Anionic and ionic coordinative polymerization of ϵ‐caprolactone

The polymerization of ?‐caprolactone initiated by two catalyst systems was studied: (1) carbazole‐potassium in the presence of 18‐crown‐6 ether and (2) NdCl₃/TBP/TIBA (neodymiumtrichloride/tri‐n‐butyl‐phosphate/triisobutylaluminium) at the molar ratio 1/3/1. For both initiator systems conversion/time plots were determined and the polymers were characterized by IR, GPC and by ¹H‐ and ¹³C?NMR spectroscopy. Polyesters with the highest molecular weight (M _n?44 000 g/mol) were obtained for the polymerizations initiated by the carbazole‐potassium/18‐crown‐6 ether system. The features of the polymerization initiated by the carbazole‐potassium/18‐crown‐6 ether system are discussed on the basis of a simple scheme. The nature of this polymerization is non‐living. Copyright © 2000 John Wiley & Sons, Ltd.     

Synthesis and Stereochemistry of Novel Dibrominated 1,5-Dioxaspiro[5.5]undecane Derivatives

Summary.  The synthesis and stereochemistry of new dibrominated spiro-1,3-dioxane derivatives are reported. Investigations by means of NMR methods and single crystal X-ray diffraction for two compounds revealed the high regio- and diastereoselectivity of the bromination reaction of some new spiro-1,3-dioxanes and the asymmetric induction of the chiral carbon atom located in the spiro skeleton. Received July 13, 1999. Accepted October 21, 1999     

An operator approach to zero-sum repeated games

We consider two person zero-sum stochastic games. The recursive formula for the valuesvλ (resp.v _n) of the discounted (resp. finitely repeated) version can be written in terms of a single basic operator Φ(α,f) where α is the weight on the present payoff andf the future payoff. We give sufficient conditions in terms of Φ(α,f) and its derivative at 0 for limv _n and limvλ to exist and to be equal. We apply these results to obtain such convergence properties for absorbing games with compact action spaces and incomplete information games.     

Assembly of the Entire Carbon Backbone of a Stereoisomer of the Antitumor Marine Natural Product Hemicalide

A strategy for the assembly of the entire carbon backbone of a stereoisomer of the antitumor marine natural product hemicalide has been investigated. The devised convergent approach relies on Horner–Wadsworth–Emmons and Julia–Kocienski olefination reactions for the construction of the C6=C7 and C34=C35 double bonds, respectively, an aldol reaction to create the C27−C28 bond, and a Suzuki–Miyaura cross-coupling as the endgame to form the C15−C16 bond.     

The Map Between Conformal Hypercomplex/ Hyper-Kähler and Quaternionic(-Kähler) Geometry

We review the general properties of target spaces of hypermultiplets, which are quaternionic-like manifolds, and discuss the relations between these manifolds and their symmetry generators. We explicitly construct a one-to-one map between conformal hypercomplex manifolds (i.e. those that have a closed homothetic Killing vector) and quaternionic manifolds of one quaternionic dimension less. An important role is played by `ξ-transformations', relating complex structures on conformal hypercomplex manifolds and connections on quaternionic manifolds. In this map, the subclass of conformal hyper-Kähler manifolds is mapped to quaternionic-Kähler manifolds. We relate the curvatures of the corresponding manifolds and furthermore map the symmetries of these manifolds to each other.     

Comparative instrumental investigations of some bile acids

Journal of Thermal Analysis and Calorimetry - In this work, solifenacin succinate (SOLS), flavoxate HCl (FLXHC) and tolterodine tartrate (TOLT) drugs were investigated using thermal analysis (TA)...     

On the normal bundle of a complex submanifold of a locally conformal Kaehler manifold

We investigate the existence of parallel sections in the normal bundle of a complex submanifold of a locally conformal Kaehler manifold with positive holomorphic bisectional curvature. Also, ifM is a quasi-Einstein generalized Hopf manifold then we show that any complex submanifoldM with a flat normal connection ofM is quasi-Einstein, too, provided thatM is tangent to the Lee field ofM. As an application of our results we study the geometry of the second fundamental form of a complex submanifold in the locally conformal Kaehler sphereQ _m (of a complex Hopf manifoldS ^2m+1 ×S ¹).     

Empirical force-field assessment: The interplay between backbone torsions and noncovalent term scaling

The kinetic and thermodynamic aspects of the helix-coil transition in polyalanine-based peptides have been studied at the ensemble level using a distributed computing network. This study builds on a previous report, which critically assessed the performance of several contemporary force fields in reproducing experimental measurements and elucidated the complex nature of helix-coil systems. Here we consider the effects of modifying backbone torsions and the scaling of noncovalent interactions. Although these elements determine the potential of mean force between atoms separated by three covalent bonds (and thus largely determine the local conformational distributions observed in simulation), we demonstrate that the interplay between these factors is both complex and force field dependent. We quantitatively assess the heliophilicity of several helix-stabilizing potentials as well as the changes in heliophilicity resulting from such modifications, which can "make or break" the accuracy of a given force field, and our findings suggests that future force field development may need to better consider effect that vary with peptide length. This report also serves as an example of the utility of distributed computing in analyzing and improving upon contemporary force fields at the level of absolute ensemble equilibrium, the next step in force field development.     

Direct calculation of the binding free energies of FKBP ligands

Direct calculations of the absolute free energies of binding for eight ligands to FKBP protein were performed using the Fujitsu BioServer massively parallel computer. Using the latest version of the general assisted model building with energy refinement (AMBER) force field for ligand model parameters and the Bennett acceptance ratio for computing free-energy differences, we obtained an excellent linear fit between the calculated and experimental binding free energies. The rms error from a linear fit is 0.4 kcal/mol for eight ligand complexes. In comparison with a previous study of the binding energies of these same eight ligand complexes, these results suggest that the use of improved model parameters can lead to more predictive binding estimates, and that these estimates can be obtained with significantly less computer time than previously thought. These findings make such direct methods more attractive for use in rational drug design.