Determination of Enantiomeric Compositions of Analytes Using Novel Fluorescent Chiral Molecular Micelles and Steady State Fluorescence Measurements

Abstract

Novel fluorescent chiral molecular micelles (FCMMs) were synthesized, characterized, and employed as chiral selectors for enantiomeric recognition of non-fluorescent chiral molecules using steady state fluorescence spectroscopy. The sensitivity of the fluorescence technique allowed for investigation of low concentrations of chiral selector (3.0×10 −5 M) and analyte (5.0×10 −6 M) to be used in these studies. The chiral interactions of glucose, tartaric acid, and serine in the presence of, and poly(sodium N-undecanoyl-L-phenylalininate) [poly-SUF] were based on diastereomeric complex formation. Poly-L-SUW had a significant fluorescence emission spectral difference as compared to poly-L-SUY and poly-L-SUF for the enantiomeric recognition of glucose, tartaric acid, and serine. Studies with the hydrophobic molecule α-pinene suggested that poly-L-SUY and poly-L-SUF had better chiral discrimination ability for hydrophobic analytes as compared to hydrophilic analytes. Partial-least-squares regression modeling (PLS-1) was used to correlate changes in the fluorescence emission spectra of poly-L-SUW due to varying enantiomeric compositions of glucose, tartaric acid, and serine for a set of calibration samples. Validation of the calibration regression models was determined by use of a set of independently prepared samples of the same concentration of chiral selector and analyte with varying enantiomeric composition. Prediction ability was evaluated by use of the root-mean-square percent relative error (RMS%RE) and was found to range from 2.04 to 4.06%.

A versatile chiral selector for determination of enantiomeric composition of fluorescent and nonfluorescent chiral molecules using steady‐state fluorescence spectroscopy

“…Characterization of poly-L-SUF and its photophysical properties have previously been reported in the absence of any analyte. 13 …”

Syntheses and Highly Enantioselective Fluorescent Recognition of α‐Aminocarboxylic Acid Anions Using Chiral Oxacalix[2]arene[2]bisbinaphthes

“…The bisbinaphthyl‐based tweezers fluorescence sensors are found to carry out enantioselective fluorescence probe in the recognition of α‐aminocarboxylic acid derivatives. The compounds acted as a selective flurescence probe in the recognition of α‐aminocarboxylic acid anions with the dramatic change of fluorescence intensity . Following clusters pioneering work, the macrocyclic host molecules crown ethers have attacted increasing interest in recent years.…”

“…[22][23][24][25][26][27][28][29][30] Amongst many of the enantioselective methods under investigation, such as nuclear magnetic resonance (NMR), high-performance liquid chromatography, circular dichroism, especially the use of fluorescence has attracted a sizable interest because it can offer the advantages of real-time analysis, high sensitivity, multiple sensing modes, widely available instrumentation, and remote detection capabilities. [31][32][33][34][35][36][37] Several fluorescent sensors, including those developed within our group, have been reported to show high enantioselectivity in the recognition of mandelic acid and/or tartaric acid or -NH 2 protected by acetyl-group, Boc-group or benzoyl-group amino acid. [38][39][40] However, the enantioselective recognition of native a-aminocarboxylic acid is poor; therefore, the development of enantioselective fluorescent sensors for native a-aminocarboxylic acid has become a major challenge in this area.…”

“…The compounds acted as a selective flurescence probe in the recognition of a-aminocarboxylic acid anions with the dramatic change of fluorescence intensity. [31][32][33][34][35][36][37] Following clusters pioneering work, the macrocyclic host molecules crown ethers have attacted increasing interest in recent years. Owing to the fine-tuned cavity structures, the crown ethers can be an emerging generation for molecule recognition.…”

Ephedrinium‐based protic chiral ionic liquids for enantiomeric recognition

“…52,53 The exact mechanism of chiral recognition is still unclear. Further studies are currently underway to determine the mechanism of chiral recognition by PCILs for analytes of varying chirality.…”