Enantioselective voltammetric sensor based on mesoporous graphitized carbon black Carbopack X and fulvene derivative.

For medicine and pharmaceuticals, the problem of determining and recognizing the enantiomers of biologically active compounds is an actual issue because the enantiomers of the same substance can have different effects on living organisms. This paper describes the development of an enantioselective voltammetric sensor (EVS) based on a glassy carbon electrode (GCE) modified with mesoporous graphitized carbon black Carbopack X (CpX) and a fulvene derivative (1S,4R)-2-cyclopenta-2,4-dien-1-ylidene-1-isopropyl-4-methylcyclohexane (CpIPMC) for recognition and determination of tryptophan (Trp) enantiomers. Synthesized CpIPMC was characterized by 1 H and 13 C nuclear magnetic resonance (NMR), chromatography-mass spectrometry, and polarimetry. The proposed sensor platform was studied by Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). Using the square-wave voltammetry (SWV), it was established that the developed sensor is an effective chiral platform for the quantitative determination of Trp enantiomers, including in a mixture and in biological fluids like urine and blood plasma, with adequate precision and recovery ranged from 96% to 101%.

QCM based enantioselective discrimination of enantiomers by a pair of serine derived homochiral coordination polymers.

Decoding enantioselective molecular interactions between sensors and guests into readable signal represents a great challenge in developing selective sensing technology. In this work, a pair of serine derivatives based homochiral coordination polymer (HCP) enantiomers, (L)-SA-Cd and (D)-SA-Cd, were synthesized and explored as enantioselective sensors towards guest enantiomers. Quartz crystal microbalance (QCM) technology was employed to indicate the gravimetric change of (L)- and (D)-SA-Cd towards variable chiral guests, and an enantioselective factor of 1.72 ±â€¯0.15, 1.81 ±â€¯0.08, 1.37 ±â€¯0.03 and 2.89 ±â€¯0.09 were achieved for lactic acid, menthol, valinol and 1-phenylethylamine (PEA), respectively. PEA was further selected to comprehensively study the enantioselectivity via electrochemical tests, HPLC analysis and theoretical calculations. By comparison with state-of-art works, the enantioselective discrimination for PEA enantiomers is better than a vast majority of similar reports. (L)- and (D)-form of SA-Cd exhibited mirror behaviors towards guest enantiomers, and control experiments indicated the role of HCP construction in enhancing enantioselectivity. H-bonding effect was found to be the binding force between SA-Cd and PEA, as verified by FT-IR and UV-Vis titration studies. Further DFT calculations revealed the existence of conformation oriented H-bonding between the chiral -OH groups of serine fragment and -NH2 group of PEA. The findings indicate that HCP construction represents an effective strategy for promoting enantioselectivity, and monitoring gravimetric change could be a promising general method in decoding most of the enantioselective recognition process.

Discriminative sensing of DOPA enantiomers by cyclodextrin anchored graphene nanohybrids.

Discriminative sensing of chiral species with a convenient and robust system is a challenge in chemistry, pharmaceutics and particularly in biomedical science. Advanced nanohybrid materials for discrimination of these biologically active molecules can be developed by combination of individual obvious advantages of different molecular scaffolds. Herein, we report on the comparison of the performance of cyclodextrin functionalized graphene derivatives (x-CD/rGO, x: α-, ß-, γ-) for discrimination of DOPA enantiomers. Within this respect, electrochemical measurements were conducted and the experimental results were compared to molecular docking method. Thanks to cavity size of γ-CD and the unique properties of graphene, rGO/γ-CD nanohybrid is capable of selective recognition of DOPA enantiomers. Limit of detection (LOD) value and sensitivity were determined as 15.9 µM and 0.2525 µA µM-1 for D-DOPA, and 14.9 µM and 0.6894 µA µM-1 for L-DOPA.