Commercial Screen-Printed Electrode Decorated with Carbonaceous Binary Sulfides for Direct Glucose Detection in Human Fluid Samples
Authors: Ataei Kachouei Matin , Hekmat Farzaneh , Shahrokhian Saeed , Unalan Husnu 
Published: July 2022

We hereby demonstrate a highly controllable, green, and rapid synthesis strategy for the production of binary metal sulfides on carbon nano-horns (CNHs) for the fabrication of non-enzymatic glucose sensor using commercial graphite screen-printed electrodes (GSPEs). CNHs were synthesized using the submerged arc discharge method as described elsewhere. In the next step, one droplet (50 µL) of the well-dispersed CNHs was carefully cast on the surface of the GCE (and GSPE). In the final step of preparing the modified electrodes, CNH/GCEs were covered by a thin layer of nickel cobalt sulfide by a simple electrochemical deposition procedure.

Following the structural examination of the prepared electrocatalyst were examined. In this regard, several microscopic methods like FE-SEM or TEM were used to know more regard the morphology of the material. The FE-SEM images confirmed the successful formation of sponge like nanosheets of NiCo-S on carbonaceous material. Since CNHs are prepared from graphene sheets with open ends in horn-like shapes, they can be considered as being formed from the origami-like or crushing contortion of a single graphene sheet. According to the FE-SEM images, the agglomeration of CNHs establishes discrete nano-sphere structures with diameters in the range of 50 to 150 nm. The TEM images also confirm this nano-sphere strictures.

Following detailed structural characterization, the electrocatalytic activity of the fabricated NiCo-S/CNH electrodes toward electro-oxidation of glucose is examined in detail. The cyclic voltammetry was also used for glucose electro-oxidation mechanism investigation. In addition, parameter optimization was also done by utilizing cyclic voltammetry technique. These include medium pH, deposition cycles, and metals mole ration. Moreover, the effect of the presence and absence of CNH on the electrochemical performance of glucose oxidation were also examined. It shows that in the presence of CNH the peak current density for glucose oxidation is higher that is perfect for analytical purposes and increase the analytical sensitivity. The structural properties and electrochemical response of the fabricated electrodes were also compared to their corresponding mono-metallic counterparts.

The amperometric method was utilized as one of the most prevalent and momentous techniques for the quantitative determination of glucose. The applied potential in amperometric tests was optimized to be +0.5 V (vs. Ag/AgCl). The proposed electrodes were operated within two distinct linear dynamic ranges of 0.001- 0.330 mM and 0.330 - 4.53 mM of standard glucose with sensitivities of 1842 µA.mM-1.cm-2, and 854 µA.mM-1.cm-2, respectively. On the other hand, an analytical sensitivity of 467 µA.mM-1.cm-2, within the linear dynamic range of 0.5 - 6 mM was obtained for the static chronoamperometric measurements for modified commercial screen-printed electrode (GSPE). The proposed sensor showed outstanding selectivity against iso-structures and co-existing interferences, long-term durability, rapid response (1.7 s), excellent poisoning resistance against chloride ions, good repeatability, and reproducibility. The tested interferences were 0.1 mM solutions of fructose, galactose, sucrose, lactose, ascorbic acid, uric acid, dopamine hydrochloride, and NaCl. In order to demonstrate the capability of the fabricated electrodes and to evaluate their potential for glucose measurements in real physiological specimens, the glucose level was successfully measured in human blood serum, urine, and saliva samples, without any sample pre-treatment. All in all, the encouraging results make NiCo-S/CNH electrodes immensely promising for clinical and physiological glucose-level measurements.

Figure 1. (a) FE-SEM image of CNH. (b) FE-SEM image of NiCo-S/CNH. (c) TEM image of CNHs. (d) Cyclic voltammogarm of NiCo-S/CNH in the absence and presence of various concentration of glucose. (e) The amperometric responses of the NiCo-S/CNH/GCEs after addition of 1 mM glucose followed by successive injection of 0.1 mM fructose, galactose, sucrose, lactose, AA, UA, DA, and NaCl. (f) Chrono amperograms of the NiCo-S/CNH/GSPEs in the presence of the different glucose concentration ranging from 0.5 ~ 10.0 mM under applying +0.5 V. Amperogram of the NiCo-S/GCEs current response obtained from the addition of (g) 50 µL human blood serum, (h) 200 µL urine, and (i) 100 µL saliva followed by injection of 400 µM standard glucose solutions under the optimum potential of +0.5 V, the amperograms of five successive glucose addition.

Figure 1