Synthesis,characterization, duplex-DNA interactions,and anticancer activities of novel octahedral [Ni(phen)2(dppz-idzo)]2+ and [Co(phen)2(dppz-idzo)]3+ complexes

Two new octahedral [Ni(phen)₂(dppz-idzo)]²⁺ and [Co(phen)₂(dppz-idzo)]³⁺ complexes have been synthesized and characterized by CHN analysis, electrospray ionization-MS, nuclear magnetic resonance, and UV–Vis spectra. The DNA-binding ability of these complexes was spectrophotometrically, hydrodynamically, and electrophoretically evaluated which indicated that they strongly intercalate into the DNA double helix, and that both induced severe DNA damage in the presence of peroxide. The complexes also showed strong antiproliferative effect against HepG2 and MDA-MB-231 cells. By contrast, they were found to be inactive against the MCF-7 cell line. The ligand itself was found to be inactive against the cells tested.     

On the existence of $$\kappa $$-existentially closed groups

Using explicit constructions of the Weierstrass mock modular form and Eisenstein series coefficients, we obtain closed formulas for the generating functions of values of shifted convolution L-functions associated to certain elliptic curves. These identities provide a surprising relation between weight 2 newforms and shifted convolution L-values when the underlying elliptic curve has modular degree 1 with conductor N such that \(\text {genus}(X_0(N)) = 1\).     

Origin of magnetic interactions and their influence on the structural properties of Ni2MnGa and related compounds

In this work, we perform first-principles DFT calculations to investigate the interplay between magnetic and structural properties in Ni(2)MnGa. We demonstrate that the relative stability of austenite (cubic) and non-modulated martensite (tetragonal) phases depends critically on the magnetic interactions between Mn atoms. While standard approximate DFT functionals stabilize the latter phase, a more accurate treatment of electronic localization and magnetism, obtained with DFT+U, suppresses the non-modulated tetragonal structure for the stoichiometric compound, in better agreement with experiments. We show that the Anderson impurity model, with Mn atoms treated as magnetic impurities, can explain this observation and that the fine balance between super-exchange RKKY type interactions mediated by Ni d and Ga p orbitals determines the equilibrium structure of the crystal. The Anderson model is also demonstrated to capture the effect of the number of valence electrons per unit cell on the structural properties, often used as an empirical parameter to tune the behavior of Ni(2)MnGa based alloys. Finally, we show that off-stoichiometric compositions with excess Mn promote transitions to a non-modulated tetragonal structure, in agreement with experiments.     

Segmental dynamics in poly(methyl acrylate) on silica: molecular-mass effects

The effect of molecular mass on the segmental dynamics of poly(methyl acrylate) (PMA) adsorbed on silica was studied using deuterium quadrupole-echo nuclear magnetic resonance (NMR) and modulated differential scanning calorimetry. Samples adsorbed on silica (all about 1.5 mg PMA/m2 silica) were shown to have more restricted segmental mobility, and higher Tg's, than the corresponding bulk PMA samples. Around the glass-transition region, adsorbed samples exhibited segmental mobility, which could be classified as heterogeneous due to a superposition of more-mobile and less-mobile components present in the deuterium NMR spectra. This heterogeneity was consistent with a motional gradient with more-mobile segments near the polymer-air interface and the less-mobile species near the polymer-silica interface. The mobility of the adsorbed 77 kDa PMA sample was the lowest among the four different molecular-mass samples studied. Samples studied with masses both larger and smaller than 77 kDa had larger mobile-component fractions in the adsorbed polymer. The additional mobility was attributed to the presence of either longer tail and loop conformations in the higher molecular-mass samples or the inherent mobility of the tails in the lower molecular-mass samples on the surface.     

Adhesion of biologically inspired vertical and angled polymer microfiber arrays

This paper proposes an approximate adhesion model for fibrillar adhesives for developing a fibrillar adhesive design methodology and compares numerical simulation adhesion results with macroscale adhesion data from polymer microfiber array experiments. A technique for fabricating microfibers with a controlled angle is described for the first time. Polyurethane microfibers with different hardnesses, angles, and aspect ratios are fabricated using optical lithography and polymer micromolding techniques and tested with a custom tensile adhesion measurement setup. Macroscale adhesion and overall work of adhesion of the microfiber arrays are measured and compared with the models to observe the effect of fiber geometry and preload. The adhesion strength and work of adhesion behavior of short and long vertical and long angled fiber arrays have similar trends with the numerical simulations. A scheme is also proposed to aid in optimized fiber adhesive design.     

Interaction between green tea extract and 99mTc-pertechnetate on in vivo distribution

People drink various types of tea without knowing the side effects of biological and chemical contents and radiopharmaceutical interactions. In current study, it is aimed to evaluate the effects of green tea extract in different extraction solvents on the radiolabeling of the blood constituents with ^99mTc and on the biodistribution of radiopharmaceutical sodium pertechnetate (Na^99mTcO₄) in male Wistar Albino rats. The extraction of green tea was performed in different solvents. Biodistribution studies were performed on male rats which were treated via gavage with green tea extract in different extraction solvents or saline (0.9 % NaCl) as a control group for 7 days. The radiolabeling of blood constituents performed incubating with SnCl₂ and ^99mTc. According to experimental results, radiolabeling blood components with ^99mTc were not modified in the usage of the different extraction solvents for green tea extraction, but a significant alteration (P < 0.05) of biodistribution of Na^99mTcO₄ was observed after treatment with green tea extract in distilled water. Although there is no considerable effect on radiolabeling of blood components, there is an outstanding change on the biodistribution studies especially with green tea extract in distilled water. The identified change monitored in this study may cause to reduce the risk of misdiagnosis and/or avoid the repetition of the examinations in nuclear medicine.     

Optimization of Microwave-Assisted Extraction (MAE) for the Isolation of Antioxidants from Basil (Ocimum basilicum L.) by Response Surface Methodology (RSM)

Abstract

The recovery of antioxidants from basil (Ocimum basilicum L.) was modeled with the aid of response surface methodology (RSM) using microwave-assisted extraction (MAE). Face-centered central design (FCCD) was employed to optimize the MAE operational parameters including the extraction time (1 to 7?min), extraction temperature (30 to 120?°C), solid-to-solvent ratio (0.1 to 0.4), and solvent concentration (20 to 80% ethanol, v/v), and to obtain the best possible combinations of these parameters for a high antioxidant yield from basil. The total antioxidant capacity (TAC) was expressed in trolox (TR) equivalents per gram of dried sample (DS). Three of the operational parameters (temperature, extraction time and solvent concentration) were shown to have significant effect on the extraction efficiency of antioxidants in basil extracts (p?<?0.05). The solvent concentration was shown to be the most significant factor on antioxidant yield obtained by MAE. There was a close relationship between experimental and predicted values using the proposed method. This optimized MAE method shows an application potential for the efficient extraction of antioxidants from basil in the food and pharmaceutical industries.     

Transition-Metal Catalysis of Triene 6π Electrocyclization: The π-Complexation Strategy Realized

Triene 6π electrocyclization, wherein a conjugated triene undergoes a concerted stereospecific cycloisomerization to a cyclohexadiene, is a reaction of great historical and practical significance. In order to circumvent limitations imposed by the normally harsh reaction conditions, chemists have long sought to develop catalytic variants based upon the activating power of metal–alkene coordination. Herein, we demonstrate the first successful implementation of such a strategy by utilizing [(C₅H₅)Ru(NCMe)₃]PF₆ as a precatalyst for the disrotatory 6π electrocyclization of highly substituted trienes that are resistant to thermal cyclization. Mechanistic and computational studies implicate hexahapto transition-metal coordination as responsible for lowering the energetic barrier to ring closure. This work establishes a foundation for the development of new catalysts for stereoselective electrocyclizations.     

Cobalt(II), nickel(II) and copper(II) complexes of a Schiff base ligand: synthesis,structural characterization and luminescence properties

A Schiff base ligand (HL), 2,4-dimethoxy-N-(5-chloro-2-hydroxybenzylidene)-benzenamine, derived from 5-chloro-2-hydroxybenzaldehyde and 2,4-dimethoxyaniline, and its metal complexes [Co(L)₂]·CH₃OH (1), [Ni(L)₂] (2), [Cu(L)₂] (3) have been synthesized. The compounds were characterized by analytical and spectroscopic methods. In addition, the structures of the Schiff base HL and its Co(II) complex were determined by single-crystal X-ray analysis. The Co(II) center is six-coordinate, being coordinated to two imine nitrogen, two phenolate oxygen and two methoxy oxygen atoms of two crystallographically independent Schiff base ligands. Luminescence properties of HL and its complexes were investigated both in solution and in the solid state.     

Infrared multiphoton excitation of small molecules

The collisionless infrared excitation by short CO₂ laser pulses of the molecules SO₂, OCS, NO₂, NH₃ and DN₃ is compared with that of larger molecules. The average number of photons absorbed per molecule and the fraction of molecules dissociated depends predominantly on the laser intensity, while for larger molecules with higher densities of vibrational states the excitation is primarily determined by the laser fluence.