Substituent effect on local aromaticity in mono and di‐substituted heterocyclic analogs of naphthalene

A quantitative study on local aromaticity has been performed on a series of mono‐ and di‐substituted biheterocycles (quinoline, isoquinoline, quinoxaline, quinazoline). Three electronically based indices (PDI, ATI, and FLU) have been employed to investigate the substituent effect on the π‐electron delocalization in both heterocycle and benzenoid rings. Three typical substituents (Cl, OCH₃, and CN) with different inductive and resonance power have been selected. Generally, substituent causes a reduction in aromaticity irrespective of whether it is electron attracting or electron donating. It is shown that the maximum aromaticity exhibits a similar trend of Cl > CN > OCH₃ for all the studied rings. Moreover, it is found that the substituent situation with respect to the heteroatom has a significant influence on the aromaticity. It results from our study that in di‐substituted derivatives, irrespective of whether the two substituents form a meta or para isomer, they preferably choose the position which leads to the maximum aromaticity character. Copyright © 2009 John Wiley & Sons, Ltd.     

Approximating fixed points of mappings satisfying condition (E) in Busemann space

It is well-known that in a Banach space, using the Ishikawa iterative process, one can find fixed points of nonexpansive mappings via asymptotic center’s method. In this paper, we obtain the fixed points of mappings satisfying so-called condition (E) in a uniformly convex Busemann space. Many known results in CAT (0) spaces are improved and extended by our results.     

Photocatalytic oxidation of primary and secondary benzylic alcohols to carbonyl compounds catalyzed by H3PW12O40/SiO2 under an O2 atmosphere

An efficient, selective and green procedure for the photocatalytic oxidation of primary and secondary benzylic alcohols to the corresponding aldehydes and ketones has been achieved using silica-encapsulated H₃PW₁₂O₄₀ as a recyclable heterogeneous photocatalyst in acetonitrile under oxygen gas as the sole reoxidant of the catalyst.     

Silver–palm pollen nanocomposite exhibits antiproliferative,antioxidant, and proapoptotic properties on MCF-7 breast cancer cells

The aim of the present study is to evaluate the antioxidant and proapoptotic effects of silver–palm pollen (Ag/PP) nanocomposite. The percentage of live cells after treatment with various concentrations of Ag/PP (0, 5, 10, 20, and 40 µM/mL) was determined by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) colorimetric assay. The antioxidant potential of Ag/PP was measured via the scavenging effects of 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) and molecular analysis. Apoptosis was assessed by morphological analysis, fluorescent dye, and flow cytometry, and its fundamental mechanism studied based on evaluation of Bax and Bcl2 gene expression. Ag/PP nanocomposite suppressed the viability of MCF-7 cells (dose and time dependently) and showed antioxidant properties. Morphological changes associated with cell death were observed in treated cells. Accumulation of dead cells in sub-G1 phase confirmed the occurrence of apoptosis in exposed cells. In addition, NPs induced cell death by altering Bcl-2 expression in MCF-7 cells. These results indicate that Ag/PP nanocomposite is an effective combination for removal of cancer cells by induction of apoptosis and could be useful for human health due to its antioxidant effects.     

Topical propolis improves wound healing in patients with diabetic foot ulcer: a randomized controlled trial

In this randomized controlled trial, diabetic patients with foot ulcers (Wagner grades 1 and 2) were randomly assigned to conventional therapies for diabetic foot ulcer plus topical propolis ointment (5%; twice daily) or conventional therapies alone. The process of ulcer healing was observed during 4 weeks and compared between the two groups regarding the size, erythema, exudates, white blood cell (WBC) count and erythrocyte sedimentation rate (ESR). The process of ulcer size reduction during the four-week period of study was significantly different between the groups. However, this difference was not significant between the third and fourth weeks. There was no significant difference between two groups regarding erythema and exudate reduction as well as WBC count and ESR. Administration of topical propolis ointment in addition to the conventional treatments of diabetic foot ulcer could reduce the size of ulcers with Wagner grades 1 and 2.     

New class of verdoheme analogues with weakly coordinating anions: the structure of (mu-oxo)bis[(octaethyloxoporphinato)iron(III)] hexafluorophosphate

Three new verdoheme analogues with weakly coordinating anions, [OEOPFe(II)X], where OEOP is the monoanion of octaethyloxoporphyrin and X = PF(6), ClO(4), and BF(4), have been synthesized and characterized by spectroscopic methods. (1)H NMR spectroscopy reveals that the [OEOPFe(II)X] species are paramagnetic, and the iron is five-coordinate (S = 2). The oxidation of [OEOPFe(II)PF(6)] with dioxygen yields [(OEOPFe)(2)O](PF(6))(2). The structure of (mu-oxo)bis[(octaethyloxoporphinato)iron(III)] has been determined by X-ray diffraction analysis. The eight Fe-N bond distances have an average value of 2.077(3) Angstroms. The oxygen atom sits on the inversion center, and the average axial Fe-O bond length is 1.756(3) Angstroms. The average displacement of the iron(III) atom from the mean porphinato core is 0.60 Angstroms. Crystal data: crystal system, monoclinic; a = 8.7114(10) Angstroms; b = 26.102(4) Angstroms; c = 15.8323(14) Angstroms; beta = 104.134(6) degrees ; space group P2(1)/c; V = 3491.1(7) Angstroms (3); Z = 2; R1 = 0.0546, wR2 =0.1145 for data with I > 2sigma(I).     

3D-QSAR modeling of maximum steady-state fluxes of some substituted benzenes and quinolone derivatives through polydimethylsiloxane membrane

The maximum steady-state flux of 79 compounds (substituted benzenes, and quinolones and their derivatives) with a wide range of polarity through a PDMS membrane was predicted using a comparative molecular field analysis (CoMFA) and comparative molecular similarity index analysis (CoMSIA) methods. Moreover, the contribution of partial atomic charge to mass transport phenomena was further verified by the correlation of atomic charge to apparent permeability through polydimethylsiloxane (PDMS) membranes. The obtained results indicated superiority of CoMSIA model over CoMFA model. The best CoMSIA model is developed based on the combination of electrostatic and hydrophobic and H-bond acceptor fields (CoMSIA-EHA). The contour maps of electrostatic and hydrophobic and H-bond acceptor fields of CoMSIA model provide an interpretable and logical relationship between chemicals structure and their fluxes, which give useful insights for designing new compounds with higher penetration through the membranes.     

Luminescent mononuclear and dinuclear cycloplatinated (II) complexes comprising azide and phosphine ancillary ligands

A new series of cycloplatinated (II) complexes with general formulas of [Pt (bhq)(N₃)(P)] [bhq = deprotonated 7,8‐benzo[h]quinoline, P = triphenyl phosphine (PPh₃) and methyldiphenyl phosphine], [Pt (bhq)(P^P)]N₃ [P^P = 1,1‐bis (diphenylphosphino)methane (dppm) and 1,2‐bis (diphenylphosphino)ethane] and [Pt₂(bhq)₂(μ‐P^P)(N₃)₂] [P^P = dppm and 1,2‐bis (diphenylphosphino)acetylene] is reported in this investigation. A combination of azide (N₃^?) and phosphine (monodentate and bidentate) was used as ancillary ligands to study their influences on the chromophoric cyclometalated ligand. All complexes were characterized by nuclear magnetic resonance spectroscopy. To confirm the presence of the N₃^? ligand directly connected to the platinum center, complex [Pt (bhq)(N₃)(PPh₃)] was further characterized by single‐crystal X‐ray crystallography. The photophysical properties of the new products were studied by UV–Vis spectroscopy in CH₂Cl₂ and photoluminescence spectroscopy in solid state (298 or 77 K) and in solution (77 K). Using density functional theory calculations, it was proved that, in addition to intraligand charge‐transfer (ILCT) and metal‐to‐ligand charge‐transfer (MLCT) transitions, the L′LCT (L′ = N₃, L = C^N) electronic transition has a remarkable contribution in low energy bands of the absorption spectra (for complexes [Pt (bhq)(N₃)(P)] and [Pt₂(bhq)₂(μ‐P^P)(N₃)₂]). It is indicative of the determining role of the N₃^? ligand in electronic transitions of these complexes, specifically in the low energy region. In this regard, the photoluminescence studies indicated that the emissions in such complexes originate from a mixed ³ILCT/³MLCT (intramolecular) and also from aggregations (intermolecular).     

Fluorescence and DNA-binding spectral studies of neodymium(III) complex containing 2,2′-bipyridine, [Nd(bpy)2Cl3·OH2]

The interaction of [Nd(bpy)₂Cl₃·OH₂], where bipy is 2,2′-bipyridine, with DNA has been studied by absorption, emission, and viscosity measurements. [Nd(bpy)₂Cl₃·OH₂] showed absorption decreasing in charge transfer band with increasing of DNA. The binding constant, K_b has been determined by absorption measurement and found to be (1.5 ± 0.1) × 10⁵ M^?1. The fluorescent of [Nd(bpy)₂Cl₃·OH₂] has been investigated in detail. The interaction was also studied by fluorescence quenching technique. The results of fluorescence titration revealed that DNA had the strong ability to quenching the intrinsic fluorescence of Nd(III) complex at 327 nm. The binding site number n, apparent binding constant K_b and the Stern–Volmer quenching constant K_SV have been determined. Thermodynamic parameters have been calculated according to relevant fluorescent data and Van’t Hoff equation. Characterization of bonding mode has been studied. The results suggested that the major interaction mode between [Nd(bpy)₂Cl₃·OH₂] and DNA was groove binding.