Pyrene Derivative Incorporated Ni MOF as an Enzyme Mimic for Noninvasive Salivary Glucose Detection Toward Diagnosis of Diabetes Mellitus.

Herein, we demonstrate the detection of glucose in a noninvasive and nonenzymatic manner by utilizing an extended gate field-effect transistor (EGFET) based on the organic molecule pyrene phosphonic acid (PyP4OH8) incorporated nickel metal-organic framework (NiOM-MOF). The prepared electrode responds selectively to glucose instead of sucrose, fructose, maltose, ascorbic acid, and uric acid in a 1× phosphate buffer saline solution. Also, utilizing the scanning Kelvin probe system, the sensing electrode's work function (Φ) is measured to validate the glucose-sensing mechanism. The sensitivity, detection range, response time, limit of detection, and limit of quantification of the electrode are determined to be 24.5 µA mM-1 cm-2, 20 µM to 10 mM, less than 5 s, 2.73 µM, and 8.27 µM, respectively. Most interestingly, the developed electrode follows the Michaelis-Menten kinetics, and the calculated rate constant (km) 0.07 mM indicates a higher affinity of NiOM-MOF toward glucose. The real-time analysis has revealed that the prepared electrode is sensitive to detect glucose in real human saliva, and it can be an alternative device for the noninvasive detection of glucose. Overall, the outcomes of the EGFET studies demonstrate that the prepared electrodes are well-suited for expeditious detection of glucose levels in saliva.

Lewis acidic Fe3+-driven catalytic active Ni3+ formation in Fe-free metal-organic framework for enhanced electrochemical glucose sensing.

Manipulating metal valence states and porosity in the metal-organic framework (MOF) by alloying has been a unique tool for creating high-valent metal sites and pore environments in a structure that are inaccessible by other methods, favorable for accelerating the catalytic activity towards sensing applications. Herein, we report Fe3+-driven formation of catalytic active Ni3+ species in the amine-crafted benzene-dicarboxylate (BDC-NH2)-based MOF as a high-performance electrocatalyst for glucose sensing. This work took the benefit of different bonding stability between BDC-NH2 ligand, and Fe3+ and Ni2+ metal precursor ions in the heterometallic NixFe(1-x)-BDC-NH2 MOF. The FeCl3 that interacts weakly with ligand, oxidizes the Ni2+ precursor to Ni3+-based MOF owing to its Lewis acidic behavior and was subsequently removed from the structure supported by Ni atoms, during solvothermal synthesis. This enables to create mesopores within a highly stable Ni-MOF structure with optimal feed composition of Ni0.7Fe0.3-BDC-NH2. The Ni3+-based Ni0.7Fe0.3-BDC-NH2 demonstrates superior catalytic properties towards glucose sensing with a high sensitivity of 13,435 µA mM-1 cm-2 compared to the parent Ni2+-based Ni-BDC-NH2 (10897 µA mM-1cm-2), along with low detection limit (0.9 µM), short response time (≤5 s), excellent selectivity, and higher stability. This presented approach for fabricating high-valent nickel species, with a controlled quantity of Fe3+ integrated into the structure allowing pore engineering of MOFs, opens new avenues for designing high-performing MOF catalysts with porous framework for sensing applications.

Study of highly stable electrochemiluminescence from [Ru(bpy)3]2+/dicyclohexylamine and its application in visualizing sebaceous fingerprint.

For the first time, we report a novel and highly stable visual electrochemiluminescence emission from the [Ru(bpy)3]2+/dicyclohexylamine system at physiological pH conditions, with a quantum efficiency (ΦECL) of 95.5%. Furthermore, we have successfully demonstrated the simple and rapid smartphone-based ECL mapping of sebaceous fingerprints via a non-destructive mode.

Bimodal Electrogenerated Chemiluminescence of the Luminol/Dicyclohexylamine (DCHA) System: A Novel and Highly Sensitive Detection of DCHA via ECL-Flow Injection Analysis.

Though luminol is one of the most prominent and extensively studied luminophores in ECL studies, only H2O2 has been widely used as a co-reactant. This limits the variety of applications because of the short-time radical stability and low quantum efficiency. In the present work, we identified dicyclohexylamine (DCHA) as a new and highly efficient anodic co-reactant in ECL for the luminol molecule. The electrochemical and ECL behavior of the luminol/DCHA system was studied on a simple bare GCE surface, which results in two anodic ECL peaks at the potential region of +0.38 and +0.94 V vs Ag/AgCl. The evidence of (DCHA•+) and O2•- generated in the system was detected via flat-cell electron spin resonance (ESR) spectroscopy experiments at ∼20 °C. Using the bimodal ECL system, the highly sensitive detection of luminol was achieved with the detection limit down to 1.5 pM. Further, a homebuilt electrochemiluminescent detector coupled with a flow injection analysis (ECL-FIA) system was adopted to detect the DCHA contaminant in harvested honey, which achieved higher detection and sensitivity under the optimized experimental conditions. DCHA was detected in the range of 10 nM to 100 µM with the detection limit of 2 nM (S/N = 3). The present findings of new luminol/DCHA ECL signals produced a strong ECL emission, which leads to a greater potential to meet the fast-developing analytical application of a luminol-based ECL system.

Highly sensitive novel cathodic electrochemiluminescence of tris(2,2'-bipyridine)ruthenium(ii) using glutathione as a co-reactant.

Herein, glutathione was used as a co-reactant for the first time to generate a novel, highly stable, and enhanced cathodic electrochemiluminescence (ECL) on a simple bare glassy carbon electrode (GCE) surface using the Ru(bpy)32+ molecule in an alkaline pH phosphate buffer solution (PBS).

Residual metal impurity aids facile in situ electrochemical surface derivatization of single-walled carbon nanotubes.

Residual metal impurities were exploited as reactants in the functionalization of the surface of single-walled carbon nanotubes (SWCNT) with nickel hexacyanoferrate (NiHCF) by simple electrochemical cycling in ferricyanide solutions. This facile in situ electrochemical modification process provides intimate contact between NiHCF and SWCNTs that improves the stability of the redox property and reactivity of NiHCF. The characteristic redox behavior of NiHCF on SWCNT surfaces can be used as an electrochemical probe to access qualitative and quantitative information on unknown electroactive metal impurities in SWCNTs. Significantly, the NiHCF-modified SWCNTs exhibit pseudocapacitive behavior, and the calculated specific capacitances are 710 and 36 F g(-1) for NiHCF-SWCNTs and SWCNTs respectively. Furthermore, NiHCF-SWCNTs were transformed into Ni(OH)2 /SWCNTs and used for enzymeless glucose oxidation.

Improved heterogeneous electron transfer kinetics of fluorinated graphene derivatives.

Though graphitic carbons are commercially available for various electrochemical processes, their performance is limited in terms of various electrochemical activities. Recent experiments on layered carbon materials, such as graphene, demonstrated an augmented performance of these systems in all electrochemical activities due to their unique electronic properties, enhanced surface area, structure and chemical stabilities. Moreover, flexibility in controlling electronic, as well as electrochemical activities by heteroatom doping brings further leverage in their practical use. Here, we study the electron transfer kinetics of fluorinated graphene derivatives, known as fluorinated graphene oxide (FGO) and its reduced form, RFGO. Enhanced electron transfer kinetics (heterogeneous electron transfer (HET)) is observed from these fluorinated systems in comparison to their undoped systems such as graphene oxide (GO) and reduced GO. A detailed study has been conducted using standard redox probes and biomolecules revealing the enhanced electro-catalytic activities of FGO and RFGO, and electron transfer rates are simulated theoretically. This study reveals that fluorine not only induces defects in graphitic lattice leading to an enhanced HET process but also can modify the electronic structure of graphene surface.

Background emission of electrogenerated chemiluminescence during oxidation of tri-n-propylamine from the dimeric 1Δg state of O2.

The background electrogenerated chemiluminescence (ECL) emission observed only upon electrochemical oxidation of tri-n-propylamine (TPrAH) on a platinum electrode is a limiting factor in ECL analytical techniques and is poorly understood. We studied this reaction in aerated acetonitrile (MeCN) solution with TPrAH oxidized at a constant potential at the Pt surface and observed ECL spectra with an emission band at 630 nm, which is characteristic of the emission of the dimeric (1)Δ(g) state of O(2). No ECL emission was observed when the same solution was deaerated. This background ECL emission is attributed to the reaction between dissolved oxygen and two different products of TPrAH oxidation: the TPrAH(•) radical that reduces O(2) to the superoxide ion and the TPrAH(•+) radical cation that oxidizes this species to singlet O(2).