Diagrams,orientations, and varieties

One of the central problems in the theory of ordered sets is to describe the orientations of the covering graph of an ordered set. We show that the particular operation called inversion, together with the classical constructions of retraction and product, provide a context for the classification of all such orientations. AMS subject classifications (1980). 06A10, 05C75, 05C20.     

Force field and 13C-NMR investigations of substituted cyclopentanes. A concept for the adaption of 13C NMR shifts to varying torsional arrangements in flexible conformers

MM2 Exploration of the conformational space for methylcyclopentane, in contrast to cyclopentanone yields more and flatter minima than known previously. Calculations of cyclopentanes with substituents X = F, Cl, CHMe₂, and CMe₃ with two stable conformations indicate <2° torsional angle changes with the different substituents. Cyclopentanes bearing not more than 2 substituents can accommodate all groups in pseudoequatorial positions without changing the basic envelope and twist chair geometries significantly. A model for ¹³C-shift calculation is proposed in which shift increments for the different torsional arrangements are obtained by linear interpolation between corresponding cyclohexane values. After correction for the nonequivalent carbon shifts in the hydrocarbon itself, again using the linear interpolation, a significant improvement of the shift correlations is observed. For disubstituted cyclopentanes these predict the shifts within ± 1.7 ppm with Me, CHMe₂, CMe₃, Cl, Br and OH as substituents. Configurational assignments are difficult with 1,3-di-substituted cyclopentanes, but straightforward with 1,2-di- and trisubstituted compounds. Thus, due to the presence of smaller torsional angles between, e.g. diequatorial vicinal substituents in the 1,2- cis series as compared to the trans compounds, the latter show deshielding, particularly at C2, by 1–4 ppm. Several epimers are stereo-selectively prepared by suitable ketone reduction and displacement methods.     

Hemicucurbit[6]uril a Macrocyclic Ligand with Unusual Complexing Properties

The complex formation of the macrocyclic ligand hemicucurbit[6]uril with various salts has been studied in aqueous solution. Due to the low solubility of this ligand the formation of complexes results in an increase of the amount of ligand present in solution. From these measurements the stability constants of the complexes formed are calculated. Hemicucurbit[6]uril only forms cation complexes with cobalt(II), nickel(II) and the uranylion. All other cations examined e.g. silver(I), lead(II) and copper(II) do not form detectable complexes in aqueous solution. For a better understanding of the complexation behaviour some quantum mechanical chemical calculations are performed with Gaussian.Dedicated to Prof. H. Möhwald on the occasion of his 60th birthday.     

Equilibrium interaction of solid surfaces across a polymer melt

Forces across polymer melts are poorly understood despite their importance for adhesion and fabricating composite materials. Using an atomic force microscope (AFM), this interaction was measured for poly(dimethyl siloxane) (PDMS). The structure of the polymer at the surface changed during the first approximately 10 h. Afterward, short-range attractive forces were observed with short-chain PDMS (M(w) = 4200 g/mol). Using PDMS with a molecular weight (M(w) = 18 000 g/mol) above the entanglement limit, we measured a monotonically decaying repulsive force, which indicates that a quasi-immobilized layer had formed at the solid surface. Due to the small radius of curvature of the tip, forces could be measured in equilibrium.     

Neutral and ionic aluminum,gallium, and indium compounds carrying two or three terminal ethynyl groups

The syntheses of the ionic compounds [Li(+).2 dioxane (2,6-iPr(2)C(6)H(3)N(SiMe(3))Al(C triplebond CSiMe(3))(3))(-)].0.75 dioxane (1), [(Li(+))(2).(dioxane)(7)](0.5) [2,6-iPr(2)C(6)H(3)N(SiMe(3))Ga(C triplebond CSiMe(3))(3)(-)].1.5 dioxane (2), and [(Li(+))(2).(dioxane)(7)](0.5) [2,6-iPr(2)C(6)H(3)N(SiMe(3))In(C triplebond CSiMe(3))(3)(-)].1.5 dioxane (3) by the reaction of the corresponding organo metal chloride with LiC triplebond CSiMe(3) are reported. The neutral ethynyl compounds Br-Al(C triplebond CtBu)(2).2 THF (4), Cl-Ga(C triplebond CtBu)(2).THF (5), Cl-In(C triplebond CtBu)(2).2 THF (6), Al(C triplebond CtBu)(3).C[N(Me)CMe](2) (7), Ga(C triplebond CtBu)(3).dioxane (8), and In(C triplebond CtBu)(3).NEt(3) (9) have been obtained in good yields from the reaction of AlBr(3), GaCl(3), and InCl(3) with LiC triplebond CtBu in the presence of a Lewis base. Compound 7 is the first heterocyclic carbene substituted ethynyl derivative. Aluminum and gallium compounds with three terminal ethynyl groups Al(C triplebond CPh)(3).NMe(3) (10) and Ga(C triplebond CPh)(3).NMe(3) (11) have been prepared by the reaction of AlH(3).NMe(3) or GaH(3).NMe(3) with three equivalents of phenylethyne. All the above-mentioned compounds have been structurally studied. In compound 1 the lithium ion is coordinated to the three terminal ethynyl groups, whereas in compounds 2 and 3 the lithium is coordinated to the solvent (dioxane). Compound 8 crystallizes as a coordination polymer with dioxane molecules bridging the individual gallium units.     

Microdrops on atomic force microscope cantilevers: evaporation of water and spring constant calibration

The evaporation of water drops with radii approximately 20 microm was investigated experimentally by depositing them onto atomic force microscope (AFM) cantilevers and measuring the deflection versus time. Because of the surface tension of the liquid, the Laplace pressure inside the drop, and the change of interfacial stress at the solid-liquid interface, the cantilever is deflected by typically a few hundred nanometers. The experimental results are in accordance with an analytic theory developed. The evaporation process could be monitored with high accuracy even at the last stage of evaporation because (1) cantilever deflections can be measured with nanometer resolution and (2) the time resolution, given by the inverse of the resonance frequency of the cantilever of approximately 0.3 ms, is much faster than the typical evaporation time of 1 s. Experimental results indicate that evaporation of the last thin layer of water is significantly slower than the rest of the drop, which can be due to surface forces. This drop-on-cantilever system can also be used to analyze the drop impact dynamics on a surface and to determine the spring constant of cantilevers.     

Tilt of atomic force microscope cantilevers: effect on spring constant and adhesion measurements

In atomic force microscopy, the cantilevers are mounted under a certain tilt angle alpha with respect to the sample surface. In this paper, we show that this increases the effective spring constant by typically 10-20%. The effective spring constant of a rectangular cantilever of length L can be obtained by dividing the measured spring constant by cos2 alpha(1 - 2D tan alpha/L). Here, alpha is the tilt angle and D is the size of the tip. In colloidal probe experiments, D has to be replaced by the radius of the attached particle. To determine the effect of tilt experimentally, the adhesion force between spherical borosilicate particles and planar silicon oxide surfaces was measured at tilt angles between 0 degrees and 35 degrees. The experiments revealed a significant decrease of the mean apparent adhesion force with a tilt of typically 20-30% at alpha = 20 degrees. In addition, they demonstrate that the adhesion depends drastically on the precise position of contact on the particle surface.     

Vergleichende Messungen des Zeta-Potentials von Faserstoffen durch Elektroosmose und Strömungsstrom/Strömungspotential

An apparatus for the determination of zetapotential is described, which allows measurement of both streaming potential and streaming current as well as electroosmosis with one and the same fiber diaphragm with various electrodes (calomel, Ag/AgCl, palladium). Measurements with glass fibers, fibers of polyacrylonitrile and of polyester, and with cellulose pulp show that identical values for the electrokinetic parameters are obtained independent of voltage applied during electroosmosis resp. pressure difference during streaming measurements. This allows the conclusion that the zetapotential in dilute electrolyte solution is here an unequivocally determinable figure.

Herrn Prof. Dr.R. C. Schulz mit den herzlichsten Glückwünschen zum 65. Geburtstag gewidmet.