Academic literature on the topic 'Cationic redox probe'

Ionomers are used as the solid-electrolyte in many electrochemical energy conversion technologies where they offer many functionalities such as ion conduction, electrical insulation, and water transport. These ionomers are found as nanometer-thick electrolyte thin films within the catalyst layers of fuel cells, electrolyzers, and hydrogen-based redox flow batteries where electrochemical reactions take place. The ionomer performance and durability are strongly related to their properties governed by a myriad of parameters such as chemical structure, water uptake, and morphology, all of which are stimulated differently by the external environment. Typically, the ionomer consists of the same ion-conducting polymer used as the electrode separator but exhibit disparate properties from the bulk membrane when nanometer thickness coatings are confined to a hard substrate (as in a catalyst layer), where the behavior is influenced by the ionomer affinity with the air and hard interfaces. Two motifs of ionomers exist, one as an acidic polymer (e.g. Nafion) and the alternative, and less studied, alkaline polymer (e.g. Sustainion). This talk will focus on filling in the gaps between the disparate properties of alkaline ionomers in the thin film motif that have been extensively studied for acidic ionomers. Aspects such as different backbones (e.g. perfluorinated, aliphatic, aromatic) and side chains (e.g. length, functional group) are explored in X-ray scattering, hydration, and transport measurements. Small-angle X-ray scattering is used to probe the morphology of these different polymer thin-films. Quartz crystal microbalance and spectroscopic ellipsometry under different states of humidity are used to probe hydration and free volume. The resulting correlations provide insights on not only how different polymer respond to the confined environment but how chemistry can be tuned to boost performance in alkaline electrochemical energy devices.

Developing rapid and efficient analytical methods is of great importance for food safety Herein, we present a novel homogeneous electrochemical aptasensor for ultrasensitive quantitative determination of zearalenone (ZEN) based on a nanocomposite probe and silica nanochannel film. X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and UV–Vis characterization techniques confirm that graphene oxide (GO) bears an aromatic conjugated structure, along with hydroxyl and carboxyl groups, facilitating the subsequent adsorption of cationic redox hexa-ammine-ruthenium (III) (Ru(NH3)63+) and anionic ZEN aptamer, to form a Ru(NH3)63+–ZEN aptamer–GO nanocomposite probe in a homogeneous solution. Vertically-ordered mesoporous silica films (VMSF) bearing silanol groups can be simply grown on the solid indium tin oxide (ITO) electrode surface and enable the selective preconcentration of Ru(NH3)63+, eventually leading to signal amplification. Since the detachment of Ru(NH3)63+ from the GO surface by the recognized ZEN aptamer in the presence of ZEN, more free Ru(NH3)63+ is released in solution and produces enhanced redox signals at the VMSF modified ITO electrode, allowing quantitative detection of ZEN. On the basis of the above sensing strategy, the proposed homogeneity, due to the assistance of graphene, as well as of the signal amplification and anti-fouling effects of VMSF, accurate analysis of ZEN can be realized in maize and Chinese chestnut samples.

Herein we report a highly specific electrochemical aptasenseor for AFB1 determination based on AFB1-controlled diffusion of redox probe (Ru(NH3)63+) through nanochannels of AFB1-specific aptamer functionalized VMSF. A high density of silanol groups on the inner surface confers VMSF with cationic permselectivity, enabling electrostatic preconcentration of Ru(NH3)63+ and producing amplified electrochemical signals. Upon the addition of AFB1, the specific interaction between the aptamer and AFB1 occurs and generates steric hindrance effect on the access of Ru(NH3)63+, finally resulting in the reduced electrochemical responses and allowing the quantitative determination of AFB1. The proposed electrochemical aptasensor shows excellent detection performance in the range of 3 pg/mL to 3 μg/mL with a low detection limit of 2.3 pg/mL for AFB1 detection. Practical analysis of AFB1 in peanut and corn samples is also accomplished with satisfactory results by our fabricated electrochemical aptasensor.

A rapid and convenient homogeneous aptamer sensor with high sensitivity is highly desirable for the electrochemical detection of tumor biomarkers. In this work, a homogeneous electrochemical aptamer sensor is demonstrated based on a two-dimensional (2D) nanocomposite probe and nanochannel modified electrode, which can realize sensitive detection of carcinoembryonic antigen (CEA). Using π-π stacking and electrostatic interaction, CEA aptamer (Apt) and cationic redox probe (hexaammineruthenium(III), Ru(NH3)63+) are co-loaded on graphite oxide (GO), leading to a 2D nanocomposite probe (Ru(NH3)63+/Apt@GO). Vertically ordered mesoporous silica-nanochannel film (VMSF) is easily grown on the supporting indium tin oxide (ITO) electrode (VMSF/ITO) using the electrochemical assisted self-assembly (EASA) method within 10 s. The ultrasmall nanochannels of VMSF exhibits electrostatic enrichment towards Ru(NH3)63+ and size exclusion towards 2D material. When CEA is added in the Ru(NH3)63+/Apt@GO solution, DNA aptamer recognizes and binds to CEA and Ru(NH3)63+ releases to the solution, which can be enriched and detected by VMSF/ITO electrodes. Based on this mechanism, CEA can be an electrochemical detection ranging from 60 fg/mL to 100 ng/mL with a limit of detection (LOD) of 14 fg/mL. Detection of CEA in human serum is also realized. The constructed homogeneous detection system does not require the fixation of a recognitive aptamer on the electrode surface or magnetic separation before detection, demonstrating potential applications in rapid, convenient and sensitive electrochemical sensing of tumor biomarkers.

It is well known that both the aptamer surface density and surface chemistry can have a strong influence on the analytical performance of aptasensors based on target-induced conformational changes1. In this context, we report here an improved protocol for obtaining aptasensing platforms which allows fine-tuning the DNA aptamer surface coverage. First, glassy carbon substrates were functionalized with ethynylphenyl groups through the electrochemical reduction of silyl-protected ethynylphenyl diazonium tetrafluoroborates followed by deprotection with tetrabutylammonium fluoride2. The successful removal of the protecting groups (triisopropylsilyl-, triphenylsilyl- and tris(biphen-4-yl)silyl-) was confirmed by X-ray photoelectron spectroscopy and cyclic voltammetry in the presence of Fe(CN)6 3-/4- as soluble redox probe. Following “click” post-modification with suitable derivatization reagents, the surface coverage with ethynylphenyl groups was assessed using complementary techniques such as XPS, cyclic voltammetry and chronocoulometry. For example, the F/C surface ratio of substrates derivatized with 1-(2,2,2-trifluoroethoxy)-6-azidohexane provided an indication of the functionalization degree, and the integration of Fc/Fc+ voltammetric peaks for substrates modified with N-(6-azidohexyl)ferrocenecarboxamide allowed a quantitative determination of the surface coverage. Both techniques showed a good correlation between the protective group size and the surface coverage with alkyne groups. Likewise, we observed a similar trend for substrates derivatized with azide-modified oligonucleotides, where the surface packing density was determined based on the chronocoulometric response of Ru(NH3)6 3+, a cationic redox probe which binds with the negatively charged phosphate groups from the oligonucleotide backbone. As proof of concept, we further developed an electrochemical molecular beacon aptasensor employing a ferrocene-labeled quinine aptamer. We demonstrate that the aptamer surface density, and ultimately the analytical performance of molecular beacon aptasensors, can be effectively fine-tuned by employing silyl protecting groups of different sizes. Acknowledgements This work was supported by a grant from the Romanian Ministry of Education and Research, CNCS-UEFISCDI, project number PN-III-P4-ID-PCE-2020-2474, within PNCDI III. References Onaş, A. M., Dascălu, C., Raicopol, M. D. & Pilan, L. Critical Design Factors for Electrochemical Aptasensors Based on Target-Induced Conformational Changes: The Case of Small-Molecule Targets. Biosensors 12, (2022). Leroux, Y. R., Fei, H., Noël, J.-M. M., Roux, C. & Hapiot, P. Efficient covalent modification of a carbon surface: Use of a silyl protecting group to form an active monolayer. J. Am. Chem. Soc. 132, 14039–14041 (2010).

LiNiO2 (LNO) is considered a very promising and high energy density alternative to Co-containing Li-ion battery cathodes. It is also the benchmarked cathode material of the European BIGMAP project, which aim is to combine advance operando characterization, computational modelling and artificial intelligence in order to accelerate the research and development of new generation batteries. However, the material suffers from several degradation issues resulting in fading cell performance. In particular, the presence of highly reactive Ni4+ species at the electrode/electrolyte interface1, Ni dissolution from the cathode leading to the loss of active material 2, and O2 release at high voltage are the major drawbacks precluding commercial applications. A recent in situ study1 has shown that O2 release compromises the structural stability and triggers reactions with ethylene carbonate (EC), prompting CO2evolution3,4. In parallel, solid state physics community is also largely interested into LiNiO2 in the framework of a larger investigation around the electronic and atomic structure of nickelates, in particular rare-earth nickelates. This interest rises from the fact that there is still no consensus on the atomic/electronic structure of LiNiO2, while different descriptions exist in literature. Local probe techniques demonstrate the distortion of NiO6 octahedra, and there are two on-going theories for explaining the presence of this distortion: (i) Ni3+ (t2g6 eg1) Jahn-Teller (JT) distortion, (ii) 2 Ni3+ → Ni2+ + Ni4+ bond disproportionation (BD)5. Surprisingly, the local order distortion does not result in the long-range distortion, the mechanism behind this phenomenon is not completely understood. In this contribution we present a detailed study of LNO cathode material by operando Raman and X-ray absorption spectroscopy (XAS) at the Ni K-edge, ex situ X-ray emission spectroscopy (XES) and resonant Inelastic X-ray scattering (RIXS). Distinguishing between JT and BD models is challenging, and therefore NaNiO2 reference is used, which is isoelectronic material to LiNiO2, and is known to feature long-range JT distortion. While XAS is widely established technique to probe local structure and transition metal oxidation state, RIXS is useful for assessing d-d transitions and bond disproportionation. Operando Raman spectroscopy is an excellent tool for studying phase transitions in Li-ion battery cathodes and is therefore complementary to the employed X-ray techniques6. It provides information on two characteristic for layered oxides crystalline phonon modes A1g and Eg, and sheds light on both short-range order and cationic/anionic redox. The penetration depth is estimated as top few hundred nanometers of around five micrometres sized secondary particle, therefore near-surface area is probed. The results show a complex behaviour of band positions and intensities during cycling (figure 1), corresponding to four phases transformations. Notably the peaks intensities increase considerably, while the widths are decreased, which is evidence of increased order upon material delithiation, and is in agreement with the Extended X-ray Absorption Fine Structure (EXAFS). Raman is also used to evaluate the contribution of anionic redox, since all the reduced oxygen species (superoxide, peroxide and molecular oxygen) have well-known Raman-active modes. To conclude, we demonstrate how a combination of multiple vibrational and X-rays based spectroscopies provides a better understanding of both LNO ground state electronic structure and redox mechanism. This increased fundamental understanding will stimulate the design of better strategies for prevention of the material degradation and improved cycle retention. References: de Biasi, L. et al. Phase Transformation Behavior and Stability of LiNiO2 Cathode Material for Li-Ion Batteries Obtained from In Situ Gas Analysis and Operando X-Ray Diffraction. ChemSusChem 12, 2240–2250 (2019). Klein, S. et al. Exploiting the Degradation Mechanism of NCM523 Graphite Lithium-Ion Full Cells Operated at High Voltage. ChemSusChem 14, 595–613 (2021). Jung, R., Metzger, M., Maglia, F., Stinner, C. & Gasteiger, H. A. Chemical versus Electrochemical Electrolyte Oxidation on NMC111, NMC622, NMC811, LNMO, and Conductive Carbon. J Phys Chem Lett 8, 4820–4825 (2017). Freiberg, A. T. S., Roos, M. K., Wandt, J., de Vivie-Riedle, R. & Gasteiger, H. A. Singlet Oxygen Reactivity with Carbonate Solvents Used for Li-Ion Battery Electrolytes. J Phys Chem A 122, 8828–8839 (2018). Chen, H., Freeman, C. L. & Harding, J. H. Charge disproportionation and Jahn-Teller distortion in LiNiO${}_{2}$ and NaNiO${}_{2}$: A density functional theory study. Phys Rev B 84, 85108 (2011). Flores, E., Mozhzhukhina, N., Aschauer, U. & Berg, E. J. Operando Monitoring the Insulator–Metal Transition of LiCoO 2 . ACS Appl Mater Interfaces 13, 22540–22548 (2021). Figure 1

The background: The monolayers self-assembled on the gold electrode incorporated transition metal complexes can act both as receptor (“host” molecules) immobilization sites, as well as transducer for interface recognitions of “guest” molecules present in the aqueous solutions. Their electrochemical parameters influencing the sensing properties strongly depend on the transition metal complex structures. The objectives: The electrochemical characterization of the symmetric terpyridine–M2+–terpyridine and asymmetric dipyrromethene–M2+–terpyridine complexes modified with ssDNA probe covalently attached to the gold electrodes and exploring their ssDNA sensing ability were the main aims of the research presented. The methods: Two transition metal cations have been selected: Cu2+ and Co2+ for creation of redox-active monolayers. The electron transfer coefficients indicating the reversibility and electron transfer rate constant measuring kinetic of redox reactions have been determined for all SAMs studied using: Cyclic Voltammetry, Osteryoung Square-Wave Voltammetry, and Differential Pulse Voltammetry. All redox-active platforms have been applied for immobilization of ssDNA probe. Next, their sensing properties towards complementary DNA target have been explored electrochemically. The results: All SAMs studied were stable displaying quasi-reversible redox activity. The linear relationships between cathodic and anodic current vs. san rate were obtained for both symmetric and asymmetric SAMs incorporating Co2+ and Cu2+, indicating that oxidized and reduced redox sites are adsorbed on the electrode surface. The ssDNA sensing ability were observed in the fM concentration range. The low responses towards non-complementary ssDNA sequences provided evidences for sensors good selectivity. The conclusions: All redox-active SAMs modified with a ssDNA probe were suitable for sensing of ssDNA target, with very good sensitivity in fM range and very good selectivity. The detection limits obtained for SAMs incorporating Cu2+, both symmetric and asymmetric, were better in comparison to SAMs incorporating Co2+. Thus, selection of the right transition metal cation has stronger influence on ssDNA sensing ability, than complex structures.

The intercalation of cations into electrodeposited nickel hexacyanoferrate (NiHCF) depends on the stoichiometry and oxidation state of the material. To better understand this material's performance as a cation separation matrix, the oxidation state needs to be measured independently from the stoichiometry, regardless of the particular intercalated cation. Reported is the use of Raman spectroscopy to quantify the absolute oxidation state of NiHCF thin films. Raman spectroscopy probes NiHCF's cyanide bonds, which are sensitive to the oxidation state of the matrix. The oxidation state is controlled via potentiostatic experiments in electrolytes containing Na+, K+, and Cs+ (NO3− is the common anion). Principal component analysis (PCA) on the Raman spectra shows that more than 90% of the spectral variance is captured by one principal component, with a score value shown to be directly related to the oxidation state of the film. A universal, predictive regression model was developed using these score values as the dependent variables and Raman spectra as the independent variables. The results were confirmed with electrochemistry and energy dispersive X-ray spectroscopy.

Un film orienté à base de silice mésoporeuse sur une électrode FTO a été préparé par une approche d'auto-assemblage assistée par électrochimie (EASA). Un potentiel de -1,5 V a été appliqué à l'électrode FTO contenant un précurseur de silice préhydrolysée (par exemple, l'orthosilicate de tétraéthyle), en présence d'un modèle (par exemple, le bromure de cétrimonium) et d'un électrolyte. Cette approche permet de générer des nanocanaux de silice alignés verticalement avec des tailles de pores ajustables entre 2 et 3 nm, selon le modèle. Ce travail a montré le comportement voltammétrique et la sélectivité du film de silice mésoporeuse vis-à-vis de divers cations chargés positivement de nature, de taille et de charge différentes. Les résultats ont montré une accumulation et une sélectivité favorisant l'ion le moins chargé positivement : MB⁺ > PQ²⁺ > DQ²⁺ > Ru(bpy)₃²⁺ > Ru(NH₃)₆³⁺. L'augmentation des signaux voltamétriques par rapport à l'électrode FTO nue dépendait fortement du type de sonde. L'accumulation des différentes sondes redox est attribuée à l'orientation verticale du nanocanal qui favorise le transport rapide et la diffusion à la surface de l'électrode. Une caractérisation électrochimique plus poussée a montré une interaction entre le processus contrôlé par la surface et le processus contrôlé par la diffusion, où les espèces adsorbées sont plus importantes dans les milieux dilués. Les résultats ont montré que la modification de la longueur debye et du rayon électrocinétique du nanocanal de silice en raison de la force ionique ou du diamètre du nanocanal affecte également le transport et la détection électrochimique de l'analyte paraquat. Les films de silice mésoporeuse ayant des tailles de pores différentes, préparés en utilisant différents bromure d'alkylammonium comme modèle, donnent des sensibilités différentes, qui pourraient être dues à la différence de charge électrochimique de la surface de la silice, ainsi qu'à la distribution des ions dans le nanocanal. Enfin, une tentative de modification de la surface de la paroi de silice en utilisant de la zircone a également été faite pour étudier le transport des cations, ce qui pourrait ouvrir la voie à une meilleure stabilité du film mésoporeux
Oriented mesoporous silica-based film on FTO electrode was prepared via electrochemically-assisted self-assembly approach (EASA). A potential of -1.5V was applied to the FTO electrode containing a prehydrolyzed silica precursor, (e.g. tetraethyl orthosilicate), in the presence of a template (e.g. cetrimonium bromide) and electrolyte. This approach could generate vertically-aligned silica nanochannels with pore sizes adjustable between 2 and 3 nm, depending on the template. This work showed the voltammetric behavior and the selectivity of the mesoporous silica film towards various positively-charged cations of different nature, size, and charge. Results showed an accumulation and selectivity favoring the least positive charged ion: MB⁺ > PQ²⁺ > DQ²⁺ > Ru(bpy)₃²⁺ > Ru(NH₃)₆³⁺. The enhancement of the voltammetric signals relative to the bare FTO electrode was strongly dependent on the probe type. The accumulation of the different redox probe is attributed to the due to the vertical orientation of the nanochannel favoring fast transport and diffusion unto the electrode surface. Further electrochemical characterization showed an interplay of the suface-controlled and diffusion-controlled process, wherein adsorbed species is more prominent in diluted media. Results showed that changing the debye length and electrokinetic radius of the silica nanochannel due to the ionic strength or nanochannel diameter also affects the transport and electrochemical detection of the paraquat analyte. Mesoporous silica films having different pore size, prepared using different alkyl ammonium bromide as template, yield different sensitivities, which could be due to the difference in electrochemical charge of the silica surface, as well as the distribution of ions in the nanochannel. Finally, an attempt to modify the surface of silica wall using zirconia was also made to study the transport of cations, which could pave a way for an improved stability of the mesoporous film

Scanning electrochemical microscopy (SECM) is an electrochemical technique used to measure faradaic current changes local to the surface of a sample. The incorporation of shear force (SF) feedback in SECM enables the concurrent acquisition of topographical data of substrates along with electrochemical measurements. Contemporary SECM measurements require a redox mediator such as ferrocene methanol (FcMeOH) for electrochemical measurements; however, this could prove detrimental in the imaging of biological cells. In this article, nanoscale polypyrrole membranes doped with dodecylbenzene sulfonate (PPy(DBS)) are deposited at the tip of an ultra-microelectrode (UME) to demonstrate a novel modification of the contemporary SECM-SF imaging technique that operates in the absence of a redox mediator. The effect of distance from an insulating substrate and bulk electrolyte concentration on sensor response are examined to validate this technique as a tool for correlated topographical imaging and cation flux mapping. Varying the distance of the PPy(DBS) tipped probe from the substrate in a solution containing NaCl causes a localized change in cation concentration within the vicinity of the membrane due to hindered diffusion of ions from the bulk solution to the diffusion field. The cation transport into the membrane in close proximity to the substrate is low as compared to that in the electrolyte bulk and asymptotically approaches the bulk value at the sense length. At a constant height from the base, changing the bulk NaCl concentration from 5 mM to 10 mM increases the filling efficiency from 35% to 70%. Further, the sense length of this modified electrode in NaCl is about 440 nm which is significantly lower as compared to that of a bare electrode in ferrocene methanol (5–20 μm). It is postulated that this novel technique will be capable of producing high resolution maps of surface cation concentrations, thus having a significant impact in the field of biological imaging.