Pt–NiCo Nanostructures with Facilitated Electrocatalytic Activities for Sensitive Determination of Intracellular Thiols with Long‐Term Stability

Abstract

A Pt-NiCo nanomaterial has been synthesized for developing the sensitive electrochemical determination of biological thiols that include L-cysteine (CySH), homocysteine (HCySH), and gluthione (GSH) with high sensitivity and long-term stability, in which the Pt nanoparticles are well supported on amorphous NiCo nanofilms. The electrochemical oxidation of thiols has been successfully facilitated on the optimized Pt-NiCo nanostructures, that is, two oxidation peaks of CySH have been clearly observed at potentials of +0.06 and +0.45 V. The experimental results demonstrate that the first peak for CySH oxidation may be attributed to a direct oxidation from CySH to L-cystine (CySSCy), whereas the second peak possibly results from a sequential oxidation from CySSCy to cysteic acid (CySO(3)H), together with a direct oxidation of CySH into CySO(3)H. The enhanced electrocatalytic activities at the Pt(23)-NiCo nanostructures have provided a methodology to determine thiols at a very low potential of 0.0 V with relatively high sensitivity (637 nA μM cm(-2)), a low detection limit (20 nM), and a broad linear range. The striking analytical performance, together with the characteristic properties of the Pt-NiCo nanomaterial itself, including long-term stability and strong antipoisoning ability, has established a reliable and durable approach for the detection of thiols in liver cancer cells, Hep G2.

Branched Artificial Nanofinger Arrays by Mesoporous Interfacial Atomic Rearrangement

“…4c), suggesting the potential of direct recording of GSH from complex body fluids. The introduction of N-ethylmaleimide (NEM), a well-known thiol-blocking agent that can selectively decompose GSH 42,43 , into both the cell extracts and the GSH-containing serum, reduces the signal change to the background level (Fig. 4d).…”

“…At the same time, hemin can specifically recognize the presence of trace GSH, which acts as the acceptors of photogenerated holes in hemin, which are subsequently transferred to the Ti thin film current collector, leading to a signal increase of the photocurrent (Fig. S18) [40][41][42][43] . The heminfunctionalized Sn-doped Fe 2 O 3 ANFs respond quickly and reach equilibrium within 10 s upon each injection of GSH, with the detection limit of GSH as ~ 5 nM, which is the lowest among all the detection methods reported previously (Table S3).…”

Zeolitic Imidazolate Framework-67 Rhombic Dodecahedral Microcrystals with Porous {110} Facets As a New Electrocatalyst for Sensing Glutathione

“…Clearly, the sensitivity or linear range of the catalyst-ZIF-67 rhombic dodecahedral microcrystal is better than some other GSH electrochemical sensors, such as Co-MOCP/CPE (0.0121 µA mM −1 cm −2 , 2.5 µM-0.95 mM), [ 17 ] NiO microfl owers GCE (10 µM to 0.62 mM), [ 14 ] NiO nanoparticles (50 µM to 4.56 mM), [ 39 ] NiO nanoparticles (0.2 to 6.0 mM), [ 15 ] and Pt-NiCo nanmaterials (0.637 µA µM cm −2 ). [ 8 ] It can be concluded that the as-prepared ZIF-67 rhombic dodecahedral microcrystal as a new kind of electrocatalysts is among the best GSH electrochemical sensors with a good sensitivity, a fast response speed, and a low detection limit.…”

“…[ 6 ] Electrochemical methods have been proven very effi cient for the detection of GSH as they are sensitive, selective, with very good linear range and rapid response time. [7][8][9][10][11] The nanomaterials used for electrodes including noble metals and their alloys, [ 8,12,13 ] metal oxide [ 10,[14][15][16][17] and carbon nanomaterials. [ 9,18 ] However, to develop easily available nanomaterials for high-performance GSH sensors is still required.…”

Selective electrochemical determination of glutathione from the leakage of intracellular GSH contents in HeLa cells following doxorubicin-induced cell apoptosis

“…Among these methods, the electrochemical methods based on direct detection or electrocatalytic approach have attracted greater attention due to their simplicity, sensitivity, lower cost, and so forth. [22], a nickel hexacyanoferrate film modified Pt ultramicroelectrode by introducing cetyltrimethylammonium bromide and Au nanoparticles reported by Lu et al [28], and Pt-NiCo Nanostructures modified glass carbon electrodes reported by Tian et al and so forth [20]. These nanomaterials performed high electrocatalytic activity and stability for the oxidation of GSH.…”