Guy A. Hembury

Supramolecular chirogenesis in zinc porphyrins: interaction with bidentate ligands, formation of tweezer structures, and the origin of enhanced optical activity.

The complexation behavior, binding properties, and spectral parameters of supramolecular chirality induction in the achiral host molecule, syn (face-to-face conformation) ethane-bridged bis(zinc porphyrin), upon interaction with chiral bidentate guests (diamines and amino alcohols) have been studied by means of UV-vis, CD, fluorescence, (1)H NMR, and ESI MS techniques. It was found that the guest structure plays a decisive role in the chirogenesis pathway. The majority of bidentate ligands (except those geometrically unsuitable) exhibit two major equilibria steps: the first guest ligation leading to formation of the 1:1 host-guest tweezer structure (K(1)) and the second guest molecule ligation (K(2)) forming the anti bis-ligated species (1:2). The second ligation is much weaker (K(1) >> K(2)) due to the optimal geometry and stability of the 1:1 tweezer complex. The enhanced conformational stability of the tweezer complex ensures an efficient chirality transfer from the chiral guest to the achiral host, consequently inducing a remarkably high optical activity in the bis-porphyrin.

The pH dependence of the anisotropy factors of essential amino acids

In order to examine the pH dependence of the anisotropy factor (g) of all the essential amino acids, at pHs 1, 2, 7 and 11, the molar absorption coefficient (e) and circular dichroism (Δe) were determined in aqueous solution. The g factors were high, and except for Asn and the aromatic and sulfur-containing compounds (Tyr, His, Trp, Cys and Met) the gmax values are larger than 0.01 in the pH range 1–7. Large g factors of aliphatic amino acids are observed even at pH 11. On the whole the magnitudes of the g factors at pH 1 are 2–3 times those at pH 7. The n,π* transition of the carboxylic group is the major contributor to the large g factors in amino acids such as Ala and Val. It is thought that in connection with the possible origin of amino acid homochirality generated by circularly polarised light irradiation, the % ee (≡ % op) of the amino acid generated will also be pH dependent in a manner similar to that previously reported for Leu.

Enthalpy-entropy compensation upon syn-anti conformational switching of bis-porphyrins by amines and alcohols

Upon interaction with amine and alcohol guests, Zn-Zn and Zn-2H ethane-bridged bis-porphyrin hosts undergo dramatic conformational switching from a syn to an anti form. The thermodynamic parameters obtained exhibit excellent linear enthalpy-entropy correlations, which are distinctly different for amines and alcohols but essentially independent of the host structure. Analyses of the compensation plots reveal a more rigid complex structure and more extensive desolvation upon complexation with amines than for alcohols, which may be ascribed to the different nucleophilicity, binding strength, solvation and geometry.