Separation and Thermal Racemization of the Enantiomers of Spiro[cyclohexadiene-dihydroacridines]

 The enantiomers of substituted spiro[cyclohexadiene-dihydroacridines] were separated by enantioselective liquid chromatography with the sorbent/solvent systems triacetylcellulose/methanol, tris-(3,5-dimethylphenylcarbamoyl)-cellulose/silica gel (Chiralcel OD^TM)/n-heptane/2-propanol, and (+)-poly-(trityl methacrylate)/silica gel/n-heptane/2-propanol. Interconversion barriers of the enantiomers were determined for a series of derivatives by thermal racemization. Electrocyclic ring opening/ring closure in terms of the Woodward-Hoffmann rules is discussed for the enantiomerization mechanism; the interconversion of the enantiomers by enolization is ruled out by deuterium exchange experiments.     

Analysis and numerical simulation of magnetic forces between rigid polygonal bodies. Part I: Analysis

The mathematical and physical analysis of magnetoelastic phenomena is a topic of ongoing research. Different formulae have been proposed to describe the magnetic forces in macroscopic systems. We discuss several of these formulae in the context of rigid magnetized bodies. In case the bodies are in contact, we consider formulae both in the framework of macroscopic electrodynamics and via a multiscale approach, i.e., in a discrete setting of magnetic dipole moments. We give mathematically rigorous proofs for domains of polygonal shape (as well as for more general geometries) in two and three space dimensions. In an accompanying second article, we investigate the formulae in a number of numerical experiments, where we focus on the dependence of the magnetic force on the distance between the bodies and on the case when the two bodies are in contact. The aim of the analysis as well as of the numerical simulation is to contribute to the ongoing debate about which formula describes the magnetic force between macroscopic bodies best and to stimulate corresponding real-life experiments.      

Charging of silver bromide aqueous interface: Evaluation of enthalpy and entropy of interfacial reactions from surface potential data

Dependence of surface potential (electrostatic potential at the inner Helmholtz plane, Ψ(0)) at the silver bromide aqueous electrolyte interface was measured as a function of the activities of Br(-) and Ag(+) by using a single crystal silver bromide electrode (SCr-AgBr). Absolute values of surface potentials were obtained from electrode potentials of SCr-AgBr and isoelectric points. Measurements were performed at different temperatures in the range from 10 to 50°C. Corresponding equilibrium constants of interfacial reactions were obtained using the surface complexation model and interpreted via the van't Hoff equation. As a result of the interpretation for the binding of bromide ions leading to a negative surface charge, the thermodynamic parameters obtained were Δ(n)H(°)=-33kJmol(-1) and Δ(n)S(°)=-31Jmol(-1)K(-1); and for the binding of silver ions leading to a positive surface charge, Δ(p)H(°)=-72kJmol(-1) and Δ(p)S(°)=-196Jmol(-1)K(-1). Association of counterions (CI) with oppositely charged surface sites partially compensates the surface charge. Assuming approximately the same affinities for anions (NO(3)(-)) and cations (K(+)) thermodynamic parameters for their binding were obtained as Δ(CI)H(°)≈7kJmol(-1) and Δ(CI)S(°)≈105Jmol(-1)K(-1).     

Chiral semiconductor phases: the optically pure D3[M(III)(S,S-EDDS)]2 (D=TTF, TSF) family

A new family of optically pure tetrathiafulvalenium and tetraselenafulvalenium salts, D(3)[M(III)(S,S-EDDS)](2)·nH(2)O (where D = TTF, TSF; M = Co, Fe, Cr; EDDS = ethylenediaminedisuccinato), were synthesized electrochemically. These phases are semiconductors with conductivities between 6.9 × 10(-6) and 1.3 × 10(-5) S·cm(-1) (E(a)ca. 0.3 eV) for TTF and 2.8 × 10(-4) to 2.8 × 10(-5) S·cm(-1) (E(a)ca. 0.1 eV) for TSF compounds. While some crystals suffer from twinning, other well resolved structures consist of TTF/TSF stacks which, under the influence of the chiral anion, exhibit a periodic undulation described by an elliptical helix. The crystallographic data, along with computational work, indicate charge localization in the semiconducting motifs.     

Synthetic Antitumor Vaccines Containing MUC1 Glycopeptides with Two Immunodominant Domains-Induction of a Strong Immune Response against Breast Tumor Tissues

A shot in the arm for cancer treatment: Two MUC1 tetanus toxoid vaccines were synthesized and induced a strong immune response in mice. The antibodies elicited by the vaccines show a high selectivity for the tumor cells in mammary carcinoma tissues and also distinguish between tumor tissues at different stages.     

Comment on “New methods for old Coulomb few‐body problems”

In this Comment on the above‐mentioned paper by F. E. Harris, A. M. Frolov, and V. H. Smith, we briefly review our contributions to development of new methods for solution of the Coulomb four‐body problem. We show that our research group, headed by Professor T. K. Rebane, had a priority in using the fully correlated exponential basis for variational calculations of four‐body systems. We also draw attention to the fact that our group subsequently implemented a more advanced method, which uses highly efficient exponential‐trigonometric basis functions for solution of the same problem. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Nonlinear evolution of coarse-grained quantum systems with generalized purity constraints

Constrained quantum dynamics is used to propose a nonlinear dynamical equation for pure states of a generalized coarse-grained system. The relevant constraint is given either by the generalized purity or by the generalized invariant fluctuation, and the coarse-grained pure states correspond to the generalized coherent, i.e. generalized nonentangled states. Open system model of the coarse-graining is discussed. It is shown that in this model and in the weak coupling limit the constrained dynamical equations coincide with an equation for pointer states, based on Hilbert-Schmidt distance, that was previously suggested in the context of the decoherence theory.