Toward Fluorescence-Based High-Throughput Screening for Enantiomeric Excess in Amines and Amino Acid Derivatives.
A highly accurate and reliable screening method for enantiomeric excess of amine derivatives in the presence of water is reported. The fluorescence-based screening system has been realized by self-assembly of chiral diol-type dyes (BINOL, VANOL and VAPOL), 2-formylphenylboronic acid, and chiral amines forming iminoboronate esters. The structure and chirality of the amine analytes determine the stability of the diastereomeric iminoboronate esters, which in turn display differential fluorescence. The fluorescence signal reflects the enantiomeric purity of the chiral amines and was utilized in high-throughput arrays. The arrays were able to recognize enantiomeric excess of amines, amino esters, and amino alcohols. In addition to qualitative analysis, quantitative experiments were successfully performed. Studies of the role of additives such as water or citrate were carried out to gain insight into the stability of the iminoboronate esters. It is shown that the above additives destabilize less stable esters while the stable esters remain unchanged. Thus, the presence of water and citrate leads to increased difference between the diastereomeric iminoboronates and contributes to the enantiodiscrimination of the chiral amines.
Department of Chemistry, Bowling Green State University, Bowling Green, OH, 43403, USA.
Elena G
EG
Shcherbakova
Department of Chemistry, Bowling Green State University, Bowling Green, OH, 43403, USA.
Valentina
V
Brega
Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo, 153-8505, Japan.
Tsuyoshi
T
Minami
Department of Chemistry, Bowling Green State University, Bowling Green, OH, 43403, USA.
Sara
S
Sheykhi
Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK.
Tony D
TD
James
Department of Chemistry, Bowling Green State University, Bowling Green, OH, 43403, USA. pavel@bgsu.edu.
Pavel
P
Anzenbacher
D000588:Amines / Q000737:chemistry*; D000596:Amino Acids / Q000737:chemistry*; D000605:Amino Alcohols / Q000737:chemistry*; D001547:Benzaldehydes / Q000737:chemistry*; D001897:Boronic Acids / Q000737:chemistry*; D005453:Fluorescence; D015394:Molecular Structure; D009284:Naphthols / Q000737:chemistry*; D013237:Stereoisomerism
C532809:2-formylphenylboronic acid; D000588:Amines; D000596:Amino Acids; D000605:Amino Alcohols; C406944:BINOL, naphthol; D001547:Benzaldehydes; D001897:Boronic Acids; D009284:Naphthols
chirality; fluorescence; self-assembly; sensors; supramolecular chemistry