Rigid stars: properties and functions

The properties of star-shaped adamantane multipodes with different types of rigid branches with various lengths are discussed. The expectation based on theoretical considerations was that such multipodes would display an enhanced solubility both in low molar mass solvents and in polymer matrices. These multipodes have a three-dimensional star-like shape, are able to crystallize but can also be obtained in the glassy state, and they show a relaxational behavior typical for polyarylates. They are soluble in various low molar mass organic solvents much better than linear rigid molecules of the same chemical constitution and of similar length and they are miscible in polymer matrices up to concentrations of 30 wt%. The multipodes were found to influence the dielectric and mechanical properties of the matrix polymers significantly. © 1998 John Wiley & Sons, Ltd.     

Matrix isolation, spectroscopic characterization, and photoisomerization of m-xylylene

A new efficient synthesis of m-xylylene 1 is reported. The diradical 1 was trapped in argon matrices at 10 K and characterized by IR, UV-vis, and EPR spectroscopy. The syntheses reported before only allowed generation of 1 in organic glasses, and the spectroscopic identification was limited to fluorescence and EPR spectroscopy. Diradical 1 proved to be highly photolabile, and irradiation results in the formation of three isomeric hydrocarbons 7, 9, and 11 which could be identified by comparison of their IR spectra with the results of DFT calculations.     

Synthesis of Diacetylene‐Containing Peptide Building Blocks and Amphiphiles,Their Self‐Assembly and Topochemical Polymerization in Organic Solvents

A series of functional iodoacetylenes was prepared and converted into the corresponding diacetylene‐substituted amino acids and peptides via Pd/Cu‐promoted sp–sp carbon cross‐coupling reactions. The unsymmetrically substituted diacetylenes can be incorporated into oligopeptides without a change in the oligopeptide strand's directionality. Thus, a series of oligopeptide‐based, amphiphilic diacetylene model compounds was synthesized, and their self‐organization as well as their UV‐induced topochemical polymerizability was investigated in comparison to related polymer‐substituted macromonomers. Solution‐phase IR spectroscopy, gelation experiments, and UV spectroscopy helped to confirm that a minimum of five N‐H???O?C hydrogen‐bonding sites was required in order to obtain reliable aggregation into stable β‐sheet‐type secondary structures in organic solvents. Furthermore, the non‐equidistant spacing of these hydrogen‐bonding sites was proven to invariably lead to β‐sheets with a parallel β‐strand orientation, and the characteristic IR‐spectroscopic signatures of the latter in organic solution was identified. Scanning force micrographs of the organogels revealed that compounds with six hydrogen‐bonding sites gave rise to high aspect ratio nanoscopic fibrils with helical superstructures but, in contrast to the related macromonomers, did not lead to uniform supramolecular polymers. The UV‐induced topochemical polymerization within the β‐sheet aggregates was successful, proving parallel β‐strand orientation and highlighting the effect of the number and pattern of N‐H???O?C hydrogen‐bonding sites as well as the hydrophobic residue in the molecular structure on the formation of higher structures and reactivity.     

Fluid phase separation inside a static periodic field: an effectively two-dimensional critical phenomenon

When a fluid with a bulk liquid-vapor critical point is placed inside a static external field with spatial periodic oscillations in one direction, a new phase arises. This new phase-the so-called "zebra" phase-is characterized by an average density roughly between that of the liquid and vapor phases. The presence of the zebra phase gives rise to two new phase transitions: one from the vapor to the zebra phase, and one from the zebra to the liquid phase. At appropriate values of the temperature and chemical potential, the latter two transitions become critical. This phenomenon is called laser-induced condensation [I. O. Go?tze, J. M. Brader, M. Schmidt, and H. Lo?wen, Mol. Phys. 101, 1651 (2003)]. The purpose of this paper is to elucidate the nature of the critical points, using density functional theory and computer simulation of a colloid-polymer mixture. The main finding is that critical correlations develop in two-dimensional sheets perpendicular to the field direction, but not in the direction along the field: the critical correlations are thus effectively two-dimensional. Hence, static periodic fields provide a means to confine a fluid to effectively two dimensions. Away from criticality, the vapor-zebra and liquid-zebra transitions become first-order, but the associated surface tensions are extremely small. The consequences of the extremely small surface tensions on the nature of the two-phase coexistence regions are analyzed in detail.     

Automated microaxial tomography of cell nuclei after specific labelling by fluorescence in situ hybridisation

Microaxial tomography provides a good means for microscopic image acquisition of cells or sub-cellular components like cell nuclei with an improved resolution, because shortcomings of spatial resolution anisotropy in optical microscopy can be overcome. Thus, spatial information of the object can be obtained without the necessity of confocal imaging. Since the very early developments of microaxial tomography, a considerable drawback of this method was a complicated image acquisition and processing procedure that requires much operator time. In order to solve this problem the Heidelberg 2π-tilting device has been mounted on the Brno high-resolution cytometer as an attempt to bring together advanced microscopy and fast automated computer image acquisition and analysis. A special software module that drives all hardware components required for automated microaxial tomography and performs image acquisition and processing has been developed. First, a general image acquisition strategy is presented. Then the procedure for automation of axial tomography and the developed software module are described. The rotation precision has been experimentally proved followed by experiments with a specific biological example. For this application, also a method for the preparation of cell nuclei attached to glass fibres has been developed that allows for the first time imaging of three-dimensionally conserved, fluorescence in situ hybridisation-stained cell nuclei fixed to a glass fibre.