Coherent effects in energy transport in model dendritic structures investigated by ultrafast fluorescence anisotropy spectroscopy

Measurements of ultrafast fluorescence anisotropy decay in model branched dendritic molecules of different symmetry are reported. These molecules contain the fundamental branching center units of larger dendrimer macromolecules with either three (C(3))- or four (T(d), tetrahedral)-fold symmetry. The anisotropy for a tetrahedral system is found to decay on a subpicosecond time scale (880 fs). This decay can be qualitatively explained by F?rster-type incoherent energy migration between chromophores. Alternatively, for a nitrogen-centered trimer system, the fluorescence anisotropy decay time (35 fs) is found to be much shorter than that of the tetramers, and the decay cannot be attributed to an incoherent hopping mechanism. In this case, a coherent interchromophore energy transport mechanism should be considered. The mechanism of the ultrafast energy migration process in the branched systems is interpreted by use of a phenomenological quantum mechanical model, which examines the two extreme cases of incoherent and coherent interactions.     

Copper-catalyzed amination of aromatic halides with 2-N,N-dimethylaminoethanol as solvent

A copper-catalyzed amination of aromatic halides under mild conditions using N,N-dimethylaminoethanol as solvent is described. We have studied this reaction in some detail varying the copper source, base, water content and other parameters including the scope of useful amine and aromatic halide structures. A variety of 4-halo-N,N-cycloalkylanilines and 2-N,N-cycloalkylaminothiophenes were synthesized for further elaboration into chromophores for optoelectronic applications.     

Reentrant phenomenon in cyanoaryl alkylthioxybenzoates and cyanobenzoyloxyphenyl alkylthiobenzoates

Abstract

Three new series of cyanoaryl 4-alkylthioxybenzoates have been synthesized and characterized. The 4-cyanophenyl series displays only transient mesomorphic properties while the 6-cyano-2-naphthyl and 4-cyanobiphenyl series exhibit the classical nematic and smectic A phases; a reentrant nematic phase is also found in the latter. Two other new series in which the position of the sulphur atom in the central rigid core has been varied were also prepared: the 4–[4′-cyanobenzoyloxy]-phenyl 4-alkylthiobenzoates and 4–[4′-alkylbenzoyloxy]phenyl 4-cyanothiobenzoates. As in the analogous benzoate series, the reentrant phenomenon with the sequence C, S_Are, N_re, S_A, N, I is observed with the nonyl derivatives. Comparisons between the alkoxybenzoates and the alkylthioxybenzoates are given.     

Pretilt study of double‐layer alignment film (DLAF)

A novel double‐layer alignment film (DLAF) was developed to obtain greater control of the alignment characteristics of the liquid crystal director. The DLAF consists of a thin fluorinated polymer layer on the top of a rubbed non‐fluorinated, non‐branched polyimide layer (PI 2555). Two types of fluorinated polymer with different chemical structures and wetting behaviour on PI 2555 were chosen, to provide either continuous or discontinuous top layers. The continuous top layer DLAF (DLAF‐1) exhibits an abrupt pretilt transition from planar to homeotropic as the top layer thickness increases. The discontinuous top layer DLAF (DLAF‐2) exhibits a gradual transition where the pretilt correlates with the coverage of fluorinated top layer. These two types of transitions fit with de Gennes' local Frederick's transition and Kwok's inhomogeneous alignment theories, respectively. The abrupt pretilt transition system may be promising for chemical/biosensor applications, whereas the gradual transition system is suitable for pretilt control in LCD devices.     

X-ray determination of the mean amplitudes of vibration and debye temperatures of some rare earth monochalcogenides

The x-ray diffraction intensities of Bragg reflections have been measured at room temperature for thulium selenide, samarium sulphide, samarium selenide and samarium telluride. On the basis of a common amplitude approximation, the Debye-Waller factor, the mean amplitude of vibration and the Debye temperature have been evaluated. The values of the Debye temperatures and mean amplitudes of vibration are 176±16°K, 0·185 ± 0·017 Å (TmSe), 155 ± 7°K, 0·244 ± 0·012 Å (SmS), 153 ± 14°K, 0·221 ± 0·020 Å (SmSe) and 151 ± 20°K, 0·204 ± 0·027 Å (SmTe).     

Improved depiction of small anatomic structures in MR images using Gaussian-weighted spirals and zero-filled interpolation

Partial-volume artifacts reduce the contrast and continuity of small structures in magnetic resonance images. Zero-filled interpolation (ZFI) has been known for some time as a useful technique to reduce partial-volume artifacts and improve the appearance of small structures and edges. However, its use is limited by the fact that ZFI can exacerbate image artifacts. For example, it can exacerbate Gibbs ringing, also known as the truncation artifact, which manifests itself as spurious ringing around sharp edges. Currently, the most common technique to address this problem is post-acquisition filtering, which causes blurring in the image. Using ZFI in conjunction with a variable-density sampling method designed to reduce ringing is proposed as a possible solution to this problem. This approach is demonstrated with a Gaussian-weighted spiral and is compared to conventional spiral sampling both with and without the application of a filter used to reduce ringing. The two spiral sampling techniques are compared using simulations, phantom images, and in vivo brain images. The Gaussian-weighted spiral demonstrates reduced ringing without the loss of spatial resolution commonly associated with post-acquisition filtering. Additionally, this sampling technique is shown to work well in conjunction with ZFI to reduce partial-volume artifacts without the apparent increase in Gibbs ringing usually associated with zero-filled reconstruction. This approach will be most useful for imaging techniques such as MR angiography which are known to be sensitive to partial-volume effects, as well as when imaging anatomic regions associated with more severe Gibbs ringing.     

Controlled self-assembly of triphenylene-based molecular nanostructures

Molecular nanostructures of the disc-shaped molecule hexapentyloxytriphenylene have been fabricated on length scales ranging from 30 nm to 1.5 mum following self-assembly arising from pi-pi interactions in organic solvents. The size and density of the molecular nanostructures deposited onto glass and indium tin oxide-coated glass substrates were characterized by atomic force microscopy. Dynamic light scattering and spectroscopic evidence of predeposition aggregation in solution are presented, suggesting that the nanostructures are organized in solution and then deposited onto the substrate. Correlations between the relative solvent polarity and the size of molecular nanostructures as well as between the solute concentration in dilute solutions and their density on the substrate are discussed.     

Synthesis and ferroelectric properties of laterally substituted fluoro liquid crystals derived from 4-mercaptobenzoic acid

Several new ferroelectric liquid crystals with thiobenzoate mesogenic cores have been synthesized and the influence of a single fluorine atom ortho to the alkyloxy tail on the mesomorphic properties of some two and three benzene ring core compounds has been studied. The two benzene ring derivatives do not display the ferroelectric smectic C phase but the three phenyl ring compounds exhibit a wide temperature range S_c* phase. The transition temperatures and enthalpies of transition for these compounds have been determined; the spontaneous polarization, response time and tilt angle have also been measured and are discussed as a function of the structure near to the chiral centre.