TY - GEN A1 - Snopok, Borys A1 - Laroussi, Arwa A1 - Cafolla, Clodomiro A1 - Voitchovsky, Kislon A1 - Snopok, Tetyana A1 - Mirsky, Vladimir M. T1 - Gold surface cleaning by etching polishing: Optimization of polycrystalline film topography and surface functionality for biosensing T2 - Surfaces and Interfaces N2 - Modern bio-chemical sensors rely on functional interfacial architectures with well-defined structural nano-motifs over a physical transducer. Gold-coated interfaces are of particular interest for their desirable chemical (functionalization) and optical (plasmonic) properties. Here we investigate the cleaning and polishing of polycrystalline gold films in preparation of advanced surface functionalization. We focus on soft wet chemical etching to decrease the small-scale roughness commonly observed after evaporation or sputtering of gold. We show that optimized surfaces are obtained by etching in solutions of hydrochloric acid and hydrogen peroxide. We systematically quantify the films wettability, surface nano-topography, UV-VIS spectrum and the electrochemical and Surface Plasmon Resonance (SPR) changes throughout the etching process. Optimal results are obtained by etching with a HCl(37%):H2O2(30%):H2O mixture, with a volume ratio of reagents 3:3:94 during 15-20 minutes at room temperature for the main step. This reduces by a factor two the root-mean-square roughness, removes contaminants, increases hydrophilicity and modifies the gold surface by Au(Cl)x complexes. Significantly, the resulting the surface is hydrophilic enough to prevent globular proteins such as HSA to unfold upon deposition at concentrations more than ~1 mg/mL. Our protocol offers a simple, reliable and rapid method for the preparation of gold surface in view of further functionalization including the binding of receptor layers and various micro- and nanostructures required in chemical and biochemical sensing. KW - polycrystalline gold films KW - soft wet chemical polishing KW - gold cleaning KW - hydrochloric acid and hydrogen peroxide KW - protein adsorption KW - surface plasmon resonance Y1 - 2021 U6 - https://doi.org/10.1016/j.surfin.2020.100818 SN - 2468-0230 VL - 22 ER - TY - GEN A1 - Laroussi, Arwa A1 - Kot, Małgorzata A1 - Flege, Jan Ingo A1 - Raouafi, Noureddine A1 - Mirsky, Vladimir M. T1 - Self-assembled monolayers from symmetrical di-thiols: Preparation, characterization and application for the assembly of electrochemically active films T2 - Applied Surface Science N2 - 1,3-dimercaptopropan-2-ol, a symmetrical di-thiol, has been synthesized and applied as a new type of anchor molecule to prepare a self-assembled monolayer (SAM) on the gold surface. The formed monolayers were studied by cyclic voltammetry, impedance spectroscopy, X-ray photoelectron spectroscopy, kinetic capacitance, and contact angle measurements. The SAM structure depends on the adsorption conditions. A short incubation time of the electrode at high concentration of this di-thiol leads to the predominating binding through one thiol group of the adsorbate to the gold surface, while a long incubation at low concentration leads to the predominating binding by both thiol groups. A comparative study of the desorption and replacement of SAMs indicates a strong stability increase when the SAM molecules bond gold surface by two bonds mainly. This monolayer was used to immobilize electrochemically active p-benzoquinone moiety. The surface concentration of p-benzoquinone obtained from cyclic voltammetry is 2.5 ± 0.2 × 10−10 mol·cm−2 which corresponds to the functionalization of 65 ± 5% of SAM molecules. The obtained highly stable SAM with redox-active terminal group can be applied for different tasks of chemical sensing and biosensing. As an example, an application of this system for electrocatalytical oxidation of dihydronicotinamide adenosine dinucleotide (NADH) was tested. KW - self-assembled monolayer (SAM) KW - cyclic voltammetry KW - impedance spectroscopy KW - X-ray photoelectron spectroscopy (XPS) KW - kinetic capacitance KW - contact angle Y1 - 2020 U6 - https://doi.org/10.1016/j.apsusc.2020.145827 SN - 0169-4332 SN - 1873-5584 VL - 513 ER - TY - GEN A1 - Laroussi, Arwa A1 - Raouafi, Noureddine A1 - Mirsky, Vladimir M. T1 - Electrocatalytic Sensor for Hydrogen Peroxide Based on Immobilized Benzoquinone T2 - Electroanalysis N2 - An amperometric chemosensor for the detection of hydrogen peroxide is reported. The sensor is based on 1,4-benzoquinone immobilized on the gold electrode using self-assembled monolayer of short chain symmetrical dithiol as an anchor layer. Sensor analysis was performed by cyclic voltammetry at the potential range from −0.6 V till +0.9 V as well as in the anodic or cathodic potential ranges only. The results indicate oxidative electrochemical decomposition of hydrogen peroxide at the potential of ∼+0.4 V leading to the formation of oxygen while at cathodic potentials a reduction of the formed oxygen as well as of the hydrogen peroxide occur. A decrease in the oxidation potential of hydrogen peroxide on the gold electrode coated by self-assembled monolayer with 1,4-benzoquinone in comparison with that measured on the electrodes coated by the same self-assembled monolayer without 1,4-benzoquinone, indicates electrocatalytic effect of this moiety on oxidative decomposition of hydrogen peroxide. Analytical evaluation of the sensor performance was done in the voltammetric as well as in the chronoamperometric mode. The sensor exhibited linear response over the concentration range till 2.5 mM with a limit of detection ∼4 μM. KW - Hydrogen peroxide KW - Chemical sensor KW - Electrocatalysis KW - Benzoquinone KW - Self-assembled monolaye Y1 - 2021 U6 - https://doi.org/10.1002/elan.202100113 SN - 1521-4109 VL - 33 IS - 9 SP - 2062 EP - 2070 ER - TY - GEN A1 - Efremenko, Yulia A1 - Laroussi, Arwa A1 - Sengül, Akant A1 - Corley-Wiciak, Agnieszka Anna A1 - Fischer, Inga Anita A1 - Mirsky, Vladimir M. T1 - Deposition of Polymers on Titanium Nitride Electrodes T2 - Coatings N2 - The application of titanium nitride (TiN) as an electrode for electrochemical deposition or characterization requires the removal of an insulating layer from its surface. This process was studied and optimized, and the conditions for the complete removal of this layer through treatment with oxalic acid were formulated. The obtained TiN surfaces were used for the deposition of various conducting and non-conducting polymers. Two different approaches were applied: (i) in situ electrochemical synthesis of the main classes of conducting polymers, including polyaniline, polypyrrole, polythiophene, and selected derivatives thereof, and (ii) electrostatically driven layer-by-layer (LbL) deposition of multilayers of oppositely charged polyelectrolytes. The deposited polymers were characterized by electrochemical methods. The electrochemical properties of the deposited conducting polymers and their deposition on the TiN surface were comparable to those of the metallic electrodes. The films produced via LbL deposition exhibited a pronounced influence of the charge of the last deposited polymer on the redox reaction of ferri/ferrocyanide, validating the charge alteration with each successive polymer layer deposition. The studied deposition technologies can be used for the modification of TiN surfaces required in applications of this material in chemical sensors and other devices. Y1 - 2024 U6 - https://doi.org/10.3390/coatings14020215 SN - 2079-6412 VL - 14 IS - 2 ER - TY - GEN A1 - Laroussi, Arwa A1 - Raouafi, Noureddine A1 - Mirsky, Vladimir M. T1 - Electrocatalytical Chemical Sensor for Hydrogen Peroxide T2 - Engineering Proceedings N2 - The fast and selective determination of hydrogen peroxide (H2O2) is of importance not only because of strong interest in this widely applied analyte, but also because of the development of enzymatic biosensors for glucose or other metabolites where the sensor for H2O2 can be used as the transducer. Here, we report on an electrocatalytical amperometric sensor for the detection of H2O2. It is a sensor that consists of a gold electrode covered by a self-assembled monolayer (SAM) with immobilized p-benzoquinone. To provide highly stable immobilization of p-benzoquinone at the distance of effective electron tunneling, a new anchor compound—1,3-dimercaptopropan-2-ol—was synthesized and used for preparation of the SAM. Due to two thiol groups binding gold surface, this compound provides high stability of the SAM. The surface concentration of p-benzoquinone obtained from cyclic voltammetry is 2.5 ± 0.2 × 10−10 mol·cm−2. Cyclic voltammetry and chronoamperometry experiments proved that the immobilized benzoquinone exhibited high electrocatalytic activity towards the decomposition of H2O2. Depending on the used potential range, different sensing modes can be realized. For example, one can measure electrochemical response due to the oxidation of H2O2 at anodic potentials, or due to the reduction of oxygen formed during oxidative decomposition of H2O2. Also, amperometric response at fixed potential of +0.4 V vs. Ag/AgCl corresponding to the oxidation of benzoquinone to hydroquinone was studied. The sensor exhibited a linear response over a concentration range of 0.1–2 mM with a low detection limit of 4.24 µM. The reproducibility of three different electrodes prepared was examined at the H2O2 concentration range from 0.1 till 3 mM, which resulted in a relative standard deviation below 4.2%. KW - self-assembled monolayer KW - p-benzoquinone KW - electron transfer KW - cyclic voltanmetry KW - chronoamperometry KW - hydrogen peroxide KW - electrocatalysis KW - chemical sensor Y1 - 2021 U6 - https://doi.org/10.3390/I3S2021Dresden-10168 SN - 2673-4591 N1 - Presented at the 8th International Symposium on Sensor Science, 17–28 May 2021 VL - 6 IS - 1 ER - TY - GEN A1 - Laroussi, Arwa A1 - Kot, Małgorzata A1 - Flege, Jan Ingo A1 - Raouafi, Noureddine A1 - Mirsky, Vladimir M. T1 - Self-Assembled Monolayers from Symmetrical Di-Thiols: Preparation, Characterization and Application for the Assembly of Electrochemically Active Films T2 - Engineering Proceedings N2 - 1,3-dimercaptopropan-2-ol, a symmetrical di-thiol, has been synthesized and applied as a new type of anchor molecule to prepare a self-assembled monolayer (SAM) on a gold surface. The formed monolayers were studied by cyclic voltammetry, impedance spectroscopy, X-ray photoelectron spectroscopy, kinetic capacitance, and contact angle measurements. The SAM structure depends on the adsorption conditions. A short incubation time of the electrode at high concentration of this di-thiol leads to the predominating binding through one thiol group of the adsorbate to the gold surface, while a long incubation at low concentration leads to the predominating binding by both thiol groups. A comparative study of the desorption and replacement of SAMs indicates a strong stability increase when the SAM molecules bond gold surfaces by two bonds mainly. This monolayer was used to immobilize electrochemically active p-benzoquinone moiety. The surface concentration of p-benzoquinone obtained from cyclic voltammetry is 2.5 ± 0.2 × 10−10 mol cm−2, which corresponds to the functionalization of 65 ± 5% of SAM molecules. The obtained highly stable SAM with redox-active terminal group can be applied for different tasks of chemical sensing and biosensing. As an example, an application of this system for electrocatalytical oxidation of dihydronicotinamide adenosine dinucleotide (NADH) was tested. KW - self-assembled monolayer KW - immobilization fashion KW - X-ray photoelectron spectroscopy KW - p-benzoquinone KW - electron transfer KW - cyclic voltammetry KW - NADH sensor Y1 - 2021 U6 - https://doi.org/10.3390/I3S2021Dresden-10112 SN - 2673-4591 N1 - Presented at the 8th International Symposium on Sensor Science, 17–28 May 2021 VL - 6 IS - 1 ER -