Structure and thermodynamics of alpha-, beta-, and gamma-cyclodextrin dimers. Molecular dynamics studies of the solvent effect and free binding energies

The alpha-, beta-, and gamma-cyclodextrin (CyDs) dimers were studied by molecular dynamics (MD) simulations in water as an explicit solvent. The relative stability of dimers and the involved molecular interactions were determined. Three possible starting orientations were considered for the dimers: head-to-head, head-to-tail, and tail-to-tail. MD simulations were performed over a period of 5 ns to ensure the stability of the system for both the CyD dimers and monomers. The MM-PBSA methodology was used to obtain the free binding energy of the dimers and to determine the most stable arrangement for each solvated CyD. In a vacuum, MD simulations provided the head-to-head orientation as the most stable orientation for the three CyDs, while in aqueous solution the, the head-to-tail orientation was found to be the most stable for the alpha-CyD dimer and the tail-to-tail orientation the most stable for the beta- and gamma-CyD dimers.     

Compact interval spaces in which all closed subsets are homeomorphic to clopen ones,I

A topological space X whose topology is the order topology of some linear ordering on X, is called an interval space. A space in which every closed subspace is homeomorphic to a clopen subspace, is called a CO space. We regard linear orderings as topological spaces, by equipping them with their order topology. If L and K are linear orderings, then L ^*, L+K, L·K denote respectively the reverse orderings of L, the ordered sum of L and K and the lexicographic order on L×K (so ·2=+ and 2·=). Ordinals are considered as linear orderings, and cardinals are initial ordinals. For cardinals , 0, let L(, )= + 1 + ^* . Main theorem. Let X be a compact interval space. Then X is a CO space if and only if X is homeomorphic to a space of the form + 1 + _i L( _i , _i ), where is any ordinal, n, for every ii, _i are regular cardinals and _{i i}, and if n>0, then max({ _i: i}) · . This first part is devoted to show the following result. Theorem: If X is a compact interval CO space, then X is a scattered space (that means that every subspace of X has an isolated point).Supported by the Université Claude-Bernard (Lyon-1), the Ben Gurion University of the Negev, and the C.N.R.S.: UPR 9016Supported by the City of Lyon     

Structure électronique des éthers vinylique et divinylique: Introduction de la déformation des orbitales σ

Résumé La théorie L.C.A.O. améliorée est appliquée à l'étude des éthers vinylique et divinylique. La grande différence d'électronégativité entre les orbitales atomiques entrant dans la liaison entre l'oxygène et le carbone nous a conduits à introduire la déformation réciproque de ces orbitales. Les énergies calculées pour la première transition N V, 6,5 et 6,3 eV, sont en excellent accord avec l'expérience.

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The improved L.C.A.O. theory is applied to the vinyl and divinyl ethers. The large differences of electronegativity between the atomic orbitals which enter the-bond between oxygen and carbon led us to the introduction of the mutual deformation of these orbitals. The calculated energies for the first N V transition, 6,5 and 6,3 eV are in excellent agreement with experiment.

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Zusammenfassung Die verbesserte L.C.A.O.-Theorie wird auf Vinyl- und Divinyläther angewandt. Die große Elektronegativitätsdifferenz zwischen den an der-Bindung zwischen Sauerstoff und Kohlenstoff beteiligten Atomzuständen hat uns veranlaßt, die gegenseitige Deformation dieser Zustände einzuführen. Die für die erste N V-Elektronenbande berechneten Energien, 6,5 und 6,3 eV, stimmen ausgezeichnet mit der Erfahrung überein.

     

P and n dopable semi-interpenetrating polymer networks

Electrochemical oxidation of thin films of 9-(2,3-epoxypropyl)carbazole (OEPC) oligomer deposited on an electrode leads to the formation of an in-situ cross-linked structure with biscarbazyl redox sites due to the anodic coupling of pendant carbazole units. Electrochemical, optical, and thermal characterizations confirm the formation of a conducting network containing electroactive biscarbazolyl units. When the electrochemical cross-linking takes place in a starting thin film containing a mixture of OEPC and a perylene bisimide polymer [poly(Pery-EO₃)], a semi-interpenetrating polymer network is formed which possesses both electron donor and electron acceptor properties. Indeed, the electrochemical behavior of the semi-interpenetrating polymers network (IPN) is characterized by two reversible oxidations and two reversible reduction waves corresponding to the biscarbazolyl and perylene redox moities, respectively. The energy levels of the highest occupied molecular orbital E _HOMO and lowest unoccupied molecular orbital E _LUMO of each donor and acceptor in the semi-IPN have been evaluated and indicate a possible electron transfer from biscarbazole to perylene, which could be taken advantage of in the field of solar cells application.     

An efficient, regioselective and fast enzymatic glycosylation for cyclodextrins

The introduction of a short spacer arm was necessary to obtain complete regioselectivity in the glycosylation of β-cyclodextrin (β-CD) mediated by glycosidases. Thus 6-N-(2-aminoethyl-α-d-galactopyranosyl)-6-deoxycyclomaltoheptaose was prepared in four steps from β-cyclodextrin with 30% overall yield using, in the key step, the transfer activity of green coffee bean α-galactosidase.     

High-performance gas chromatography of 1,4-naphthoquinones fromDroseraceae

Summary The analysis of natural 1,4-naphthoquinones from different species ofDroseraceae was performed by means of a direct GC method without derivatization. A simple and rapid extraction by toluene was used which did not need further purification. The sensitivity of the method allowed naphthoquinone estimation in one organ (leaf or root) only.The identity of plumbagin and 7-methyljuglone was confirmed by mass spectrometry.     

Genuine heteroleptic complexes of early rare-earth metals: synthesis, X-ray structure, and their use for stereospecific isoprene polymerization catalysis

Genuine heteroleptic neodymium and samarium complexes of formula [Cp*'Ln[(p-tol)NN](BH4)] (Cp*' = C5Me4(nPr), (p-tol)NN = (p-tol)NC(Me)CHC(Me)N(p-tol), Ln = Sm: 1a, Ln = Nd: 1b) have been synthesized for the first time. These unprecedented homologues of early lanthanocenes are prepared by a metathetic reaction between their monocyclopentadienylbisborohydrido precursors with the corresponding potassium diketiminate. Both complexes were obtained in good yields and were characterized by 1H NMR spectroscopy and elemental analysis. Complex 1 a has an non-solvated dimeric structure, as indicated by its crystallographic data. The chloroneodymium analogue [Cp*'Nd[(p-tol)NN](Cl)] (2b) was only obtained as a part of a mixture. Analysis of crystals of 2b by X-ray diffraction revealed a molecular structure very similar to that of 1a. Preliminary isoprene polymerization experiments were carried out with 1 b in the presence of an alkylmagnesium coactivator. The resulting bimetallic Nd/Mg system behaves as an efficient and highly stereospecific catalyst with the synthesis of trans-1,4-polyisoprene with more than 98% regularity. The control of the polymer structure is related to the steric hindrance around the lanthanide atom.     

Classical treatment of molecular collisions: striking improvement of the description of recoil energy distributions using Gaussian weighted trajectories

The Gaussian weighting (GW) procedure, recently used in the classical treatment of molecular collisions, is a practical way of taking into account quantization of product vibrational actions. The goal of this brief communication is to show that the GW procedure may drastically improve the predictions of the recoil energy distribution between final fragments, an observable frequently measured in molecular beam experiments.     

Study of the H+O2 reaction by means of quantum mechanical and statistical approaches: the dynamics on two different potential energy surfaces

The possible existence of a complex-forming pathway for the H+O(2) reaction has been investigated by means of both quantum mechanical and statistical techniques. Reaction probabilities, integral cross sections, and differential cross sections have been obtained with a statistical quantum method and the mean potential phase space theory. The statistical predictions are compared to exact results calculated by means of time dependent wave packet methods and a previously reported time independent exact quantum mechanical approach using the double many-body expansion (DMBE IV) potential energy surface (PES) [Pastrana et al., J. Phys. Chem. 94, 8073 (1990)] and the recently developed surface (denoted XXZLG) by Xu et al. [J. Chem. Phys. 122, 244305 (2005)]. The statistical approaches are found to reproduce only some of the exact total reaction probabilities for low total angular momenta obtained with the DMBE IV PES and some of the cross sections calculated at energy values close to the reaction threshold for the XXZLG surface. Serious discrepancies with the exact integral cross sections at higher energy put into question the possible statistical nature of the title reaction. However, at a collision energy of 1.6 eV, statistical rotationally resolved cross sections managed to reproduce the experimental cross sections for the H+O(2)(v=0,j=1)-->OH(v(')=1,j('))+O process reasonably well.