Coordination of phosphinoboranes R2PB(C6F5)2 to platinum: an alkene-type behavior

The paucity of boron-containing heteroalkene complexes prompted us to explore the coordination of phosphinoboranes. The complexes {[R(2)PB(C(6)F(5))(2)]Pt(PPh(3))(2)} (R = Cy, t-Bu) were obtained by ethylene displacement. Spectroscopic and crystallographic data indicated symmetric side-on coordination of the phosphinoborane to Pt. Thorough analysis of the bonding situation by computational means revealed important similarities but also significant differences between the phosphinoborane and ethylene complexes.     

Matched asymptotic expansions for the determination of the electromagnetic field near the edge of a patch antenna

We consider a simple but representative model incorporating the main behavior of the electromagnetic field near the edge of a patch antenna. Recall that this kind of antenna is obtained by a metal patch laying on a dielectric substrate covering a ground metallic plane. The functioning principle of such an electric device is based on the matching of an N-dimensional behavior of the field outside the antenna with an (N-1)-dimensional one inside the zone limited by the patch and the ground plane, N = 3 or 2 according to the considered model. In this study, we make use of the technique of matched asymptotic expansions and computation of singularities to describe this behavior for the two-dimensional case. Proved error estimates enable us to give a rigorous background to the underlying asymptotic analysis. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Adsorption of Toluene and Water over Cationic-Exchanged Y Zeolites: A DFT Exploration

In this study, density functional theory (DFT) calculations have been performed to investigate the adsorption mechanisms of toluene and water onto various cationic forms of Y zeolite (LiY, NaY, KY, CsY, CuY and AgY). Our computational investigation revealed that toluene is mainly adsorbed via π–interactions on alkalis exchanged Y zeolites, where the adsorbed toluene moiety interacts with a single cation for all cases with the exception of CsY, where two cations can simultaneously contribute to the adsorption of the toluene, hence leading to the highest interaction observed among the series. Furthermore, we find that the interaction energies of toluene increase while moving down in the alkaline series where interaction energies are 87.8, 105.5, 97.8, and 114.4 kJ/mol for LiY, NaY, KY and CsY, respectively. For zeolites based on transition metals (CuY and AgY), our calculations reveal a different adsorption mode where only one cation interacts with toluene through two carbon atoms of the aromatic ring with interaction energies of 147.0 and 131.5 kJ/mol for CuY and AgY, respectively. More importantly, we show that water presents no inhibitory effect on the adsorption of toluene, where interaction energies of this latter were 10 kJ/mol (LiY) to 47 kJ/mol (CsY) higher than those of water. Our results point out that LiY would be less efficient for the toluene/water separation while CuY, AgY and CsY would be the ideal candidates for this application.     

ISOGENOUS OF THE ELLIPTIC CURVES OVER THE RATIONALS

AbstractAn elliptic curve is a pair (E,O), where ?is a smooth projective curve of genus 1 and O is a point of E, called the point at infinity. Every elliptic curve can be given by a Weierstrass equationE:y2 a1xy a3y = x3 a2x2 a4x a6.Let Q be the set of rationals. E is said to be dinned over Q if the coefficients ai, i = 1,2,3,4,6 are rationals and O is defined over Q.Let E/Q be an elliptic curve and let E(Q)tors be the torsion group of points of E denned over Q. The theorem of Mazur asserts that E(Q)tors is one of the following 15 groupsE(Q)tors　Z/mZ, m = 1,2,..., 10,12,Z/2Z × Z/2mZ, m = 1,2,3,4.We say that an elliptic curve E'/Q is isogenous to the elliptic curve E if there is an isogeny, i.e. a morphism : E E' such that (O) = O, where O is the point at infinity.We give an explicit model of all elliptic curves for which E(Q)tors is in the form Z/mZ where m= 9,10,12 or Z/2Z × Z/2mZ where m = 4, according to Mazur's theorem. Morever, for every family of such elliptic curves, we give an explicit m     

DNA Nucleobase under Ionizing Radiation: Unexpected Proton Transfer by Thymine Cation in Water Nanodroplets

The effect of ionizing radiation on DNA constituents is a widely studied fundamental process using experimental and computational techniques. In particular, radiation effects on nucleobases are usually tackled by mass spectrometry in which the nucleobase is embedded in a water nanodroplet. Here, we present a multiscale theoretical study revealing the effects and the dynamics of water droplets towards neutral and ionized thymine. In particular, by using both hybrid quantum mechanics/molecular mechanics and full ab initio molecular dynamics, we reveal an unexpected proton transfer from thymine cation to a nearby water molecule. This leads to the formation of a neutral radical thymine and a Zundel structure, while the hydrated proton localizes at the interface between the deprotonated thymine and the water droplet. This observation opens entirely novel perspectives concerning the reactivity and further fragmentation of ionized nucleobases.     

A Bayesian Decision Theory Approach to Classification Problems

We address the classification problem where an item is declared to be from populationπ_jif certain of its characteristicsvare assumed to be sampled from the distribution with pdf f_j(vθ_j), wherej=1, 2, …, m. We first solve the two population classification problem and then extend the results to the generalmpopulation classification problem. Usually only the form of the pdf's is known. To use the classical classification rule the parameters,θ_j, must be replaced by their estimates. In this paper we allow the parameters of the underlying distributions to be generated from prior distributions. With this added structure, we obtain Bayes rules based on predictive distributions and these are completely determined. Using the first-order expansion of the predictive density, where the coefficients of powers ofn⁻¹remain uniformly bounded innwhen integrated, we obtain an asymptotic bound for the Bayes risk.     

Isolation of a Reactive Tricoordinate α‐Oxo Gold Carbene Complex

The [(P,P)Au=C(Ph)CO₂Et]⁺ complex 3 [where (P,P) is an o‐carboranyl diphosphine ligand] was prepared by diazo decomposition at ?40 °C. It is the first α‐oxo gold carbene complex to be characterized. Its crystallographic structure was determined and DFT calculations have been performed, unraveling the key influence of the chelating (P,P) ligand. The gold center is tricoordinate and the electrophilicity of the carbene center is decreased. Complex 3 mimics transient α‐oxo gold carbenes in a series of catalytic transformations, and provides support for the critical role of electrophilicity in the chemoselectivity of phenol functionalization (O?H vs. C?H insertion).     

A new tetrapyrazolic macrocycle. Synthesis and its use in extraction and transport of K, Na and Li

The synthesis of a new tetrapyrazolic macrocyclic structure with a functionalised arm is described. The complexing properties of this new compound towards alkali metal ions (K⁺, Na⁺, Li⁺) were studied by liquid-liquid extraction and liquid membrane transport processes. The extracted and the transport cation percentage were determined by atomic absorption measurements and UV spectroscopy.     

Incentive equilibrium in an overlapping-generations environmental game

We consider two overlapping generations that want to coordinate their strategies of working, consuming and controlling pollution. Since the cooperative solution is not an equilibrium, and hence is not a self-enforcing contract, a mechanism is required to sustain it. We show how incentive strategies, and the resulting incentive equilibrium, could provide such a mechanism. We also derive the conditions that ensure the credibility of these strategies.     

A new generalization of the KMOV cryptosystem

The KMOV scheme is a public key cryptosystem based on an RSA modulus \(n=pq\) where p and q are large prime numbers with \(p\equiv q\equiv 2\pmod 3\). It uses the points of an elliptic curve with equation \(y^2\equiv x^3+b\pmod n\). In this paper, we propose a generalization of the KMOV cryptosystem with a prime power modulus of the form \(n=p^{r}q^{s}\) and study its resistance to the known attacks.