Theoretical analysis of frontier orbitals,electronic transitions,and global reactivity descriptors of M(CO)4L2 type metal carbonyl complexes: a DFT/TDDFT study

Structural Chemistry - Metal carbonyl complexes, which have been known as effective catalysts since early days, find use in many fields both directly and indirectly. Although the use of metal...     

Study of allelopathic effects of Eucalyptus erythrocorys L. crude extracts against germination and seedling growth of weeds and wheat

Allelopathic materials inside a tree can produce positive or negative change in the survival, growth, reproduction and behaviour of other organisms if they escape into the environment. To assess these effects, this work was carried out to evaluate the allelopathic impact of Eucalyptus erythrocorys L. on seed germination and seedling growth of two weeds: Sinapis arvensis L. and Phalaris canariensis L.; on one cultivated crop: Triticum durum L. Aqueous; and on ethanolic leaf extracts of E. erythrocorys L. The study was effected using four concentrations (10, 20, 25 and 30 μL/mL) while distilled water was used as a control. The results showed that the E. erythrocorys L. crude extracts had an inhibitory effect on seed germination and seedling growth of both studied weeds and wheat. The inhibition rate was increased by the increase in extract concentration. Only ethanolic extracts of E. erythrocorys L. induced a significant inhibition of seed germination of durum wheat. The effect of E. erythrocorys L. crude extracts was more severe on weeds than on durum wheat. These results indicate that the seedling growth, especially radicle elongation, was the more sensitive indicator to evaluate the effects of extracts than was the seed germination.     

Organocatalytic asymmetric 5-hydroxyisoxazolidine synthesis: a highly enantioselective route to beta-amino acids

The highly chemo- and enantioselective organocatalytic tandem reaction between N-protected hydroxyl amines and alpha,beta-unsaturated aldehydes is presented; the reaction provides access to 5-hydroxyisoxazolidines and beta-amino acids in high yields and with 90-99% ee.     

Unexpected decomposition of the bis (trifluoromethylsulfonyl) amide anion during electrochemical copper oxidation in an ionic liquid

In this letter we report on the decomposition of the bis (trifluoromethylsulfonyl) amide (TFSA) anion under quite mild electrochemical conditions. The results show clearly that the TFSA anion can easily be decomposed during anodic oxidation of copper in the ionic liquid 1-butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl) amide [BMP] TFSA at 70 °C leading to the formation of CuF₂. At room temperature, however, no significant decomposition was obtained. Therefore, one has to be very careful in applying ionic liquids based on TFSA anions under anodic conditions at elevated temperature as the TFSA anion might decompose, depending on the anode material.     

Kinetic and mechanistic investigations on the oxidation of N’-heteroaryl unsymmetrical formamidines by permanganate in aqueous alkaline medium

Kinetic studies on the oxidation of two substituted azinyl formamidines (Azn-Fs), namely N,N-dimethyl-N’-(pyrimidin-2-yl) formamidine (Pym-F) and N,N-dimethyl-N’-(pyridin-2-yl) formamidine (Py-F), by alkaline permanganate have been performed by spectrophotometry. The spectroscopic and kinetic evidence reveals the formation of 1:1 intermediate complexes between the oxidant and substrates. The influence of pH on the oxidation rates indicated that the reactions are base-catalyzed. The reactions show identical kinetics, being first order each in [MnO₄ ^?]₀ and [Azn-F]₀, but with a fractional first-order dependence on [OH^?]. The effect of temperature on the reaction rate has been studied. Increasing ionic strength has no significant effect on the rate. The final oxidation products of Pym-F and Py-F were identified as 2-aminopyrimidine and 2-aminopyridine, respectively, in addition to dimethyl amine and carbon dioxide. Under comparable experimental conditions, the oxidation rate of Py-F is higher than that of Pym-F. A reaction mechanism adequately describing the observed kinetic behavior is proposed, and the reaction constants involved in the different steps of the mechanism have been evaluated. The activation parameters with respect to the rate-limiting step of the reactions, along with thermodynamic quantities, are presented and discussed.     

Modeling of absorption kinetics of poly(acrylamide) hydrogels crosslinked by EGDMA and PEGDMAs

In this study, acrylamide-based hydrogels are synthesized by free radical solution polymerization in aqueous solution using ethylene glycol dimethacrylate (EGDMA) and its derivative polyethylene glycol dimethacrylate (PEGDMA) with different molecular weights as crosslinkers in the solution medium. The Fourier transform infrared spectroscopy technique is used for the structural characterization of the hydrogels. Dynamic swelling tests are conducted on acrylamide-based hydrogels for the determination of the swelling characteristics with respect to different crosslinking concentrations at room temperature. The parameters of swelling kinetics and diffusion mechanisms of the hydrogels are calculated with the aid of the data obtained. Accordingly, PEGDMA and EGDMA absorption capacity is found to increase with increasing concentrations. The lowest and highest water absorption capacities in PEGDMA₈₁₀ and EGDMA crosslinked hydrogels are 22.73–48.39 and 10.15–16.02 g/g, respectively. Water intake of hydrogels crosslinked by EGDMA and PEGDMAs followed Fickian nature type diffusion except for PEGDM₈₁₀, which has a swelling exponent greater than 0.5 and so does not follow a Fickian type of diffusion. PEGDM₈₁₀ showed the fastest diffusion rate of between 5.87 × 10^?4 and 10.87 × 10^?4 cm² s^?1.     

Intramolecular energy-transfer in a europium(III) chelate with salicylidene-valinate schiff base

Summary An intense fluorescence,⁵D⁷F, of the europium(III) ion was observed at room temperature in DMSO and DMF solutions of the europium(III) chelate with salicylidene-valinate Schiff base, as a result of an intramolecular energy-transfer from the ligand to the metal ion. The metal chelate has been characterized and appears to possess an octahedral configuration. These results offer an interesting opportunity to probe the active sites of pyridoxal enzymes.     

Comparative High-Performance Liquid Chromatographic and High-Performance Thin-Layer Chromatographic Study for the Simultaneous Determination of Dapagliflozin and Metformin Hydrochloride in Bulk and Pharmaceutical Formulation

JPC – Journal of Planar Chromatography – Modern TLC - The discovery of potent antidiabetic drugs is of necessity owing to the rapid prevalence of diabetes worldwide. The investigation...     

Dodecanoyl isothiocyanate and N′-(2-cyanoacetyl) dodecanehydrazide as precursors for the synthesis of different heterocyclic compounds with interesting antioxidant and antitumor activity

Dodecanoyl isothiocyanate 1 was utilized for the construction of thioureido, 2-thioxo-2,3-dihydroquinazolin-4(1H)-one, benzo[d]-1,3-thiazin-4(H)-one and 3-amino quinazolin-4(3H)-one derivatives 2, 3, 4, and 5 respectively. However, N′-(2-cyanoacetyl) dodecanehydrazide 6 was also used as a key starting material for the construction of a variety of new pyrazolone, pyrazole, thiadiazole, pyridazine, chromeno[2,3-c]pyrazole, and dithiolane derivatives 7, 9, 12, 15, 18, and 20, respectively. The newly synthesized compounds were characterized by elemental analyses and spectral data (IR, ¹H NMR, and mass spectra). Some of the newly synthesized compounds bearing heterocyclic moieties were tested for antioxidant activity as reflected in their ability to inhibit oxidation in rat brain and kidney homogenates using 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) inhibition. Also, in vitro anticancer activity was examined using the standard (3-(4,5-dimethylthiazolyl-2)-2,5-diphenyltetrazolium bromide) (MTT) method against a panel of two human tumor cell lines namely; hepatocellular carcinoma HepG2 and mammary gland breast cancer MCF-7. Compounds 12 and 16b exhibited the highest activities as antioxidant and antitumor agents. Meanwhile, compounds 7 and 20 showed moderate activities and the rest of the tested compounds showed weak activities.