Polypyridyl-Based Copper Phenanthrene Complexes: Combining Stability with Enhanced DNA Recognition

We report a series of copper(II) artificial metallo-nucleases (AMNs) and demonstrate their DNA damaging properties and in-vitro cytotoxicity against human-derived pancreatic cancer cells. The compounds combine a tris-chelating polypyridyl ligand, di-(2-pycolyl)amine (DPA), and a DNA intercalating phenanthrene unit. Their general formula is Cu-DPA-N,N' (where N,N'=1,10-phenanthroline (Phen), dipyridoquinoxaline (DPQ) or dipyridophenazine (DPPZ)). Characterisation was achieved by X-ray crystallography and continuous-wave EPR (cw-EPR), hyperfine sublevel correlation (HYSCORE) and Davies electron-nuclear double resonance (ENDOR) spectroscopies. The presence of the DPA ligand enhances solution stability and facilitates enhanced DNA recognition with apparent binding constants (K_app) rising from 10⁵ to 10⁷ m ⁻¹ with increasing extent of planar phenanthrene. Cu-DPA-DPPZ, the complex with greatest DNA binding and intercalation effects, recognises the minor groove of guanine–cytosine (G-C) rich sequences. Oxidative DNA damage also occurs in the minor groove and can be inhibited by superoxide and hydroxyl radical trapping agents. The complexes, particularly Cu-DPA-DPPZ, display promising anticancer activity against human pancreatic tumour cells with in-vitro results surpassing the clinical platinum(II) drug oxaliplatin.     

Thermal transformation of polyacrylonitrile deposited on SBA-15 type silica

Thermogravimetry, diffuse reflectance infrared Fourier transform spectroscopy, and X-ray photoelectron spectroscopy (XPS) were used for the studying of thermally induced structural changes of polyacrylonitrile (PAN) deposited on the surface of SBA-15 type mesoporous silica. Polymer was introduced onto the support by the precipitation polymerization of acrylonitrile in aqueous suspension of SBA-15. Low temperature transformation (to 723?K) of the deposited PAN was analyzed. It was found that at about 523?K, exothermic cyclization of polymer chains to the so-called ladder form of PAN occurred. However, the total cyclization of PAN required higher carbonization temperatures, at which gradual dehydrogenation followed by graphitization was initiated. XPS revealed that the cyclic form of PAN and a relatively large amount of carbonyl species, formed during the carbonization of the PAN/SBA-15 composite at 623?K, were responsible for the high sorption capacity in the methyl?Cethyl ketone (MEK) vapor elimination. The efficiency in the MEK adsorption was also influenced by the content of PAN-derived carbon deposited on the SBA-15 surface.     

A continuous updating weighted least squares estimator of tail dependence in high dimensions

Likelihood-based procedures are a common way to estimate tail dependence parameters. They are not applicable, however, in non-differentiable models such as those arising from recent max-linear structural equation models. Moreover, they can be hard to compute in higher dimensions. An adaptive weighted least-squares procedure matching nonparametric estimates of the stable tail dependence function with the corresponding values of a parametrically specified proposal yields a novel minimum-distance estimator. The estimator is easy to calculate and applies to a wide range of sampling schemes and tail dependence models. In large samples, it is asymptotically normal with an explicit and estimable covariance matrix. The minimum distance obtained forms the basis of a goodness-of-fit statistic whose asymptotic distribution is chi-square. Extensive Monte Carlo simulations confirm the excellent finite-sample performance of the estimator and demonstrate that it is a strong competitor to currently available methods. The estimator is then applied to disentangle sources of tail dependence in European stock markets.     

On symmetric stochastic games of resource extraction with weakly continuous transitions

We study stochastic games of resource extraction, in which the players have identical preferences. The transition probability is either non-atomic or a convex combination of transition probabilities depending on the investment with coefficients also dependent on the investment. Our approach covers the unbounded utility case, which was not examined in this class of games beforehand. We prove the existence of a stationary Markov perfect equilibrium in a non-randomised class of strategies.     

The numerical duplication of a numerical semigroup

In this paper we present and study the numerical duplication of a numerical semigroup, a construction that, starting with a numerical semigroup S and a semigroup ideal E?S, produces a new numerical semigroup, denoted by S? ^b E (where b is any odd integer belonging to S), such that S=(S? ^b E)/2. In particular, we characterize the ideals E such that S? ^b E is almost symmetric and we determine its type.     

Oxygenase‐Catalyzed Desymmetrization of N,N‐Dialkyl‐piperidine‐4‐carboxylic Acids

γ‐Butyrobetaine hydroxylase (BBOX) is a 2‐oxoglutarate dependent oxygenase that catalyzes the final hydroxylation step in the biosynthesis of carnitine. BBOX was shown to catalyze the oxidative desymmetrization of achiral N,N‐dialkyl piperidine‐4‐carboxylates to give products with two or three stereogenic centers.