Free Amino Acid Recognition: A Bisbinaphthyl-Based Fluorescent Probe with High Enantioselectivity

Abstract

A novel fluorescent probe based on a bisbinaphthyl structure has been designed and synthesized. This compound in combination with Zn­(II) has exhibited highly enantioselective fluorescence enhancement with 13 common free amino acids. For example, its enantiomeric fluorescent enhancement ratios (ef or ΔI L/ΔI D) in the presence of the following amino acids are extremely high: 177 for valine, 199 for methionine, 186 for phenylalanine, 118 for leucine, and 89 for alanine. The observed high enantioselectivity and the extent of the substrate scope are unprecedented in the fluorescent recognition of free amino acids. This fluorescent probe can be applied to determine the enantiomeric composition of the structurally diverse chiral amino acids. NMR and mass spectroscopic investigations have provided clues to elucidate the observed high enantioselectivity.

Simultaneous Determination of Concentration and Enantiomeric Composition of Amino Acids in Aqueous Solution by Using a Tetrabromobinaphthyl Dialdehyde Probe

“…[1][2][3] They also serve as important synthons andc hirality sourcesf or diversef unctional organic molecules. [6,7] The use of fluorescence in chiral recognition not only provides rapid analysis of the chiral composition of the substrates, [8] but maya lso allow direct imagingo ft he enantiomers of amino acids in cells. [6,7] The use of fluorescence in chiral recognition not only provides rapid analysis of the chiral composition of the substrates, [8] but maya lso allow direct imagingo ft he enantiomers of amino acids in cells.…”

“…[4,5] In recent years, the development of fluorescent molecular probes to discriminate the enantiomerso fa minoa cids hasr eceived significant attention. [6,7] The use of fluorescence in chiral recognition not only provides rapid analysis of the chiral composition of the substrates, [8] but maya lso allow direct imagingo ft he enantiomers of amino acids in cells. [6l] Previously,w ereported that (S)-3,3'diformyl-1,1'-bi-2-naphthol ((S)-1), in combination with Zn 2 + , could be used to conduct fluorescent discrimination of the enantiomers of functional amines, including severala mino acids, in methanol.…”

Biphasic Enantioselective Fluorescent Recognition of Amino Acids by a Fluorophilic Probe

“…We prepared compound 1,a2,6-dibromomethylp yridine with ah ighly fluorinated alkyl chain, as ap recursort oaf luorophilic probe (Scheme 1). Reaction of 1 with the 1,1'-binaphthyl-based aldehyde (R)-2 8 in the presence of base followed by acidic deprotection gave the bis(binaphthyl) compound (R,R)-3.T his compound was found to be soluble in af luorous solvent 1H,1H,2H,2H-perfluoro-1-octanol( PFOH)a nd showed no fluorescence in this solvent.…”

“…[7] Recently,w ef ound that ab is(binaphthyl)-based fluorescent probe can carry out highly enantioselective fluorescent recognition of amino acids in acetonitrile solution. [8,9] On the basis of this work, we have synthesized af luorophilic probe by incor-porating ah ighly fluorinated alkyl chain. We have demonstrated that in ab iphasic aqueous/fluorous system, the probe can carry out highly enantioselective fluorescent detection of amino acids by selectively extracting the substrates from the aqueous phase into the fluorous phase.…”

A Chirality/Light Dual‐Responsive Calixarene‐Functionalized Gold Surface for the Separation of Naproxen Enantiomers

“…[14][15][16][17][18] Certain chromophores, such as spiropyran, azobenzene and diarylethene are well known molecular switches, which can be well utilized to develop photo-responsive chiral supramolecular systems. [19][20][21][22][23] However, recognition of the chiral drugs with the photoresponsive system were usually focused only on the molecular level, [24][25][26][27][28][29] while macroscopic recognition of drugs with the photo-responsive system is a challenging task. [30][31] Even though such a challenge can be overcome by designing a system that can form an effect of enantioselective host-guest complex with the drug molecule.…”