Amino acids chiral, recognition

Ligand 62 [83] was prepared for the enantioselective recognition of amino acids. Chiral carboxylates are bound by cooperative binding by electrostatic... 

Metal complexes of dimers linked with flexible spacers give rise to polymeric complexes at a higher concentration of diamine. Two metalloporphyrins with C2 symmetry linked with a rigid chiral amine spacer (Troger s base) show diastereomeric recognition for optically active, basic amino acids.- - Chiral diamine derivatives such as basic amino-acid esters are tightly bound with moderate enantioselec-tivity to the zinc porphyrin tweezers in the inner-homochiral cavity of the host (Figure 7). It is noted that... 

ABSTRACT. The copper(n) complexes of p-cyclodextrins functionalized with aliphatic or pseudoaromatic amines were used for the chiral recognition of unmodified amino acids. Molecular recognition, assisted by non-covalent interactions, was proved by means of thermodynamic and spectroscopic (c.d., e.p.r. and fluorescence) measurements. A cis-disposition of amino groups seems to assist enantiomeric selectivity. The copper(II)-p-cyclodextrin complexes can be used as mobile phase additives in HPLC to separate enantiomeric mixtures of unmodified aromatic amino acids. 

Moussa A, Pham C, Bommireddy S, Muller G. Importance of Hydrogen-Bonding Sites in the Chiral Recognition Mechanism Between Racemic D3 Terbium(III) Complexes and Amino Acids. Chirality 2009 21 497-506. 

Biological systems depend on specific detailed recognition of molecules that distinguish between chiral forms. The translation machinery for protein synthesis has evolved to utilize only one of the chiral forms of amino acids, the L-form. All amino acids that occur in proteins therefore have the L-form. There is, however, no obvious reason why the L-form was chosen during evolution and not the D-form... 

The term chiral recognition refers to a process in which some chiral receptor or reagent interacts selectively with one of the enantiomers of a chiral molecule. Very high levels of chiral recognition are cormnon in biological processes. (—)-Nicotine, for example, is much more toxic than (-F)-nicotine, and (-F)-adrenaline is more active than (—)-adrenaline in constricting blood vessels. (—)-Thyroxine, an amino acid of the thyroid gland that speeds up metabolism, is one of the most widely used of all prescription... 

Early examples of enantioselective extractions are the resolution of a-aminoalco-hol salts, such as norephedrine, with lipophilic anions (hexafluorophosphate ion) [184-186] by partition between aqueous and lipophilic phases containing esters of tartaric acid [184-188]. Alkyl derivatives of proline and hydroxyproline with cupric ions showed chiral discrimination abilities for the resolution of neutral amino acid enantiomers in n-butanol/water systems [121, 178, 189-192]. On the other hand, chiral crown ethers are classical selectors utilized for enantioseparations, due to their interesting recognition abilities [171, 178]. However, the large number of steps often required for their synthesis [182] and, consequently, their cost as well as their limited loadability makes them not very suitable for preparative purposes. Examples of ligand-exchange [193] or anion-exchange selectors [183] able to discriminate amino acid derivatives have also been described. 

Polysaccharide analogue, polyether 15, prepared through anionic cyclopolymerization, was chemically bonded to silica gel.73 The CSP resolved several a-amino acids the chiral recognition abilities of the analogue of 15 have been evaluated.74... 

Extractions of aqueous solutions of racemic amino-acid ester salts with solutions of / -6/s(dinaphthyl)-22-crown-6 [284] in chloroform revealed the dependence of the enantiomeric distribution constant on the structure of the amino acid ester (Table 64). In order to limit the concentrations of complex in the aqueous phase, inorganic salts were added. In the case of tyrosine, serine and alanine no extraction of salt was observed obviously these salts form very hydrophilic complexes. The highest degree of chiral recognition was found with [284] and p-hydroxyphenylglycine methyl ester hexafluorophosphate [A(AG°)... 

Effects of group (R) on the chiral recognition of racemic amino-acid esters by [285] and [2901 at 0°C"... 

Most of the work on chiral recognition has been carried out with amino-acid ester salts. The limited number of available data of similar experiments with amino-acid salts point to an increased enantiomeric differentiation (Table 69 Peacock and Cram, 1976). The reason might be the higher -acidity of the carboxyl group (vide ir fra). In solid-liquid chromatography (see Table 68) the difference between amino-acid salts and amino-acid ester salts is not consistent and not always in favour of the amino-acid salts. However, it should be... 

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