tBuP(NH2)2--a reactive synthon for the synthesis of molecular imidophosphinates of group 13 metals

Reactions of tBuP(NH(2))(2) with Group 13 trialkyls MR(3) (M=Al, Ga, In; R=Me, tBu) were investigated in detail. According to variable-temperature (VT) NMR investigations, the reaction proceeds stepwise with the initial formation of aminophosphane adducts, which subsequently react to give iminophosphorane adducts and finally the heterocyclic metallonitridophosphinates. BP86/TZVPP (DFT) calculations were performed to verify this reaction pathway, to elucidate the influence of the central Group 13 element on the stability of the reaction intermediates and the heterocycles, as well as to assess the thermodynamics of their formation. The relative stability of free and complexed aminophosphane RP(NH(2))(2) and iminophosphorane R(H(2)N)(H)P=NH (adducts) with P(III) and P(V) centers was studied in more detail with DFT and MP2 methods. In addition, the influence of the substituent R was investigated by variation of R from H to Me, tBu, F, and NH(2). In general, the aminophosphane form was found to be favored for the free ligand, however, upon complexation with MR(3) (M=Al, Ga; R=alkyl) both forms are almost equal in energy.     

Electronic and vibrational properties of fluorenone in the channels of zeolite L

Fluorenone (C13H8O) was inserted into the channels of zeolite L by using gas-phase adsorption. The size, structure, and stability of fluorenone are well suited for studying host-guest interactions. The Fourier transform IR, Raman, luminescence, and excitation spectra, in addition to thermal analysis data, of fluorenone in solution and fluorenone/zeolite L are reported. Normal coordinate analysis of fluorenone was performed, based on which IR and Raman bands were assigned, and an experimental force field was determined. The vibrational spectra can be used for nondestructive quantitative analysis by comparing a characteristic dye band with a zeolite band that has been chosen as the internal standard. Molecular orbital calculations were performed to gain a better understanding of the electronic structure of the system and to support the interpretation of the electronic absorption and luminescence spectra. Fluorenone shows unusual luminescence behavior in that it emits from two states. The relative intensity of these two bands depends strongly on the environment and changes unexpectedly in response to temperature. In fluorenone/zeolite L, the intensity of the 300 nm band (lifetime 9 micros) increases with decreasing temperature, while the opposite is true for the 400 nm band (lifetime 115 micros). A model of the host-guest interaction is derived from the experimental results and calculations: the dye molecule sits close to the channel walls with the carbonyl group pointing to an Al3+ site of the zeolite framework. A secondary interaction was observed between the fluorenone's aromatic ring and the zeolite's charge-compensating cations.     

Correlation between host-guest binding and host amplification in simulated dynamic combinatorial libraries

We present a versatile computer model of diverse dynamic combinatorial libraries, and examine how molecular recognition between library members and a template can be used to amplify the best binders. The correlation between host-guest binding and amplification was examined for a set of 50 libraries with >300 components each over a wide range of template and building block concentrations. Depending on these concentrations correlations vary from poor (when using a large excess of template) to good (for very dilute libraries and/or substoichiometric template concentrations), highlighting the need to choose the experimental conditions for dynamic combinatorial libraries thoughtfully.     

Asymptotic stability in perturbed delay difference systems

Consider the delay difference system

     

Robust H ∞ Filtering for a Class of Nonlinear Discrete-Time Markovian Jump Systems

This paper considers the problem of the robust H filtering for a class of nonlinear discrete-time Markovian jump systems with real time-varying norm-bounded parameter uncertainty. For each mode, the nonlinearity is assumed to satisfy the global Lipschitz conditions and appears in both the state and measured output equations. The problem that we address is the design of a nonlinear filter which ensures robust stochastic stability and a prescribed H performance level of the filtering error system for all admissible uncertainties. A sufficient condition for the solvability of this problem is obtained in terms of a set of linear matrix inequalities; an explicit expression of a desired nonlinear H filter is also given. Finally, an example is provided to demonstrate the effectiveness of the proposed approach.     

Structure of positive solutions for quasilinear elliptic systems—degenerate ecological models

We study the degenerate ecological models where are positive numbers. The structure of positive solutions of the models is discussed via bifurcation theory and monotone techniques. Copyright © 2004 John Wiley & Sons, Ltd.     

On the existence of an invariant measure for Markov-Feller operators

Let X be a Polish space and P a Markov operator acting on the space of Borel measures on X. We will prove the existence of an invariant measure with respect to P, provided that P satisfies some condition of a Prokhorov type and that the family of functions is equi-continuous with respect to the Prokhorov distance at some point of the space X. Moreover, we will construct a counterexample which show that the above equi-continuity condition cannot be dropped.     

Existence of homoclinic solution for the second order Hamiltonian systems

An existence theorem of homoclinic solution is obtained for a class of the nonautonomous second order Hamiltonian systems , ∀t∈R, by the minimax methods in the critical point theory, specially, the generalized mountain pass theorem, where L(t) is unnecessary uniformly positively definite for all t∈R, and W(t,x) satisfies the superquadratic condition W(t,x)/|x|²→+∞ as |x|→∞ uniformly in t, and need not satisfy the global Ambrosetti-Rabinowitz condition.     

Boundedness of solutions for semilinear reversible systems

In this paper we will study the boundedness of all solutions for second-order differential equations

where and satisfies the sublinear growth condition. Since the system in general is non-Hamiltonian, we have to introduce reversibility assumptions to apply the twist theorem for reversible mappings. Under some suitable conditions we then obtain the existence of invariant tori and thus the boundedness of all solutions.

     

Real bounds, ergodicity and negative Schwarzian for multimodal maps

We consider smooth multimodal maps which have finitely many non-flat critical points. We prove the existence of real bounds. From this we obtain a new proof for the non-existence of wandering intervals, derive extremely useful improved Koebe principles, show that high iterates have `negative Schwarzian derivative' and give results on ergodic properties of the map. One of the main complications in the proofs is that we allow to have inflection points.