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Spectroelectrochemical Devices for Monitoring of Intermediates and Products on Carbonbased Composite Electrodes
Vaněčková, Eva ; Šikula, M. ; Hrdlička, Vojtěch ; Sebechlebská, Táňa ; Kolivoška, Viliam
Spectroelectrochemistry (SEC), as an interdisciplinary field, provides us with more comprehensive information about electroactive molecules involved in charge transfer reactions. Commercially\navailable SEC cells most often have an incorporated platinum working electrode, which can limit the range of the usable potential window and, in addition, can complicate the analysis due to the\nabsorption phenomenon. In this work, we designed and manufactured two types of custom-made SEC cells employing optically transparent carbon-based working electrodes for UV-Vis monitoring of reactants and electrogenerated intermediates and products. The first SEC cell is entirely manufactured by 3D printing using fused deposition modeling (FDM) by combining optically transparent (PET) and electrically conductive (PLA-CB) filaments. The second SEC cell employs pencil graphite (PG) rods as the working electrode (PGE) and its body is manually assembled from quartz slides. The functionality of the FDM 3D printed SEC cell and manually assembled quartz SEC cell were verified by cyclic voltammetry with in situ UV-Vis spectroscopic absorption monitoring of ruthenium(III) acetylacetonate (Ru(ac)3) redox-active probe dissolved in an aqueous or non-aqueous deaerated solvent, respectively. Both presented cells enable complete redox reversible conversion and strictly oxygen-free conditions.
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3D-printed Electrodes with Nearly Ideal Charge Transfer Characteristics
Vaněčková, Eva ; Sebechlebská, Táňa ; Kolivoška, Viliam
3D printing is an outstanding manufacturing tool for prototyping customized designs at reduced time and costs, having found applications in fields such as medicine or the automotive industry. The development of printable electrically conductive composite materials brought a revolution to electrochemistry, with 3D-printed electrodes being intensively studied from the viewpoint of\nanalytical performance and stability. However, it is often reported that 3D-printed electrodes have poor charge transfer characteristics, typically due to limited exposure of the electrically conductive phase at the composite surface to the surrounding solution. In this work, we devise and apply simple electrochemical activation procedures that lead to a significant improvement of charge transfer characteristics of 3D printed electrodes.
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Optimization of Parameters Used in the Application of Elimination Voltammetry with Linear Scan
Navrátil, Tomáš ; Trnková, L. ; Hrdlička, Vojtěch ; Li, X.
Elimination Voltammetry with Linear Scan (EVLS) is a well-established mathematical method that aids in understanding an analyzed electrochemical system. In almost 30 years since its derivation, it has become a “black-box” technique that is applied automatically (in most cases due to its incorporation into a voltammetric software) without thinking about its fundamentals. However, the choice of optimum parameters under which DC voltammetric data (from which elimination curves are calculated) is crucial. This contribution deals with revealing the optimum ratio of applied scan rates and their absolute values (i.e., times of recording) in dependence on the character of the investigated system (diffusion-controlled process, adsorption-controlled process, etc.).
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A New Hollow Fiber-Based Liquid-Phase Microextraction Method for the Determination of Antihypertensive Drug Lercanidipine in Biological Samples
Labzova, O. ; Hrdlička, Vojtěch ; Navrátil, Tomáš ; Šelešovská, R.
A new hollow fiber-based liquid-phase microextraction (HF-LPME) method for the determination of antihypertensive drug lercandipine (LCN) in biological samples was developed. HF-LPME was\ncombined with optimized square wave voltammetry (SWV) on a cathodically pre-treated screenprinted boron-doped diamond electrode (SP-BDDE). Optimum HF-LPME conditions were:\nsupported liquid membrane (SLM) dodecane, 0.02 mol L-1 Britton-Robinson buffer (BRB, pH = 3) acceptor phase, BRB (pH = 7) donor phase, and time of extraction 30 min. Limits of quantification (LOQ) and detection (LOD) were 3.3 and 1.1 nmol L-1, respectively. The applicability of the developed method was verified on human urine, blood serum, and blood plasma with 20 and 100 nmol L-1 LCN addition.
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A New Approach to Determining the Drug Guaifenesin Using Voltammetric and Flow Injection Analysis
Kelíšková, P. ; Matvieiev, O. ; Sokolová, Romana ; Janíková, L. ; Behúl, M. ; Šelešovská, R.
This study presents a new method for detecting guaifenesin (GFE) in pharmaceutical samples. We employed screen-printed sensors with a boron-doped diamond electrode (BDDE) to develop and validate both voltammetric and flow amperometric methods. These approaches were effectively used to analyze model solutions, pharmaceutical preparations, and serum samples spiked with GFE, producing accurate results comparable to those obtained with HPLC/DAD analysis. The developed methods provide straightforward, sensitive, and selective means for determining GFE in various sample matrices, underscoring the potential of SP/BDDE in electrochemical analysis.
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Reaction Mechanisms of Psychoactive Compounds
Sokolová, Romana ; Beneš, Marek ; Jiroušková, Eliška ; Degano, I.
The reaction mechanism of selected new psychoactive substances (NPS) 4-methylpentedrone and 2-(((4-ethyl-2,5-dimethoxyphenethyl)amino)methyl)phenol was investigated based on their\nelectrochemical and spectroelectrochemical properties. Both drugs were examined by means of cyclic voltammetry using diagnostic parameters for particular reaction schemes, UV/Vis, and IR\nspectroelectrochemistry. Since water participates in the redox mechanism of both studied compounds, the reaction mechanism was studied under a controlled amount of water in an\nacetonitrile environment.
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Surfactant-free silver nanofluids as liquid systems with neuromorphic potential
Nikitin, D. ; Biliak, K. ; Lemke, J. ; Protsak, M. ; Pleskunov, P. ; Tosca, M. ; Ali-Ogly, S. ; Červenková, V. ; Adejube, B. ; Bajtošová, L. ; Černochová, Zulfiya ; Prokeš, J. ; Křivka, I. ; Biederman, H. ; Faupel, F. ; Vahl, A. ; Choukourov, A.
Neuromorphic engineering is a rapidly developing branch of science that aims to implement the unique attributes of biological neural networks in artificial devices. Most neuromorphic devices are based on the resistive switching effect, which involves changing the device’s conductivity in response to an external electric field. For instance, percolating nanoparticle (NP) networks produced by gas aggregation cluster sources (GAS) show collective spiking behavior in conductivity reminiscent of brain-like dynamics. Nevertheless, the problem of dynamic spatial reconfiguration in solid-state neuromorphic systems remains unsolved. Herein, novel nanofluids with resistive switching properties are proposed as neuromorphic media. They are produced by depositing silver NPs from GAS into vacuum-compatible liquids (paraffin, silicon oil, and PEG) without the use of surfactants or other chemicals. When the electric field is applied between two electrodes, the migration of NPs toward biased electrode is detected in all liquids. The electrophoretic nature of the NP movement was proved by means of ζ-potential measurements. Such movement led to the self-assembly of NPs in conductive paths connecting the electrodes and, as a result, to resistive switching. The electrical response was strongly dependent on the dielectric constant of the base liquid. The Ag-PEG nanofluid demonstrated the best switching performance reproducible during several tens of current-voltage cycles. The growth of flexible and reconfigurable conductive filaments in nanofluids makes them suitable media for potential realization of 3D neural networks.
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Temoporfin-conjugated upconversion nanoparticles for NIR-induced photodynamic therapy of pancreatic cancer
Shapoval, Oleksandr ; Větvička, D. ; Kabešová, M. ; Engstová, Hana ; Horák, Daniel
Photodynamic therapy (PDT), a clinically approved cancer treatment strategy, has the potential to cure pancreatic cancer with minimal side effects. PDT primarily uses visible wavelengths to directly activate hydrophobic photosensitizers, which may be insufficient for deep-seated cancer cells in clinical practice due to poor penetration. Upconversion nanoparticles (UCNPs) serve as an indirect excitation source to activate photosensitizers (PSs) in the NIR region, overcoming the limitations of molecular PSs such as hydrophobicity, non-specificity, and excitation in the UV/Vis region. Here, monodisperse upconversion NaYF4:Yb3+, Er3+, Fe2+ nanoparticles (UCNPs) have been surface-engineered with poly(methyl vinyl ether-alt-maleic acid) (PMVEMA) and temoporfin (mTHPC), a clinically used PDT prodrug, for near-infrared (NIR) light-triggered PDT of pancreatic cancer. The incorporation of Fe2+ ions into the particles increased the fluorescence intensity in the red region matching the activation wavelength of mTHPC. Covalent binding of mTHPC to the surface of UCNP@PMVEMA particles provided colloidally stable conjugates enabling generation of singlet oxygen. In vitro cytotoxicity and photodynamic activity of the particles were evaluated using INS-1E rat insulinoma and Capan-2 and PANC-01 human pancreatic adenocarcinoma cell lines. The PDT efficacy of UCNP@PMVEMA-mTHPC conjugates after irradiation with 980 nm NIR light was tested in vivo in a pilot study on Capan-2 human pancreatic adenocarcinoma growing subcutaneously in athymic nude mice. The intratumoral administration of the nanoconjugates significantly hindered tumor growth and demonstrated promising PDT efficacy against human pancreatic cancer.
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Electrochemical Valorization of Lignocellulosic Biomass Amination of Furfural and 5-Hydroxymethylfurfural
Donkeng Dazie, Joel ; Koláčná, Lucie ; Urban, Jiří ; Lamač, Martin ; Ludvík, Jiří
Furfural (FF) and 5-hydroxymethylfurfural (HMF) isolated from waste lignocellulosic biomass represent renewable sources. The present contribution deals with the transformation of FF and HMF into furfuryl amines which are important precursors namely for pharmaceutical synthesis. First, FF and HMF underwent condensation reactions with various amines which were electrochemically monitored to optimize the process. The resulting Schiff bases were identified by NMR and subsequently electrochemically reduced in basic media. The vicinal diamine (aminopinacol) was the main product besides the expected furfuryl amines. This reaction is a contribution to green synthesis because it was performed electrochemically, in water, and without any metallic catalysts.
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