Large Water-Soluble Cyclophanes with Convergent Intracavity Functionality

New tricyclic spacers, readily available through fourfold Mannich reaction of substituted dibenzyl ketones, were introduced into a series of ten H₂O-soluble cyclophanes with spacious preorganized cavity binding sites. These spacers provide H₂O-solubility with amine or crown-ether functionality remote from the cyclophane cavity while directing functional groups such as keto or OH groups in a precise geometrical array inside the cavity. The cyclophanes were designed to include organic substrates via a combination of apolar and specific polar functional group interactions. The X-ray crystal-structure analysis of the tritopic receptor 18 with one potential neutral-molecule and two cation-binding sites showed a large rectangular open cavity with dimensions of roughly 9 × 14 Å and a spacing of 9.7 Å between the O-atoms of two convergent C?O groups. Despite the binding-site preorganization, cyclophanes incorporating two of the new spacers did not show any substrate binding in aqueous solutions. The failure of these systems to function as receptors is mainly due to steric hindrance to important cyclophane aromatic ring-guest interactions. Also, the favorable solvation of the intracavity functionality may prevent the formation of complexes. Hybrid receptors constructed from the novel spacers and diphenylmethane units were found to bind flat aromatic substrates as well as bulky [4.2]paracyclophanes. The observed large differences in stability (ΔΔG°> 2 kcal mol^?1) of the complexes formed by three structurally closely related hybrid receptors with convergent C?O, OH or CH₂ groups and 6-hydroxynaphthalene-2-carbonitrile as guest can be explained by a strong solvation effect of the convergent functional groups on apolar inclusion complexation.     

Energy levels of small titanium oxide clusters obtained from SCF calculations

The energy levels of small titanium oxide clusters [(TiO₂)₂, and (TiO₂H)₃, and (TiO₂H)₂] have been calculated using ab initio SCF methods. Both crystal and relaxed geometries have been considered. Systematic changes in the valencelevel structure resulting from geometry relaxation are found, which may be related to band-gap changes experimentally observed for small titanium oxide particles. In addition, a Ti? OH local surface state is found to be well described within a limited cluster model. © 1994 John Wiley & Sons, Inc.     

Exfoliation of Coatings from Silicon Crystals Electroless-Plated with Nickel and Electroplated with Gold

The microhardness and content of carbon in electroplated gold coatings were studied as influenced by the operation time of citrate and citrate-phosphate gold-plating electrolytes. Such physicomechanical properties as porosity, microhardness, internal stress, plasticity, and microstructure of electroless-plated and electroplated nickel coatings were studied and analyzed.     

An Inverse Problem for a Model of a Hierarchical Structure

We consider the inverse problem for the identification of the coefficient in a parabolic equation. The model is applied to describe the functioning of a hierarchical structure [1]; it is also relevant for heat-conduction theory [2]. Unique solvability of the inverse problem is proved.     

Boundary-value problem for the nonlinear Schrödinger equation

A mixed boundary-value problem for the nonlinear Schrödinger equation and its generalization is studied by the method used for the inverse scattering problem. A connection is established between conservation laws and boundary conditions in integrable boundary-value problems for higher nonlinear Schrödinger equations. It is shown that the generalized boundary-value problem requires a joint consideration of regular and singular solutions for the nonlinear Schrödinger equation with repulsion.Translated from Zapiski Nauchnykh Seminarov Leningradskogo Otdeleniya Matematicheskogo Instituta im. V. A. Steklova AN SSSR, Vol. 169, pp. 151–165, 1988.