Evaporation of water droplets on polymer surfaces

The evaporation of water droplets on polymer surfaces was investigated by using a digital image analysis technique. There were three distinct stages in the water evaporation process: a constant contact area mode, a constant contact angle mode, and a mixed mode that is independent of both the initial quantity of water droplets and the hydrophobic properties of the polymer surfaces. The physical factors influencing the first and second transitions in the evaporation process were found to be the attainment of the receding angle on the polymer surfaces and the Marangoni instability in the evaporating water droplets, which result from the concentration gradient of contaminants. This study also provides qualitative information about the microfluid flows inside the evaporating water droplets and the morphology of drying stains on polymer surfaces. The contaminants were found to be concentrated at the perimeter of the stains, in agreement with the observed outward microfluid flow in the mixed mode of the evaporation process.     

Cubic and Columnar Supramolecular Architectures of Rod–Coil Molecules in the Melt State

The liquid crystalline behavior of compounds 1 (n = 7, 12, 15) differs significantly from that exhibited for conventional rodlike molecules. They organize into layered smectic, bicontinuous cubic or hexagonal columnar mesophases depending on the temperature or the volume fraction of coil segments.     

Cover Picture: Solid‐State Scrolls from Hierarchical Self‐Assembly of T‐Shaped Rod–Coil Molecules (Angew. Chem. Int. Ed. 9/2009)

Solid scrolls are reversibly formed by self‐assembly of rod‐shaped molecules with laterally attached coil units, in contrast to the layered structures formed from self‐assembly of planar molecules. As described by M. Lee and co‐workers in their Communication on page 1664 ff., the core structure of the scrolls, which are either filled cylinders or hollow tubes, can be controlled by variation of the length of the coil unit. The cover picture shows aligned tubular scrolls displaying well‐defined in‐plane ordering of the rod segments.

     

Assemblies of supramolecular porphyrin dimers in pentagonal and hexagonal arrays exhibiting light-harvesting antenna function

Porphyrin-based supramolecular macrocyclic arrays were synthesized as mimics of photosynthetic light-harvesting (LH) antennae. Pentameric and hexameric macrocyclic porphyrin arrays EP5 and EP6 were constructed by complementary coordination of m-bis(ethynylene)phenylene-linked zinc-imidazolylporphyrin Zn-EP-Zn. The proton NMR spectra of noncovalently linked N-EP5 and N-EP6 indicate fast rotation of the porphyrin moieties along the ethyne axis. These macrocycles were covalently linked and identified as C-EP5 (6832 Da) and C-EP6 (8199 Da) by mass spectrometry. Fluorescence quantum yields of C-EP2 (10.0%), C-EP5 (10.1%), and C-EP6 (11.0%), even larger than that of the unit coordination dimer C-EP1 (9.3%), were significantly increased from those of the series without the ethynylene linkage. The order of increasing fluorescence quantum yields was parallel to that of decreasing fluorescence lifetimes (C-EP1 (1.65 ns), C-EP2 (1.45 ns), C-EP5 (1.42 ns), and C-EP6 (1.38 ns)), indicating that the radiative decay rate kF increased relative to the other decay rates with an increase in the number of ring components. Based on the exciton-exciton annihilation and anisotropy depolarization times, the excitation energy hopping (EEH) times in these macrocyclic systems were obtained as 21 ps for C-EP5 and 12.8 ps for C-EP6. EEH times depend strongly on the orientation factor of the component transition dipoles in the macrocyclic arrays. The hexagonal macrocyclic array with an orientation of better transition dipole coupling resulted in faster EEH time compared to the pentagonal one.     

Self-organization of bent rod molecules into hexagonally ordered vesicular columns

Bent-shaped rigid-core molecules with flexible chiral dendrons grafted to the outer side of the bend were synthesized and characterized by circular dichroism, differential scanning calorimetry, X-ray scatterings, and transmission electron microscopy in solution and the solid state. The bent aromatic rods based on hepta- and nonaphenylene with nitrile groups at both ends self-assemble into well-ordered hollow tubular structures in aqueous solution, while the bent rod based on heptaphenylene without nitrile groups showed no apparent aggregations in aqueous solution. In the solid state, the rigid-flexible molecules based on heptaphenylene rod without the nitrile group self-assemble into a 2D oblique columnar structure with the columnar cross-section containing two interlocked molecules. Remarkably, the rigid flexible molecules based on hepta-, nona-, and undecaphenylene with nitrile groups self-assemble into a hexagonal columnar structure with weak 3D order. A model of vesicular channel structure is proposed based on small- and wide-angle X-ray diffraction on oriented fibers, density measurement, reconstruction and simulation of electron density maps, and molecular dynamics simulation. In contrast to the hollow tubular structure found in solution, in the solid both the outside and the interior of the columns are filled by the pendant aliphatic coils. Filling of the interior of these vesicular channels is made possible by some bent rod molecules turning their obtuse apex inward. One in 7, 2 in 8, and 4 in 10 molecules are thus inverted in a column slice in compounds with hepta-, nona-, and undecaphenylene cores, respectively. These are new examples of vesicular double-segregated columnar structures recently discovered in some dendrons.     

Coherent phonon dynamics in short-period InAs/GaSb superlattices

We have performed ultrafast pump-probe spectroscopy studies on a series of InAs/GaSb-based short-period superlattice (SL) samples with periods ranging from 46 Å to 71 Å. We observe two types of oscillations in the differential reflectivity with fast (∼$\sim$1–2 ps) and slow (∼$\sim$24 ps) periods. The period of the fast oscillations changes with the SL period and can be explained as coherent acoustic phonons generated from carriers photoexcited within the SL. This mode provides an alternative method for determining the SL period. The period of the slow mode depends on the wavelength of the probe pulse and can be understood as a propagating coherent phonon wavepacket modulating the reflectivity of the probe pulse as it travels from the surface into the sample.     

Studies on cyclic dipeptides, II. Methylated modifications ofcyclo-[Phe-His]

Summary Synthesis of seven new cyclic dipeptides and their conformational analysis based on¹HNMR spectra is reported as well as their application as models to elucidate the mechanism of cyclic dipeptide catalysis in enantioselective mandelonitrile formation. Further evidence is presented to support the view that a highly ordered supramolecular complex of dipeptides acts as catalyst.

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Untersuchungen an cyclischen Dipeptiden, 2. Mitt.: Methylierte Derivate von cyclo-[Phe-His]

Zusammenfassung Es wird die Synthese sieben neuer cyclischer Dipeptide, ihre Konformationsanalyse (basierend auf¹H-NMR-Daten) und ihre Anwendung als Modelle zur Aufklärung des Mechanismus der dipeptidkatalysierten enantioselektiven Mandelsäurenitrilsynthese beschrieben. Weitere Hinweise zur Stützung der Annahme, daß ein hoch geordneter supramolekularer Komplex aus Dipeptiden für die Katalyse ausschlaggebend ist, werden vorgelegt.