Studies in stereoselective [2+2]-cycloadditions with dichloroketene

During the investigation of the reaction of dichloroketene with cyclic enoxy-lactones and acyclic enoxy-ester substrates it was found that only the acylic variants effectively participated in the [2+2]-cycloaddition. Although a complete understanding of the reasons for this are lacking, molecular mechanics calculations do suggest that an out of plane twist of the cabonyl group in the acyclic compounds may be partially responsible. After screening a variety of chiral auxiliaries it was found that useful levels of diastereoselectivity (2.6-10.8:1) could be obtained in this cycloaddition reaction when (R)-2,2-diphenylcyclopentanol was used as the chiral auxiliary.     

Structural, volumetric, and thermodynamic characterization of a micellar sphere-to-rod transition

The thermotropic sphere-to-rod transition of nonionic surfactants was characterized in terms of a large set of parameters: the transition temperature and width, the partial volume, coefficient of thermal volume expansion, enthalpy, isobaric heat capacity, and structural parameters, such as radius of gyration and hydrodynamic radius. Data were recorded as a function of concentration of surfactants in H2O and in D2O. To this end, pressure perturbation calorimetry (PPC), small angle neutron scattering (SANS), dynamic light scattering (DLS), differential scanning calorimetry (DSC), and isothermal titration calorimetry (ITC) were applied in a study of aqueous solutions containing myristyl, tridecyl, and lauryl maltoside and heptaethyleneglycoltetradecyl ether (C14EO7). Small changes in the thermodynamic and volumetric parameters (e.g., the partial volume change is approximately +2 per thousand) are discussed in detail as the result of three effects governing the transition. (i) Reduction of the water accessible hydrophobic surface area (ASA(ap)) drives the transition. (ii) Shrinking in headgroup size by thermal dehydration triggers the transition. (iii) Hypothesized gradual ordering of the chains may control the effect of chain length on the transition.     

Conformation of poly(L-lysine)-graft-poly(ethylene glycol) molecular brushes in aqueous solution studied by small-angle neutron scattering

Small-angle neutron scattering (SANS) has been employed for the analysis of conformations of poly(L-lysine)-graft-poly(ethylene glycol) (PLL-g -PEG) molecular bottle brushes in aqueous solutions. The degree of polymerisation of the PEG chains was systematically varied in order to unravel dependence of the conformational properties of the bottle brushes on the molecular weight of the grafted chains. The grafting density was kept constant and high enough to ensure strong overlap of the PEG chains. The scattering spectra were fitted on the basis of the model of an effective worm-like chain with the account of average radial distribution and local fluctuations of the PEG density in the bottle brush. The results of the fits indicate that molecular brushes retain weakly bent configuration on the length scale of the order of (or larger than) the brush thickness. This finding is in agreement with earlier simulation and recent theoretical results.     

On the stoichiometry of the organic metal bis(ethylenedioxy)-tetrathiafulvalene chloride

We report on Shubnikov-de Haas and de Haas-van Alphen measurements of an organic metal based on the molecular donor bis(ethylenedioxy)-tetrathiavulvalene (= BEDO-TTF) and the anion Cl^- with H₂O molecules. The observed single oscillation frequency perfectly follows the two-dimensional dependence with T. The Fermi-surface area of of the first Brillouin zone proves a quarter-filled band, i.e., a 2:1 stoichiometry of the BEDO-TTF donor with respect to the anion. The apparent discrepancy to X-ray data which give a 1:1 ratio between BEDO-TTF and Cl^- is understood by replacement of H₂O molecules with (H₃O)⁺ ions. The proposed stoichiometry therefore is (BEDO-TTF)₂ ⁺(H₅O₂)⁺(Cl^-)₂. The cyclotron effective mass is when deduced from the temperature dependence of the fundamental oscillation amplitude, but strongly reduced when extracted from higher harmonics. This and the strong harmonic content of the oscillations signals an influence of the two-dimensional electronic structure and can be qualitatively understood by applying the concept of magnetic interaction to the effect of the oscillatory chemical potential. Received: 16 April 1998 / Revised: 7 July 1998 / Accepted: 9 July 1998     

Untersuchung von Kartoffeln, Gerste und Malz

Ohne Zusammenfassung     

Phase behaviour and physical properties of the cationic quaternary system tetradecyldimethylamine oxide hydrochloric acid 1-hexanol water

 The phase behaviour and properties of the tetradecyldimethylamine oxide/HCl/hexanol/water quaternary surfactant system have been studied by means of electric conductivity, rheology, freeze-fracture transmission electron microscopy (FF-TEM) and small-angle neutron scattering (SANS). In this system the originally zwitterionic surfactant can become increasingly charged by protonation through the addition of HCl, i.e. the degree of charging can be changed continuously. An interesting, isotropic phase (L₁ ^* phase) of low viscosity was observed for intermediate degrees of charging. From viscosity and conductivity measurements this phase can clearly be distinguished from the conventional L₁ phase that is composed of micelles. Investigation of the structures present by means of FF-TEM and SANS showed that the L₁ ^* phase is made up of unilamellar vesicles of extremely small diameter of 8–10 nm. Evidently such highly curved structures are stabilized by the electrostatic conditions in this system. Received: 11 July 1999/Accepted: 25 August 1999     

Phase Behavior, Structure, and Physical Properties of the Quaternary System Tetradecyldimethylamine Oxide, HCl, 1-Hexanol, and Water

The phase diagram of the ternary surfactant system tetradecyldimethylamine oxide (TDMAO)/HCl/1-hexanol/water shows with increasing cosurfactant concentration an L(1) phase, two L(alpha) phases (a vesicle phase L(alpha1) and a stacked bilayer phase L(alphah)), and an L(3) phase, which are separated by the corresponding two-phase regions L(1)/L(alpha) and L(alpha)/L(3). In this investigation, the system was studied where some of the TDMAO was substituted by the protonated TDMAO. Under these conditions, one finds for constant surfactant concentration of 100 mM TDMAO a micellar L(1) phase, an L(alpha1) phase (consisting of multilamellar vesicles), and an interesting isotropic L(1)(*) phase in the middle of the L(1)/L(alpha) two-phase region. The L(1)(*) phase exists at intermediate degrees of charging of 30-60% and for 40-120 mM TDMAO and 70-140 mM hexanol concentration. At surfactant concentrations less than 80 mM the L(1)(*)-phase borders directly on the L(1) phase. The phase transition between the L(1) phase and the L(1)(*) phase was detected by electric conductivity and rheological measurements. The conductivity values show a sharp drop at the L(1)/L(1)(*) transition, and the zero shear viscosity of the L(1)(*) phase is much lower than in L(1) phase. The form and size of the aggregates in L(1)(*) were detected with FF-TEM and SANS. This phase contains small unilamellar vesicles (SUV) of about 10 nm and some large multilamellar vesicles with diameters up to 500 nm. The system exhibits another peculiarity. For 100 mM surfactant, the clear L(alpha1)-phase exists only at chargings below 30%. With oscillating rheological measurements a parallel development of the storage modulus G' and the loss modulus G" was observed. Both moduli are frequency independent and the system possesses a yield stress. The storage modulus is a magnitude larger than the loss modulus. Copyright 2000 Academic Press.     

教师教学水平的时齐马尔可夫链评估方法

采用时齐马尔可夫链方法给出了一种评估教师教学水平的方法,对文［１］所给方法做了适当的改进,拓宽了该方法的应用范围,在多民族院校,使用本法可以克服由于学生基础不同等多方面的原因造成难以比较教师教学水平的难题．