ABSTRACT
The identification of cysteine enantiomers is of great significance in the biopharmaceutical industry and medical diagnostics. Herein, we develop an electrochemical sensor to discriminate cysteine (Cys) enantiomers based on the integration of a copper metal-organic framework (Cu-MOF) with an ionic liquid. Because the combine energy of D-cysteine (D-Cys) with Cu-MOF (-9.905 eV) is lower than that of L-cysteine (L-Cys) with Cu-MOF (-9.694 eV), the decrease in the peak current of the Cu-MOF/GCE induced by D-Cys is slightly higher than that induced by L-Cys in the absence of an ionic liquid. In contrast, the combine energy of L-Cys with an ionic liquid (-1.084 eV) is lower than that of D-Cys with an ionic liquid (-1.052 eV), and the ionic liquid is easier to cross-link with L-Cys than with D-Cys. When an ionic liquid is present, the decrease in the peak current of the Cu-MOF/GCE induced by D-Cys is much higher than that induced by L-Cys. Consequently, this electrochemical sensor can efficiently discriminate D-Cys from L-Cys, and it can sensitively detect D-Cys with a detection limit of 0.38 nM. Moreover, this electrochemical sensor exhibits good selectivity, and it can accurately measure the spiked D-Cys in human serum with a recovery ratio of 100.2-102.6%, with wide applications in biomedical research and drug discovery.
Subject(s)
Ionic Liquids , Metal-Organic Frameworks , Humans , Cysteine , Copper , Stereoisomerism , Electrochemical Techniques , Limit of DetectionABSTRACT
Chirality is an important property of nature and it regulates fundamental phenomena in nature and organisms. Here, we develop a chiral electrochemical sensor based on copper-amino acid mercaptide nanorods (L-CuCys NRs) to discriminate tryptophan (Trp) isomers. The chiral L-CuCys NRs are prepared in alkaline solution based on the facile coordination reaction between the sulfhydryl groups of L-Cys and copper ions. Since the stability constant (K) of L-CuCys NRs with L-Trp (752) are much higher than that of L-CuCys NRs with D-Trp (242), the cross-linking bonds between L-CuCys NRs and L-Trp are more stable than those between L-CuCys NRs and D-Trp. Consequently, this electrochemical sensor can selectively recognize the Trp isomers with an enantiomeric electrochemical difference ratio (IL-Trp/ID-Trp) of 3.22, and it exhibits a detection limit of 0.26 µM for L-Trp. Moreover, this electrochemical sensor can quantitatively measure Trp isomers in complex samples. Importantly, this electrochemical sensor has the characteristics of high stability, good repeatability, easy fabrication, low cost, and efficient discrimination of tryptophan (Trp) isomers.
Subject(s)
Nanotubes , Tryptophan , Tryptophan/chemistry , Amino Acids , Copper/chemistry , Stereoisomerism , Electrochemical TechniquesABSTRACT
Herein, we explore a new carbon source for preparation of carbon quantum dots (CQDs) with controllable composition using a porous organic polymer (POP) derived porous carbon via a nitric acid oxidation method. The POP used for the preparation of CQDs was synthesized by mechanochemical Friedel-Crafts alkylation under solvent free conditions. Using the as-prepared CQDs, we develop a simple and effective electrochemiluminescence (ECL) detection method for dopamine (DA) using a CQD/chitosan-graphene composite modified glassy carbon electrode (GCE). Both the electrochemical and ECL behaviors were studied in detail with ammonium persulfate as a coreactant. The complementary structure and synergistic function of the composite give the ECL sensor special properties. Apart from the high stability, it also presents good repeatability and high sensitivity to DA with a wide linear range from 0.06 to 1.6 µM. And a satisfactory detection limit of 0.028 µM (S/N = 3) was achieved for the prepared sensor. Furthermore, the ECL also shows high selectivity toward DA with an excellent interference resistance ability at a high concentration ratio of 100 (C interference : C DA = 100). In addition, the ECL sensor was successfully applied for effective detection and quantitative analysis of the actual dopamine in human body fluids for disease diagnosis and pathological studies.
