One-pot synthesis,spectroscopic characterization and DFT study of novel 8-azacoumarin derivatives as eco-friendly insecticidal agents

A series of sixteen 8-azacoumarin derivatives bearing aryl moieties at C-5 and C-7 was designed and synthesized by a concise and facile procedure utilizing grinding and ultrasound approaches. The efficient multi-component protocols proceeded smoothly and in the absence of solvent to furnish the target products in moderate to good yields. All the synthesized molecules were characterized via ¹HNMR, ¹³CNMR, IR, mass spectra, and elemental analyses. The density functional theory (DFT) was then used to discover the structural and electronic characteristics of such compounds. Finally, an insecticidal study against Plutella xylostella and Helicoverpa armigera on the synthesized compounds is reported. The bioassay results indicated that some of the tested compounds showed potency ranging from good to moderate. In particular, analogs 6i and 6l, among the tested compounds, showed even more potency than commercial chlorpyrifos. On the other hand, the rest of the tested compounds showed moderate to weak activities.     

Arylhydrazonals as the aldehyde component in Baylis-Hillman reactions

Arylhydrazonals were added to acrylonitrile or methyl vinyl ketone in the presence of DABCO or benzotriazole to yield the intermediate Baylis-Hillman adduct that cyclized under the reaction conditions with water elimination to yield dihydropyridazines. A pyridazine reacted with DMAD to yield a pyridine via a [4+2] Diels-Alder addition followed by retro Diels-Alder elimination of methylene aniline. Two pyridazines were condensed with DMFDMA to yield the corresponding enaminones that reacted with NH₂NH₂ to afford the pyrazolylpyridazines.     

Gas‐phase thermolysis of benzotriazole derivatives. Part 4. Pyrolysis of 1‐acylbenzotriazole phenylhydrazones. Interesting direct routes towards N‐aminobenzimidazoles

Flash vacuum pyrolysis (FVP) of 1‐acylbenzotriazole phenylhydrazones gave benzonitriles, aniline and 2‐arylbenzimidazole derivatives. Static pyrolysis of the same substrates at 180 °C gave exclusively the corresponding N‐anilino‐2‐arylbenzimidazole derivatives. Pyrolysis of the isomeric 2‐acylbenzotriazole phenylhydrazones gave similar products.     

MIDA- and TIDA-Boronates Stabilize α-Radicals Through B−N Hyperconjugation

Multifunctional organoboron compounds increasingly enable the simple generation of complex, Csp³-rich small molecules. The ability of boron-containing functional groups to modify the reactivity of α-radicals has also enabled a myriad of chemical reactions. Boronic esters with vacant p-orbitals have a significant stabilizing effect on α-radicals due to delocalization of spin density into the empty orbital. The effect of coordinatively saturated derivatives, such as N-methyliminodiacetic acid (MIDA) boronates and counterparts, remains less clear. Herein, we demonstrate that coordinatively saturated MIDA and TIDA boronates stabilize secondary alkyl α-radicals via σ_B-N hyperconjugation in a manner that allows site-selective C−H bromination. DFT calculated radical stabilization energies and spin density maps as well as LED NMR kinetic analysis of photochemical bromination rates of different boronic esters further these findings. This work clarifies that the α-radical stabilizing effect of boronic esters does not only proceed via delocalization of radical character into vacant boron p-orbitals, but that hyperconjugation of tetrahedral boron-containing functional groups and their ligand electron delocalizing ability also play a critical role. These findings establish boron ligands as a useful dial for tuning reactivity at the α-carbon.     

Isobaric metabolite interferences and the requirement for close examination of raw data in addition to stringent chromatographic separations in liquid chromatography/tandem mass spectrometric analysis of drugs in biological matrix

In addition to matrix effects, common interferences observed in liquid chromatography/tandem mass spectrometry (LC/MS/MS) analyses can be caused by the response of drug-related metabolites to the multiple reaction monitoring (MRM) channel of a given drug, as a result of in-source reactions or decomposition of either phase I or II metabolites. However, it has been largely ignored that, for some drugs, metabolism can lead to the formation of isobaric or isomeric metabolites that exhibit the same MRM transitions as parent drugs. The present study describes two examples demonstrating that interference caused by isobaric or isomeric metabolites is a practical issue in analyzing biological samples by LC/MS/MS. In the first case, two sequential metabolic reactions, demethylation followed by oxidation of a primary alcohol moiety to a carboxylic acid, produced an isobaric metabolite that exhibits a MRM transition identical to the parent drug. Because the drug compound was rapidly metabolized in rats and completely disappeared in plasma samples, the isobaric metabolite appeared as a single peak in the total ion current (TIC) trace and could easily be quantified as the drug since it was eluted at a retention time very close to that of the drug in a 12-min LC run. In the second example, metabolism via the ring-opening of a substituted isoxazole moiety led to the formation of an isomeric product that showed an almost identical collision-induced dissociation (CID) MS spectrum as the original drug. Because two components were co-eluted, the isomeric product could be mistakenly quantified and reported by data processing software as the parent drug if the TIC trace was not carefully inspected. Nowadays, all LC/MS data are processed by computer software in a highly automated fashion, and some analysts may spend much less time to visually examine raw TIC traces than they used to do. Two examples described in this article remind us that quality data require both adequate chromatographic separations and close examination of raw data in LC/MS/MS analyses of drugs in biological matrix.     

Convergence and superconvergence analyses of HDG methods for time fractional diffusion problems

We study the hybridizable discontinuous Galerkin (HDG) method for the spatial discretization of time fractional diffusion models with Caputo derivative of order 0 < α < 1. For each time t ∈ [0, T], when the HDG approximations are taken to be piecewise polynomials of degree k ≥ 0 on the spatial domain Ω, the approximations to the exact solution u in the L _∞(0, T; L ₂(Ω))-norm and to ?u in the \(L_{\infty }(0, \textit {T}; \mathbf {L}_{2}({\Omega }))\)-norm are proven to converge with the rate h ^k+1 provided that u is sufficiently regular, where h is the maximum diameter of the elements of the mesh. Moreover, for k ≥ 1, we obtain a superconvergence result which allows us to compute, in an elementwise manner, a new approximation for u converging with a rate h ^k+2 (ignoring the logarithmic factor), for quasi-uniform spatial meshes. Numerical experiments validating the theoretical results are displayed.     

The Sextic Centrifugal Distortion Terms for an Open-Shell Complex Consisting of a Diatomic Molecule in a Σ Electronic State and a Closed-Shell Partner

An effective Hamiltonian for calculating rotational energy levels of an open-shell diatomic molecule, in a ^2S+1Σ electronic state, weakly bonded to a closed-shell partner was presented (W. M. Fawzy, J. Mol. Spectrosc. 191, 68–80 (1998)). The Hamiltonian was given as H = H_ev + H_rot + H_sr + H_ss + H_cd + H_srcd + H_sscd, where all the quartic centrifugal distortion correction terms were included in the Hamiltonian term H_cd but the sextic centrifugal distortion terms were ignored. This Hamiltonian is useful in cases where the complex has a well-defined equilibrium geometry and if the barrier to large-amplitude motion is large compared to the rotational constant of both the closed-shell molecule and its paramagnetic partner; if the barrier to large-amplitude motion is small compared to the rotational constant of one or both of the fragments, then a different treatment is required. In this paper, we introduce the new Hamiltonian terms H^sex(A)_cd and H^sex(S)_cd, which represent the sextic centrifugal distortion correction terms for an asymmetric rotor. We also introduce all the nonvanishing matrix elements of each of the H^sex(A)_cd and H^sex(S)_cd operators. These operators and their matrix elements are required for calculating the rotational energy levels of relatively high J values in the described type of weakly bonded open-shell complexes. The terms H^sex(A)_cd and H^sex(S)_cd and their matrix elements are also valid for any stable asymmetric rotor in a nondegenerate electronic state. A brief discussion of the new Hamiltonian terms and their matrix elements is given.     

Evaluation of the Antimicrobial Effect of Thymoquinone against Different Dental Pathogens: An In Vitro Study

This study aimed to evaluate the antimicrobial effect of Thymoquinone (TQ) on four different oral microorganisms. Minimum Bactericidal Concentration (MBC), Minimum Inhibition Concentration (MIC), Broth microdilution, and Well diffusion tests were used to determine the optimum antimicrobial concentrations of TQ against Streptococcus salivarius, Streptococcus oralis, Streptococcus mutans, and Staphylococcus aureus over 1, 3, 6, 12 and 24 h. Chlorhexidine 0.12% was selected as a positive control. The inhibitory effect of TQ on bacterial growth was most noticeable with S. salivarius, while the least affected was S. aureus. TQ’s MBC and MIC for S. oralis and S. aureus were comparable 2 mg/mL and 3 mg/mL, respectively. S. salivarius was most resistant to TQ and displayed a value of 5 mg/mL and 4 mg/mL for MIC and MBC, respectively. The viable count of different strains after exposure to TQ’s MBC values was most noticeable with S. aureus followed by S. oralis and S. mutans, while S. salivarius was least affected. This study emphasized the promising antimicrobial effect of TQ against the four main oral microorganisms. It has a potential preventive effect against dental caries as well as other oral diseases.