New (1R,4R)-2-arylidene-p-menthan-3-ones with a bridging ester group in the arylidene fragment. Synthesis and behavior in liquid-crystalline systems

(1R,4R)-2-(4-Hydroxybenzylidene)- and (1R,4R)-2-(4′-hydroxybiphenyl- 4-yl)methylene-p-menthan-3-ones were synthesized by condensation of (-)-menthone with O-tetrahydropyran-2-yl derivatives of 4-hydroxybenzaldehyde and 4′-hydroxy-4-formylbiphenyl, respectively, in a DMSO - base medium followed by the removal of the protective group. The reactions of these hydroxy derivatives with 4-alkylbenzoic, 4-alkyloxybenzoic, trans-4-alkylcyclohexane-4- carboxylic, and 4′-alkylbiphenyl-4-carboxylic acids afforded three series of new chiral esters. Compounds containing the arylidene moiety with three benzene rings were found to exhibit liquid-crystalline properties. The characteristic features of these compounds are discussed based on the results of studies by polarizing microscopy, differential scanning calorimetry, and small-angle X-ray scattering. It was found that the mesomorphic compounds under study can form a smectic A mesophase, twist grain boundary mesophases (TGBA), and blue phases in a wide temperature range. Upon dissolution of certain of chiral compounds in 4′-cyano-4-pentylbiphenyl, a rather high twisting power and the thermal stabilizing effect on mesophases were observed.

A family of simple benzene 1,3,5-tricarboxamide (BTA) aromatic carboxylic acid hydrogels.

We present the characterisation of a hydrogel forming family of benzene 1,3,5-tricarboxamide (BTA) aromatic carboxylic acid derivatives. The simple, easy to synthesise compounds presented here exhibit consistent gel formation at low concentrations through the use of a pH trigger.

Detection of molecular interactions with modified ferrocene self-assembled monolayers.

Ferrocene-terminated self-assembled monolayers (Fc-SAMs) are one of the most studied molecular aggregates on metal electrodes. They are easy to fabricate and provide a stable and reproducible system to investigate the effect of the microenvironment on the electron transfer parameters. We propose a novel application for Fc-SAMs, the detection of molecular interactions, based on the modification of the SAM with target-specific receptors. Mixed SAMs were fabricated by coimmobilization on Au electrodes of thiolated alkane chains with three different head groups: hydroxy terminating head group, ferrocene head group, and a functional head group such as biotin. Upon binding, the intrinsic electric charge of the target (e.g., streptavidin) modifies the electrostatic potential at the plane of electron transfer, causing a shift in the formal potential E degrees '. The SAMs were characterized by AC voltammetry. The detection mechanism is confirmed by measurements of formal potential as a function of electrolyte pH.

Ferroelectric liquid crystal mixtures containing chiral ether and ester compounds with the 2-arylidene-p-menthan-3-one skeleton

Some 1R,4R-2-(4-phenylbenzylidene)-p-menthane-3-one derivatives containing the ether or ester linking group between benzene rings of the arylidene fragment have been studied as chiral dopants in ferroelectric liquid crystal systems based on the eutectic mixture (1:1) of two phenylbenzoate derivatives CmH2m+1OC6H4COOC6 H4OCnH2n+1 (n = 6; m = 8, 10). The ferroelectric properties of these compositions (spontaneous polarization, rotation viscosity, smectic tilt angle as well as quantitative characteristics of their concentration dependences) were compared with those for systems including chiral dopants containing no linking group. Ferroelectric parameters of the induced ferroelectric compositions studied have been shown to depend essentially on the presence of the linking group between benzene rings and its nature as well as on the number of the benzene rings in the rigid molecular core of the chiral dopants used. For all ferroelectric liquid crystal systems studied, the influence of the chiral dopants on the thermal stability of N*, SmA and SmC* mesophases has been quantified. The influence of the linking group nature in the dopant molecules on the characteristics of the systems studied is discussed taking into account results of the conformational analysis carried out by the semi-empirical AM1 and PM3 methods.

Europium-directed self-assembly of a luminescent supramolecular gel from a tripodal terpyridine-based ligand.

Eu(III), the last piece in the puzzle: Europium-induced self-assembly of ligands having a C(3)-symmetrical benzene-1,3,5-tricarboxamide core results in the formation of luminescent gels. Supramolecular polymers are formed through hydrogen bonding between the ligands. The polymers are then brought together into the gel assembly through the coordination of terpyridine ends by Eu(III) ions (blue dashed arrow: distance between two ligands in the strand direction).