The relationship between the chemical structure of nematic liquid crystals and their pretilt angles

About 50 different additives in one or more of three different nematic mixtures have been investigated to clarify the relationship between the chemical structure of the liquid crystal and the pretilt angle on a polyimide surface. The pretilts found for cells have been explained within our recently proposed population distribution model. For compounds with cyano-groups at one end, we find that the in-plane order is governed both by the surface-mesogen interaction and by the relative strength of the intermolecular interactions in the nematic phase. This strength is nearly linear in alkyl chain length for the compounds investigated. Changes in the strength due to variations in the core of the molecules can be calculated easily by using group contributions from the known Parachors. The in-plane order can be treated as a simple product of the contributions from the liquid crystal and from the polyimide. Different polar end groups will give different angles between the surface and the optical axis of the individual mesogens in the first monolayer. The cyano-group gives the highest angle and alkyl groups the lowest. For nitro-compounds the dimers formed are so strongly bound that they do not break up at the surface. Nitro-compounds will thus act as dialkyl compounds. For dialkyl compounds the pretilt angles are dominated by the difference between the chain lengths at the two ends of the molecule.     

Dansyl-Modified γ-Cyclodextrin as a fluorescent sensor for molecular recognition

The crystal structure of thiamine iodide sesquihydrate has been determined by X-ray diffraction methods as a host-guest model for coenzyme-substrate interactions. The asymmetric unit contains two chemical units. Both the thiamine molecules A and B, which are crystallographically independent, assume the usualF conformation and have a disordered hydroxyethyl side chain. An iodide anion (or a water molecule) bridges the pyrimidine and thiazolium rings of molecule A (or B) by forming a hydrogen bond with the amino group and an electrostatic contact with the thiazolium ring to stabilize the molecular conformation. In the crystal the thiamine molecules self-associate to form a pipe-like polymeric structure, in which four thiamine hosts surround an iodide guest and hold it through C(2)-H...I hydrogen bonds and thiazolium...I electrostatic interactions. Crystal data: C₁₂H₁₇N₄OS⁺·I^– · 1.5 H₂O, monoclinic,P2₁/c, a=12.585(2), b=25.303(5), c=12.030(2) Å, =115.15(1)°,V=3468(1) ų,Z=8,D _c=1.606 g cm^–3,R=0.045 for 3328 observed reflections. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP. 82156 (13 pages).     

Chemical constituents of Glycosmis citrifolia (Willd.) Lindl. Structures of four new acridones and three new quinolone alkaloids

The structures of two new dimeric acridone alkaloids, glycobismine-D (1) and -E (2), having a novel linkage as binary acridones, three monomeric acridones, glycocitrine-IV (3), -V (4), and -VI (5), and three quinolone alkaloids, glycocitlone-A (6), -B (7), and -C (8) from Glycosmis citrifolia (Willd.) Lindl. (Rutaceae) have been elucidated by spectrometric studies.     

Action spectra for photoreactivation of mutation of prototrophy in strains of Escherichia coli possessing and lacking photoreactivating-enzyme activity

Abstract— The action spectrum and dose-rate dependence for photoreactivation of mutation to prototrophy in late-lag-phase cultures of Escherichia coli H³r30 (which lacks active photo-reactivating enzyme) are roughly similar to those for photoprotection from killing in other strains. It is suggested that photoreactivation of this mutation in H/r30 is an indirect effect, similar in mechanism to photoprotection. The action spectrum and dose-rate dependence for photoreactivation of mutation to prototrophy in late-lag-phase cultures of E. coli H³r30-R (which possesses active photoreactivating enzyme) are roughly similar to those for photoreactivation of killing in most other strains. It is suggested that photoreactivation of this mutation in H/r30-R is a direct effect at long wavelengths, but that there is an indirect component at short wavelengths. A quite different interpretation of these data is noted. Finally, it is found that, under the conditions of these experiments, indirect photoreactivation of killing in H/r30 and H/r30-R is weak or nonexistent.     

Effect of hydrophobic amino acids on the conformational change of decapeptides in micellar environments

A series of peptides containing various hydrophobic amino acids [methionine (Met), leucine (Leu), norleucine (Nle), phenylalanine (Phe), 2-aminooctanoic acid (Aoc), and 2-aminodecanoic acid (Ade)] were synthesized and their conformations were studied using circular dichroism (CD) spectroscopy in different solvents such as water, methanol, and aqueous solution of ammonium tetradecanesulfonate. Peptides containing hydrophobic amino acids with linear side chains formed -sheets in water and methanol. Electrostatic interaction between the charged side chain (lysine) and a micelle consisting of an anionic surfactant, ammonium tetradecanesulfonate, is necessary for the formation of -helices in micellar environments. The conformational transition from -helix to -sheet structure required moderate hydrophobicity and linear side chains. This conformational transition depended on the surfactant concentration.     

Photoinduced face-inversion of conjugated tetraene ligands on a Pd-Pd-Pd moiety

The linear sandwich tripalladium complexes [Pd3{Ar(CH=CH)4Ar}2[BArf]2 (Ar = Ph, p-t-Bu-C6H4, p-styryl-C6H4) undergo photoinduced isomerization involving face-inversion of the tetraene ligands. Irradiation of these complexes with visible light (>510 nm) resulted in rac (staggered sandwich) to meso (eclipsed sandwich) isomerization. The structures of rac and meso isomers are determined by X-ray crystallographic analyses.     

Measurement of hyperfine structure constants,g values and tensor polarizability of excited states of Sm I

Atomic-beam laser spectroscopy with fluorescence detection is applied to investigate the hyperfine structure (hfs), Stark and Zeeman effects of the electric dipole transitions of Sm i. The measurements are performed for the four transitions of 0 → 15650.55, 292.58 → 15650.55, 292.58 → 15567.32, and 1489.55 → 16890.59 cm^-1. The hfs constants of the upper and lower levels and the isotope shifts of the transitions are determined. The tensor polarizability of the 15650.55 cm^-1 level is found to be α₂ = -556.2 ± 11.8 kHz/(kV/cm)². Thanks to the accurate g values of the lower levels [Childs, W.J., Goodman, L.S.: Phys. Rev. A 6, 2011 (1972)], the g values of the upper levels are obtained from the observed Zeeman splittings. The values are found to be -0.115907(79), 2.22259(20) and 1.599968(51) for the 15650.55 cm^-1 .1, 15567.32 cm^-1 and 16890.59.cm^-1 levels, respectively.     

A comparison of supercritical carbon dioxide and organic solvents for the intercalation of 4-phenylazoaniline into a pillared clay mineral

The intercalation of 4-phenylazoaniline (PAA) in supercritical carbon dioxide (SC-CO(2)) into montmorillonite (TMA-Mnt) pillared with tetramethylammonium ions at 313 K and 15 MPa was investigated. The adsorption rate and equilibrium PAA uptake were compared with those in n-hexane, CCl(4) and benzene solutions at 313 K. The XRD and N(2) adsorption/desorption analyses showed that TMA-Mnt after adsorption of PAA in SC-CO(2) had the same pore structure as after adsorption of PAA in normal solvents. SC-CO(2) was found to be a good medium for PAA adsorption owing to its having a relatively high adsorption rate and the highest adsorptivity at the same PAA concentration. The properties of PAA adsorption on TMA-Mnt could be well elucidated by the difference in solubility parameters between liquid and solid phases.     

Control of viscoelasticity using redox reaction

The viscoelasticity of a fluid was tuned with the Faradaic reaction of (11-ferrocenylundecyl)trimethylammonium bromide (FTMA), a "redox-switchable" surfactant. An aqueous solution of the reduced form of FTMA exhibited a remarkable viscoelasticity in the presence of sodium salicylate (NaSal) because of the formation of three-dimensional entanglement of wormlike micelles. Electrolytic oxidation of FTMA caused the viscosity of the system to dramatically decrease and the elasticity to disappear. This drastic decrease in viscoelasticity arose from the disruption of wormlike micelles. This novel electrorheological phenomenon is expected to be applicable to ink for inkjet printers, the electrochemically controlled release of substances entrapped in wormlike micelles of FTMA, and fluid flow rate control using electric signals.