M?ssbauer study of peroxynitrito complex formation with FeIII-chelates

The reaction of the μ-oxo-diiron(III)-L complex (L = EDTA, ethylene diamine tetraacetate, HEDTA, hydroxyethyl ethylene diamine triacetate, and CyDTA, cyclohexane diamine tetraacetate) with peroxynitrite in alkaline solution was studied by M?ssbauer spectroscopy using rapid-freezing technique. These complexes yield an (L)Fe^III(η ²-O $_{2})^{3-}$ complex ion when they react with hydrogen peroxide and the formation of the peroxide adduct results in a deep purple coloration of the solution. The same color appears when the reaction occurs with peroxinitrite. Although spectrophotometry indicated some difference between the molar extinction coefficients of the peroxo and the peroxinitrito adducts, the M?ssbauer parameters proved to be the same within experimental error. It is concluded that the peroxynitrite ion decomposes when reacting with Fe^III(L) and the peroxo adduct forms.     

Conotoxin engineering: dual pharmacophoric noradrenaline transport inhibitor/integrin binding peptide with improved stability

A dual-pharmacophoric peptide was engineered by grafting the integrin binding RGD motif between the C- and N-termini of a disulfide-rich noradrenaline transporter inhibiting χ-conotoxin resulting in a stable backbone cyclized peptide. The construct maintained two independent biological activities and showed increased plasma stability with no adverse effects observed following administration to rats, highlighting the potential value of pharmacophore grafting into constrained peptide scaffolds.     

Quantum Ergodic Restriction Theorems. I: Interior Hypersurfaces in Domains with Ergodic Billiards

Quantum ergodic restriction (QER) is the problem of finding conditions on a hypersurface H so that restrictions \({\phi_j |_H}\) to H of Δ-eigenfunctions of Riemannian manifolds (M, g) with ergodic geodesic flow are quantum ergodic on H. We prove two kinds of results: First (i) for any smooth hypersurface H in a piecewise-analytic Euclidean domain, the Cauchy data \({(\phi_j|H,\partial_{\nu}^H \phi_j|H)}\) is quantum ergodic if the Dirichlet and Neumann data are weighted appropriately. Secondly, (ii) we give conditions on H so that the Dirichlet (or Neumann) data is individually quantum ergodic. The condition involves the almost nowhere equality of left and right Poincaré maps for H. The proof involves two further novel results: (iii) a local Weyl law for boundary traces of eigenfunctions, and (iv) an ‘almost-orthogonality’ result for Fourier integral operators whose canonical relations almost nowhere commute with the geodesic flow.     

Structural effects of lipophilic methotrexate conjugates on model phospholipid biomembranes

Lipophilic conjugates of the antitumor drug methotrexate (MTX) with lipoamino acids (LAAs) have been previously described as a tool to enhance MTX passive entrance into cells, overcoming a form of transport resistance which makes tumour cells insensitive to the antimetabolite. A knowledge of the mechanisms of interaction of such lipophilic derivatives with cell membranes could be useful for planning further lipophilic MTX derivatives with an optimal antitumour activity. To this aim, a calorimetric study was undertaken using a biomembrane model made from synthetic 1,2-dipalmitoyl-glycero-3-phosphocholine (DPPC) multilamellar liposomes. The effects of MTX and conjugates on the phase transition of liposomes were investigated using differential scanning calorimetry.

The interaction of pure MTX with the liposomes was limited to the outer part of the phospholipid bilayers, due to the polar nature of the drug. Conversely, its lipophilic conjugates showed a hydrophobic kind of interaction, perturbing the packing order of DPPC bilayers. In particular, a reduction of the enthalpy of transition from the gel to the liquid crystal phase of DPPC membranes was observed. Such an effect was related to the structure and mole fraction of the conjugates in the liposomes.

The antitumour activity of MTX conjugates was evaluated against cultures of a CCRF–CEM human leukemic T-cell line and a related MTX resistant sub-line. The in vitro cell growth inhibitory activity was higher for bis(tetradecyl) conjugates than for both the other shorter- and longer-chain derivatives. The biological effectiveness of the various MTX derivatives correlated very well with the thermotropic effects observed on the phase transition of DPPC biomembranes.     

Quasilinear Molecule par Excellence,SrCl2: Structure from High‐Temperature Gas‐Phase Electron Diffraction and Quantum‐Chemical Calculations—Computed Structures of SrCl2×Argon Complexes.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.     

Poly(methyl methacrylate)-Assisted Exfoliation of Graphite and Its Use in Acrylonitrile-Butadiene-Styrene Composites

One of the applications of graphene in which its scalable production is of utmost importance is the development of polymer composites. Among the techniques used to produce graphene flakes, the liquid-phase exfoliation (LPE) of graphite stands out due to its versatility and scalability. However, solvents suitable for the LPE process are generally toxic and have a high boiling point, making the processing challenging. The use of low boiling point solvents could be convenient for the processing, due to the easiness of their removal. In this study, the use of poly(methyl methacrylate) (PMMA) as a stabilizing agent is proposed for the production of graphene flakes in a low boiling point solvent, that is, acetone. The graphene dispersions produced in the mixture acetone-PMMA have higher concentration, +175 %, and contain a higher percentage of few-layer graphene flakes (<5 layers), that is, +60 %, compared to the dispersions prepared in acetone. The as-produced graphene dispersions are used to develop graphene/acrylonitrile-butadiene-styrene composites. The mechanical properties of the pristine polymer are improved, that is, +22 % in the Young's modulus, by adding 0.01 wt. % of graphene flakes. Moreover, a decrease of ≈20 % in the oxygen permeability is obtained by using 0.1 wt. % of graphene flakes filler, compared to the unloaded matrix.     

Best Partial Covering of a Convex Domain by Congruent Circles of a Given Total Area

Generalizing results of L. Fejes Toth [3], [5], we prove the following theorem. Let R be a convex domain of area |R| and let S be a finite family of at least two congruent circles of total area t. Then for the area |F| of the part of R covered by the circles of S, the inequality |F|< tf(|R|/t) holds, where f(x) is the area of the intersection of a circle of unit area and a regular hexagon of area x concentric with the circle.     

Balanced optimization problems

Suppose we are given a finite set E, a family F of ‘feasible’ subsets of E and a real weight c(e) associated with every e?E. We consider the problem of finding S?F for which max {c(e)?c(e′): e, e′ ?S} is minimized. In other words, the differenc value between the largest and smallest value used should be as small as possible. We show that if we can efficiently answer the feasibility question then we can efficiently solve the optimization problem. We specialize these results to assignment problems and thereby obtain on O(n⁴) algorithm for ‘balanced’ assignment problems.     

The α -decay properties of 186Bi

The α decay of ¹⁸⁶Bi was investigated via the ⁹⁷Mo(⁹²Mo, p2n) reaction and the use of a fragment mass analyzer with a double-sided Si strip detector. In contrast to an earlier work wherein only one α transition was reported, we observed two transitions arising from two isomers in ¹⁸⁶Bi with energies and half-lives of: 7158(20) keV, T_1/2 = 15.0(17) ms; and 7261(20) keV, T_1/2 = 9.8(13) ms.