Mechanistic investigation and DFT calculation of the new reaction between S-methylisothiosemicarbazide and methyl acetoacetate

A study on the synthesis and mechanistical aspects of formation of 3-methyl-5-oxo-3-pyrazolin-1-carboxamide (MOPC) starting from S-methylisothiosemicarbazide hydrogen iodide and methyl acetoacetate was performed. In the alkaline aqueous solution, the intermediate methyl acetoacetate S-methylisothiosemicarbazone undergoes substitution of CH₃S^? anion by hydroxide anion, cyclization, carbanion formation, and elimination of methanol, thus yielding corresponding Na-enolate salt of pyrazol-5-one derivative. The structure of the compound obtained after protonation of the formed enolate salt was determined by means of spectroscopic techniques and single-crystal X-ray diffraction analysis. The mechanism of conversion of methyl acetoacetate S-methylisothiosemicarbazone into MOPC was investigated by means of the B3LYP functional, and it was found that the reaction is thermodynamically controlled.     

Kinetic Study of the CCl2 Radical Recombination Reaction by Laser‐Induced Fluorescence Technique

An experimental setup that coupled IR multiple‐photon dissociation (IRMPD) and laser‐induced fluorescence (LIF) techniques was implemented to study the kinetics of the recombination reaction of dichlorocarbene radicals, CCl₂, in an Ar bath. The CCl₂ radicals were generated by IRMPD of CDCl₃. The time dependence of the CCl₂ radicals’ concentration in the presence of Ar was determined by LIF. The experimental conditions achieved allowed us to associate the decrease in the concentration of radicals to the self‐recombination reaction to form C₂Cl₄. The rate constant for this reaction was determined in both the falloff and the high‐pressure regimes at room temperature. The values obtained were k₀ = (2.23 ± 0.89) × 10^?29 cm⁶ molecules^?2 s^?1 and k_∞ = (6.73 ± 0.23) × 10^?13 cm³ molecules^?1 s^?1, respectively.     

New N-Substituted (±)-Dehydronorglaucine Analogs

The aporphine alkaloid N-carbethoxydehydronorglaucine (1) was found to have promising in vitro antitumor activity, but poor water solubility. We report the synthesis of 1, the efficient hydrolysis of its urethane group and the further transformation into several new dehydronorglaucine analogs.     

Efficient Two-Step Synthesis of 11,11′-Dithiobis[1-(2-bromo-2-methylpropionyloxy)undecane], a Conventional Initiator for Grafting Polymer Brushes from Gold Surfaces via ATRP

11,11′-Dithiobis[1-(2-bromo-2-methylpropionyloxy)undecane], a conventional initiator for grafting polymers from gold surfaces, was synthesized in two steps from 11-mercapto-1-undecanol in 88–92% overall yield. Oxidative dimerization of 11-mercapto-1-undecanol with a catalytic amount of sodium iodide and 30% hydrogen peroxide in ethyl acetate proceeded in 96% yield. Esterification with 2-bromoisobutyryl bromide in dichloromethane was clean and almost quantitative (92% yield) with pyridine used as base, whereas triethylamine gave a messy reaction (64% yield). Alternatively, esterification with 2-bromo-2-methyl-propanoic acid in dichloromethane occurred readily under Steglich's conditions with N,N′-dicyclohexylcarbodiimide (DCC) and a catalytic amount of dimethylaminopyridine (DMAP; 88% yield).     

A computational study on the stability–aromaticity correlation of triply N-confused porphyrins: CMMSE-09

The B3LYP density functional theory methodology in conjunction with the 6-31G(d,p) basis set has been used to characterize triply N-confused meso-tetraphenylporphyrins. According to our computations, there is no a direct correlation between stability and aromaticity as already found for non-substituted confused porphyrins. The inclusion of these substituents in the calculations provokes a decrease of the planarity and aromaticity of these macrocycles along with a notable rise of their relative stability with respect to the non-substituted case. Steric repulsions, both among phenyl rings and β atoms in the pyrrolic rings, and among H atoms in the core of the macrocycles, dominate over aromaticity in the establishment of the most stable conformation of each isomer.     

Hydrogen-bonded LC nanocomposites: characterisation of nanoparticle-LC interactions by solid-state NMR and FTIR spectroscopies

Although the molecular-level nanoparticle-liquid crystal (NP-LC) interactions are key for forming stable NP dispersions in LC, characterisation of these interactions is scarce in the literature. Recently, we have developed hydrogen-bonded LC nanocomposites based on mesogenic carboxylic acids and NPs functionalised with hydrogen-bond acceptor/donor groups. Here, we apply solid-state ¹H and ¹³C NMR and Fourier transform infrared spectroscopies to model systems consisting of mixtures of trans-4-n-butylcyclohexanecarboxylic acid (4-BCHA), 4-hexylbenzoic acid (6BA) and 4,4?-bipyridine. The binary mixture, 4-BCHA:6BA, was also studied. The results were compared to monolayer quantities of 6BA and 4-BCHA adsorbed on pyridine functionalised zirconia NPs (ZrO₂-n₃-pyridine) to understand the different effects of the functionalised NPs on the LC properties.     

Parallel Newton Two-Stage Multisplitting Iterative Methods for Nonlinear Systems

Parallel Newton two-stage iterative methods to solve nonlinear systems are studied. These algorithms are based on both the multisplitting technique and the two-stage iterative methods. Convergence properties of these methods are studied when the Jacobian matrix is either monotone or an H-matrix. Furthermore, in order to illustrate the performance of the algorithms studied, computational results about these methods on a distributed memory multiprocessor are discussed.This revised version was published online in October 2005 with corrections to the Cover Date.     

Dispersive micro-solid phase extraction of 16 priority polycyclic aromatic hydrocarbons from water by using thermally treated clinoptilolite,and their quantification by GC-MS

The authors report on a novel sorbent (thermally treated natural zeolite; clinoptilolite) for use in dispersive micro-solid phase extraction (D-μ-SPE) of polycyclic aromatic hydrocarbons (PAHs) from water samples. The method was applied to the D-μ-SPE of 16 priority PAHs which then were quantified by gas chromatography with mass spectrometric detection (GC-MS). The method was validated in terms of specificity and selectivity, linearity and linear range, accuracy, precision, uncertainty, limits of detection and quantification. Figures of merit include (a) linear analytical ranges between 2.08 and 208 ppb, and (b) detection limits in the range from 0.01 to 0.92 ppb. The method was successfully applied to the determination of PAHs in river waters.

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Graphical abstract Schematic representation of dispersive micro-solid phase extraction (D-μ-SPE) of trace levels of PAHs in water samples by using thermally treated clinoptilolite as sorbent prior to gas chromatography-mass spectrometry analysis (GC-MS).

     

Chopped CW laser-induced optogalvanic effect in a neon hollow cathode discharge

A detailed model for the optogalvanic effect in a neon hollow cathode discharge irradiated by a chopped CW dye laser is presented. A rate equation formalism is used to calculate the evolution of the first and second electronic configuration populations coupled by the laser and of the electric charges number density. Processes as ambipolar-like electrons loss, electronic collisional coupling of level populations and electron emission by the cathode due to VUV radiation from the 1s ₂ resonant level are taken into account and further discussed.The transients and steady-state magnitude of the optogalvanic signal are calculated, compared with experimental data and related to population changes. We predict sign changes of the optogalvanic signal when the laser is tuned over transitions originating from the resonant level with respect to transitions involving the metastables states. The optogalvanic signal is shown to be basically determined by the laser-induced variations of the excited-state populations while changes in the electron temperature, due to laser energy transfer by collisions between electrons and excited atoms, play a negligible role.     

Comprehensive comparison of ligand-based virtual screening tools against the DUD data set reveals limitations of current 3D methods

In recent years, many virtual screening (VS) tools have been developed that employ different molecular representations and have different speed and accuracy characteristics. In this paper, we compare ten popular ligand-based VS tools using the publicly available Directory of Useful Decoys (DUD) data set comprising over 100?000 compounds distributed across 40 protein targets. The DUD was developed initially to evaluate docking algorithms, but our results from an operational correlation analysis show that it is also well suited for comparing ligand-based VS tools. Although it is conventional wisdom that 3D molecular shape is an important determinant of biological activity, our results based on permutational significance tests of several commonly used VS metrics show that the 2D fingerprint-based methods generally give better VS performance than the 3D shape-based approaches for surprisingly many of the DUD targets. To help understand this finding, we have analyzed the nature of the scoring functions used and the composition of the DUD data set itself. We propose that to improve the VS performance of current 3D methods, it will be necessary to devise screening queries that can represent multiple possible conformations and which can exploit knowledge of known actives that span multiple scaffold families.