogen bond (Z = Ar,Kr and Xe): a comparative study

An ab initio study is performed on O₃Z···NCM···NCX (Z = Ar, Kr and Xe; M = H and Li; X = H, F and CH₃) complexes to investigate cooperativity effects between aerogen and hydrogen or lithium bonding interactions in these systems. To understand the cooperative effects, a detailed analysis of the binding distances, interaction energies and bonding properties is performed on these complexes. The results indicate that all Z···N and H/Li···N binding distances in the ternary complexes are shorter than those of corresponding binary systems. For a given M or X, cooperative energies increase as Z = Xe > Kr > Ar. Moreover, O₃Z···NCLi···NCX complexes exhibit a larger cooperative energy than O₃Z···NCH···NCX ones. The non-covalent interaction (NCI) index analysis indicates that the formation of an H/Li···N interaction in the ternary complexes shifts the location of the spike associated with the Z···N interaction towards the negative λ₂ρ values. This indicates that NCI analysis can be regarded as a useful tool for the study of cooperative effects between two different non-covalent interactions. Also, cooperative effects in O₃Z···NCM···NCX complexes make a decrease in ¹⁴N nuclear quadrupole coupling constants of NCH or NCLi molecule.     

Homotopy analysis method to obtain numerical solutions of the Painlevé equations

In this paper, the homotopy analysis method (HAM) is presented to obtain the numerical solutions for the two kinds of the Painlevé equations with a number of initial conditions. Then, a numerical evaluation and comparison with the results obtained via the HAM are included. It illustrates the validity and the great potential of the HAM in solving Painlevé equations. Although the HAM contains the auxiliary parameter, the convergence region of the series solution can be controlled in a simple way. Copyright © 2012 John Wiley & Sons, Ltd.     

Towards Magnetic Carbo‐meric Molecular Materials

Numerous studies have underlined the putative diradical character of π‐conjugated molecules that can be described by closed‐shell Lewis structures, for instance, p‐dimethylene p–n phenylenes, or long polyacenes. In the latter compounds, the only way to save the aromaticity of the six‐membered rings is to give up the Lewis electron pairing in the singlet biradical ground state. The present work considers the possibility of doing the same by using the basic C₂ units of carbo‐meric architectures. A series of acyclic and cyclic carbo‐meric architectures is studied by using UB3LYP DFT broken‐symmetry calculations, including spin decontaminations and subsequent geometry optimization of the singlet diradical. The C₂ units are shown to stabilize the singlet biradical by spin delocalization, two of them playing approximately the same role as one radical‐insulating 1,4 phenylene moiety. The results are generalized to the investigation of open‐shell polyradical singlet states of rigid hydrocarbon structures, the symmetry and rigidity of which can assist cooperativity and self spin polarization effect. Several synthesis targets with challenging magnetic/spin properties are suggested in the carbo‐mer series.     

Kinetics and Mechanistic Study of Acetaminophen‐Captopril Interaction by Electrochemical Methods

In this work kinetics parameters and electrochemical mechanism for electrooxidation of acetaminophen in the absence and presence of captopril in a condition close to acetaminophen natural oxidation pathway was investigated. The electrooxidation of acetaminophen in the presence of captopril was investigated by voltammetry and coulometry methods. The results of this work show that acetaminophen is oxidized to its respective p‐quinoneimine. The quinoneimine attacked by captopril, forms thioether. The proposed electrochemical mechanism is ECEC. The estimated value for homogeneous rate constant k_obs is 3.1×10⁴±155 M^?1s^?1 and k_f/k_b is 1.6×10⁸±8.0×10⁵.     

Evaluation of char combustion models: measurement and analysis of variability in char particle size and density

Char samples representing a range of combustion conditions and extents of burnout were obtained from a well-characterized laminar flow combustion experiment. Individual particles from the parent coal and char samples were characterized to determine distributions in particle volume, mass, and density at different extent of burnout. The data were then compared with predictions from a comprehensive char combustion model referred to as the char burnout kinetics model (CBK). The data clearly reflect the particle-to-particle heterogeneity of the parent coal and show a significant broadening in the size and density distributions of the chars resulting from both devolatilization and combustion. Data for chars prepared in a lower oxygen content environment (6% oxygen by vol.) are consistent with zone II type combustion behavior where most of the combustion is occurring near the particle surface. At higher oxygen contents (12% by vol.), the data show indications of more burning occurring in the particle interior. The CBK model does a good job of predicting the general nature of the development of size and density distributions during burning but the input distribution of particle size and density is critical to obtaining good predictions. A significant reduction in particle size was observed to occur as a result of devolatilization. For comprehensive combustion models to provide accurate predictions, this size reduction phenomenon needs to be included in devolatilization models so that representative char distributions are carried through the calculations.     

Prediction of the thermal conductivity of the constituents of fiber reinforced composite laminates

Three empirical formulas are developed to predict the thermal conductivities of fiber-reinforced composite laminates (FRCL) and its constituents. The inherent two or three-dimensional problem that is common in composites is simplified to a one-dimensional problem. The validity of the models is verified through finite element analysis. This method utilizes the parallel and series thermal models of composite walls. The models are tested at different fiber-to-resin volume ratios (30:70–75:25) and various fiber-to-resin thermal conductivity ratios (0.2–5). The predicted thermal conductivity of the fiber can be accurately predicted throughout the spectrum via two models. The first model is a first-order formula (R ² = 0.94) while the second model is a second-order formula (R ² = 0.976). These two models can be used to predict the fiber thermal conductivity based on the easily measured resin and laminate values. A third model to predict the overall laminate thermal conductivity is introduced. The thermal conductivity of the composite panel is predicted with very high accuracy (R ² = 0.995). The thermal conductivity predicted via the use of these models has an excellent agreement with the experimental measurements. Another use of these models is to determine the fiber-to-resin volume ratio (if all thermal conductivities of fiber, resin and laminate are known).     

Numerical prediction of the thermal conductivity of fibers

The need to determine the thermal conductivity of fibers for design purposes of new composite materials and the inherent difficulties in the direct measurement of the thermal conductivity of fibers motivated the present work due to its importance for energy conservation purposes. In this work, a correlation formula is developed to predict the thermal conductivities of fiber as function of the effective thermal conductivity of a fiber-reinforced composite laminates and their constituents which are easy to measure. The parallel and series thermal models of composite walls have been utilized in developing this correlation equation. The coefficients of this formula can be given as functions of the voids volume fraction for each fiber to resin volume ratio considered. The validity of the models is verified through finite element analysis. This model also shows excellent agreement with the available experimental values.     

A computational investigation on the potential energy surface of thiosulfeno with O(3P) reaction

The reaction paths of thiosulfeno radical (HS₂) with O(³P) have been investigated at the UB3LYP/aug-cc-pV(T + d)Z and UCCSD(T)/aug-cc-pV(T + d)Z//B3LYP levels. Two stable collision intermediates, HSSO and SS(H)O, have been considered for the HS₂ + O(³P) reaction. Four products of S + HSO, H + SSO, HS + SO, and S₂ + OH are obtained by starting from HSSO and SS(H)O. The calculated results show that the most feasible paths for the formation of S + HSO, H + SSO, and HS + SO products include no transition states in reaction path, while that of S₂ + OH product includes relatively high energy barriers of 23.0 kcal/mol. Therefore, S + HSO, H + SSO, and HS + SO are main products (with the stability other of HS + SO > H + SSO > S + HSO) and S₂ + OH is the second product in HS₂ + O(³P) reaction. Because, all intermediates, transition states, and products involved in the reaction paths lie below the initial reactants, the HS₂ + O(³P) reaction is expected to be rapid even at low temperatures.