Revelation of the chiral recognition of alanine and leucine in an l-phenylalanine-based metal–organic framework

Abstract

An l-phenylalanine-based Zn-MOF, namely [Zn2(l-Phe)2(bpe)2]n, was designed for experimentally revealing the chiral recognition mechanism to alanine and leucine by means of 13C CP MAS NMR spectroscopy, XPS and control experiment.

Chiral Detection with Coordination Polymers

“…[48] restricted to a handful of amino acid and TFPE derivatives, yielding small chemical shift differences. [49] It is only in the last few years that these values have been extended beyond 1.0 ppm, but this increase in enantioselectivity gives hope for the future of the sensing field's applicability. The increased ability of chemists to design MOFs and CPs with highly complementary pores for the encapsulation of the chiral analyte and use of lanthanide metal ions will enable larger chemical shift differences to be obtained.…”

“…The use of MOFs and CPs as chiral shift reagents in NMR is still new, with limited examples. Chiral analytes have been restricted to a handful of amino acid and TFPE derivatives, yielding small chemical shift differences [49] . It is only in the last few years that these values have been extended beyond 1.0 ppm, but this increase in enantioselectivity gives hope for the future of the sensing field's applicability.…”

Enantioselective Recognition of Racemic Amino Alcohols in Aqueous Solution by Chiral Metal‐Oxide Keplerate {Mo132} Cluster Capsules

“…The development of extended chiral metal‐organic frameworks and their application to NMR chiral recognition methods has thus far been limited to solid‐state analyses. [ 8 , 9 , 10 , 11 ] Despite this, the use of discrete inorganic hosts, such as polyoxometalates (POMs), for the same role has not yet been achieved. These chiral inorganic nanostructures can be separated into two general classes, 1) purely inorganic molecules and 2) inorganic‐organic hybrid structures, with the latter possessing chirality in either the inorganic, the organic component, or both.…”

Complete and Versatile Post‐Synthetic Modification on Iron‐Triazole Spin Crossover Complexes: A Relevant Material Elaboration Method

“…Therefore the synthesis of a wide variety of molecules is facilitated and this is of particular interest in the fields of catalysis (where the catalytic activity is highly dependent on the structure of the catalyst) and sensors (where the selectivity towards guest molecules could be modulated by the electronic and steric hindrance of the functionalized group on the MOF). [2,17,19,[28][29][30][31][32][33] This strategy allows to have better control in the final material; two important examples of this are: 1) in the biological area; once the protein is biosynthesized, it can be covalently modified on the amino acid side chain or in the backbone of the protein, the phosphorylation being the most common post-translational modification (PTM). [34] 2) in coordination chemistry, to generate co-catalysts associating MOF with multimetal sites to avoid competition between the metal sites, [22,29,35] for example, Neppolian et al [35] synthesized Ti-MOF complexes and then associated them by the coordination of the amino functional group on the Ti-MOF to transition metals such as Ni or Cu.…”

“…An advantage of biphasic reaction is that the material can be simply isolated and recovered since it is not in the same phase than other reagents. Therefore the synthesis of a wide variety of molecules is facilitated and this is of particular interest in the fields of catalysis (where the catalytic activity is highly dependent on the structure of the catalyst) and sensors (where the selectivity towards guest molecules could be modulated by the electronic and steric hindrance of the functionalized group on the MOF) [2,17,19,28–33] . This strategy allows to have better control in the final material; two important examples of this are: 1) in the biological area; once the protein is biosynthesized, it can be covalently modified on the amino acid side chain or in the backbone of the protein, the phosphorylation being the most common post‐translational modification (PTM) [34] .…”