Composite Silica-Based Films as Platforms for Electrochemical Sensors.

Sol-gel-derived silica thin films generated onto electrode surfaces in the form of organic-inorganic hybrid coatings or other composite layers have found tremendous interest for being used as platforms for the development of electrochemical sensors and biosensors. After a brief description of the strategies applied to prepare such materials, and their interest as electrode modifier, this review will summarize the major advances made so far with composite silica-based films in electroanalysis. It will primarily focus on electrochemical sensors involving both non-ordered composite films and vertically oriented mesoporous membranes, the biosensors exploiting the concept of sol-gel bioencapsulation on electrode, the spectroelectrochemical sensors, and some others.

Electrochemical approaches based on micro- and nanomaterials for diagnosing oxidative stress.

This review article comprehensively discusses the various electrochemical approaches for measuring and detecting oxidative stress biomarkers and enzymes, particularly reactive oxygen/nitrogen species, highly reactive chemical molecules, which are the byproducts of normal aerobic metabolism and can oxidize cellular components such as DNA, lipids, and proteins. First, we address the latest research on the electrochemical determination of reactive oxygen species generating enzymes, followed by detection of oxidative stress biomarkers, and final determination of total antioxidant activity (endogenous and exogenous). Most electrochemical sensing platforms exploited the unique properties of micro- and nanomaterials such as carbon nanomaterials, metal or metal oxide nanoparticles (NPs), conductive polymers and metal-nano compounds, which have been mainly used for enhancing the electrocatalytic response of sensors/biosensors. The performance of the electroanalytical devices commonly measured by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in terms of detection limit, sensitivity, and linear range of detection is also discussed. This article provides a comprehensive review of electrode fabrication, characterization and evaluation of their performances, which are assisting to design and manufacture an appropriate electrochemical (bio)sensor for medical and clinical applications. The key points such as accessibility, affordability, rapidity, low cost, and high sensitivity of the electrochemical sensing devices are also highlighted for the diagnosis of oxidative stress. Overall, this review brings a timely discussion on past and current approaches for developing electrochemical sensors and biosensors mainly based on micro and nanomaterials for the diagnosis of oxidative stress.

Laser Cutting Coupled with Electro-Exfoliation to Prepare Versatile Planar Graphene Electrodes for Energy Storage.

The study of planar energy storage devices, characterized by low-cost, high capacity, and satisfactory flexibility, is becoming a valuable research hotspot. Graphene, monolayer sp2 hybrid carbon atoms with a large surface area, always acts as its active component, yet there is a tension between its high conductivity and ease of implementation. Although the difficult-to-assemble graphene can easily achieve planar assemblies in its highly oxidized form (GO), the undesirable conductivity, even after proper reduction, still restricts its further applications. Here, a facile "Top-down" method has been proposed to prepare the graphene planar electrode via in situ electro-exfoliation of graphite supported on a piece of laser-cutting patterned scotch tape. Detailed characterizations have been performed to study its physiochemical property evolution during electro-exfoliation. The obtained flexible graphene planar electrodes show decent energy storage performance, e.g., 40.8 mF cm-2 at a current density of 0.5 mA cm-2 and an 81% capacity retention at a current density of 8 mA cm-2 for the optimized sample G-240. Their high conductivity also makes it possible to couple them with other redox-active materials through electrodeposition to improve their performance, e.g., ferrocene-functionalized mesoporous silica film (Fc-MS), MnO2, and polyaniline (PANI). The highest capacity was achieved with the PANI functionalized sample, which achieved a 22-fold capacity increase. In a word, the versatility, practicality, and adaptability of the protocol to prepare the planar graphene electrode proposed in this work make it a potential candidate to meet the continuously growing energy storage demands.

Electroinduced Surfactant Self-Assembly Driven to Vertical Growth of Oriented Mesoporous Films.

Supramolecular soft-templating approaches to mesoporous materials have revolutionized the generation of regular nanoarchitectures exhibiting unique features such as uniform pore structure with tunable dimensions, large surface area, and high pore volume, variability of composition, and/or ease of functionalization with a wide range of organo-functional groups or good hosts for the in situ synthesis of nano-objects. One appealing concept in this field is the development of ordered mesoporous thin films as such a configuration has proven to be essential for various applications including separation, sensing, catalysis (electro and photo), energy conversion and storage, photonics, solar cells, photo- and electrochromism, and low-k dielectric coatings for microelectronics, bio and nanobio devices, or biomimetic surfaces. Supported or free-standing mesoporous films are mostly prepared by evaporation induced self-assembly methods, thanks to their good processing capability and flexibility to manufacture mesostructured oxides and organic-inorganic hybrids films with periodically organized porosity.One important challenge is the control of pore orientation, especially in one-dimensional nanostructures, which is not straightforward from the above evaporation induced self-assembly methods. Accessibility of the pores represents another critical issue, which can be basically ensured in the event of effective interconnections between the pores, but the vertical alignment of mesopore channels will definitely offer the best configuration to secure the most efficient transfer processes through the mesoporous membranes. The orthogonal growth of mesochannels is however not thermodynamically favored, requiring the development of methods enabling self-organization through nonequilibrium states. We found that electrochemistry afforded a real boon to tackle this problem via the electrochemically assisted self-assembly (EASA) method, which not only provides a fast and versatile way to generate highly ordered and hexagonally packed mesopore channels but also constitutes a real platform for the development of functionalized oriented films carrying a wide range of organo-functional groups of adjustable composition and properties.This Account introduces the EASA concept and discusses its development along with the significant progress made from its discovery, notably in view of recent advances on the functionalization of oriented mesoporous silica films, which expand their fields of application. EASA is based on the in situ combination of electrochemically triggered pH-induced polycondensation of silica precursors with electrochemical interfacial surfactant templating, leading to the very fast (a few seconds) growth of vertically aligned silica walls through self-assembly around surfactant hemimicelles transiently formed onto the underlying support. This method benefits from the possibility to deposit uniform thin films onto surfaces of different natures and complex morphologies including at the microscale. From this discovery, our research expanded to cover domains beyond the simple production of bare silica films, turning to the challenge of incorporation and exploitation of organo-functional groups or nanofilaments. So far, the great majority of methods developed for the functionalization of mesoporous silica is based on postsynthesis grafting or co-condensation approaches, which suffer from serious limitations with oriented films (pore blocking, lack of ordering). We demonstrated the uniqueness of EASA combined with click chemistry to afford a versatile and universal route to oriented mesoporous films bearing organo-functional groups of multiple composition. This opened perspectives for future developments and applications, some of which (sensing, permselective coatings, energy storage, electrocatalysis, electrochromism) are also considered in this Account.

Polyaniline nanowire arrays generated through oriented mesoporous silica films: effect of pore size and spectroelectrochemical response.

Indium-tin oxide electrodes modified with vertically aligned silica nanochannel membranes have been produced by electrochemically assisted self-assembly of cationic surfactants (cetyl- or octadecyl-trimethylammonium bromide) and concomitant polycondensation of the silica precursors (tetraethoxysilane). They exhibited pore diameters in the 2-3 nm range depending on the surfactant used. After surfactant removal, the bottom of mesopores was derivatized with aminophenyl groups via electrografting (i.e., electrochemical reduction of in situ generated aminophenyl monodiazonium salt). These species covalently bonded to the ITO substrate were then exploited to grow polyaniline nanofilaments by electropolymerization of aniline through the nanochannels. Under potentiostatic conditions, the length of polyaniline wires is controllable by tuning the electropolymerization time. From cyclic voltammetry characterization performed either before or after dissolution of the silica template, it appeared that both the polyaniline/silica composite and the free polyaniline nanowire arrays were electroactive, yet with much larger peak currents in the latter case as a result of larger effective surface area offered to the electrolyte solution. At identical electropolymerization time, the amount of deposited polyaniline was larger when using the silica membrane with larger pore diameter. All polyaniline deposits exhibited electrochromic properties. However, the spectroelectrochemical data indicated more complete interconversion between the coloured oxidized form and colourless reduced polyaniline for the arrays of nanofilaments in comparison to bulky films. In addition, the template-free nanowire arrays (i.e., after silica dissolution) were characterized by faster electrochromic behaviour than the polyaniline/silica hybrid, confirming the potential interest of such polyaniline nano-brushes for practical applications.

Weak Coordinating Character of Organosulfonates in Oriented Silica Films: An Efficient Approach for Immobilizing Cationic Metal-Transition Complexes.

Iron (II) tris(2,2'-bipyridine) complexes, [Fe(bpy)3]2+, have been synthesized and immobilized in organosulfonate-functionalized nanostructured silica thin films taking advantage of the stabilization of [Fe(H2O)6]2+ species by hydrogen bonds to the anionic sulfonate moieties grafted to the silica nanopores. In a first step, thiol-based silica films have been electrochemically generated on indium tin oxide (ITO) substrates by co-condensation of 3-mercaptopropyltrimethoxysilane (MPTMS) and tetraethoxysilane (TEOS). Secondly, the thiol function has been modified to sulfonate by chemical oxidation using hydrogen peroxide in acidic medium as an oxidizing agent. The immobilization of [Fe(bpy)3]2+ complexes has been performed in situ in two consecutive steps: (i) impregnation of the sulfonate functionalized silica films in an aqueous solution of iron (II) sulfate heptahydrate; (ii) dipping of the iron-containing mesostructures in a solution of bipyridine ligands in acetonitrile. The in situ formation of the [Fe(bpy)3]2+ complex is evidenced by its characteristic optical absorption spectrum, and elemental composition analysis using X-ray photoelectron spectroscopy. The measured optical and electrochemical properties of immobilized [Fe(bpy)3]2+ complexes are not altered by confinement in the nanostructured silica thin film.

Multi-stimuli Photo and Redox-active Nanostructured Mesoporous Silica Films on Transparent Electrodes.

Silica matrices hosting transition metal guest complexes may offer remarkable platforms for the development of advanced functional devices. We report here the elaboration of ordered and vertically oriented mesoporous silica thin films containing covalently attached tris(bipyridine)iron derivatives using a combination of electrochemically assisted self-assembly (EASA) method and Huisgen cycloaddition reaction. Such a versatile approach is primarily used to bind nitrogen-based chelating ligands such as (4-[(2-propyn-1-yloxy)]4'-methyl-2,2'-bypiridine, bpy') inside the nanochannels. Further derivatization of the bpy'-functionalized silica thin films is then achieved via a subsequent in-situ complexation step to generate [Fe(bpy)2 (bpy')]2+ inside the mesopore channels. After giving spectroscopic evidences for the presence of such complexes in the functionalized film, electrochemistry is used to transform the confined diamagnetic (S=0) FeLSbpy2bpy'2+ species to paramagnetic (S=1/2) oxidized FeLSbpy2bpy'3+ species in a reversible way, while blue light irradiation (λ=470 nm) enables populating the short-lived paramagnetic (S=2) FeHSbpy2bpy'2+ excited state. [Fe(bpy)2 (bpy')]2+ -functionalized ordered films are therefore both electro- and photo-active through the manipulation of the oxidation state and spin state of the confined complexes, paving the way for their integration in optoelectronic devices.

Electrogeneration of a Free-Standing Cytochrome c-Silica Matrix at a Soft Electrified Interface.

Interactions of a protein with a solid-liquid or a liquid-liquid interface may destabilize its conformation and hence result in a loss of biological activity. We propose here a method for the immobilization of proteins at an electrified liquid-liquid interface. Cytochrome c (Cyt c) is encapsulated in a silica matrix through an electrochemical process at an electrified liquid-liquid interface. Silica condensation is triggered by the interfacial transfer of cationic surfactant, cetyltrimethylammonium, at the lower end of the interfacial potential window. Cyt c is then adsorbed on the previously electrodeposited silica layer, when the interfacial potential, Δowϕ, is at the positive end of the potential window. By cycling of the potential window back and forth, silica electrodeposition and Cyt c adsorption occur sequentially as demonstrated by in situ UV-vis absorbance spectroscopy. After collection from the liquid-liquid interface, the Cyt c-silica matrix is characterized ex situ by UV-vis diffuse reflectance spectroscopy, confocal Raman microscopy, and fluorescence microscopy, showing that the protein maintained its tertiary structure during the encapsulation process. The absence of denaturation is further confirmed in situ by the absence of electrocatalytic activity toward O2 (observed in the case of Cyt c denaturation). This method of protein encapsulation may be used for other proteins (e.g., Fe-S cluster oxidoreductases, copper-containing reductases, pyrroloquinoline quinone-containing enzymes, or flavoproteins) in the development of biphasic bioelectrosynthesis or bioelectrocatalysis applications.

Electron transfers in graphitized HZSM-5 zeolites.

In the present work, we report the electron transfers occurring after ionization of the guest molecules of t-stilbene incorporated in graphitized HZSM-5 zeolites and we compare these results with the data obtained previously for graphite-free zeolites. Complementary diffuse reflectance UV-vis and Raman scattering spectroscopies provide evidence for stabilization of long lived charge separated states as observed in non-graphitized ZSM-5. The spectral features indicate that these species are located in the channels of the zeolite structure. However, the pulsed EPR technique shows strong coupling between unpaired electrons and the 13C atoms in the case of graphitized zeolites while this interaction is not observed in normal zeolites. This is assigned to the presence of charge transfer complexes in the close vicinity of graphite areas and to the possible electron transfer to the graphitized domain. Using cyclic voltammetry, an electrochemical response is observed for the first time in such systems demonstrating the role played by graphite in the electron transfers.

Synthesis of Vertically Aligned Porous Silica Thin Films Functionalized by Silver Ions.

In this work, we have developed a chemical procedure enabling the preparation of highly ordered and vertically aligned mesoporous silica films containing selected contents of silver ions bonded inside the mesopore channels via anchoring propyl-carboxyl units. The procedure involves the electrochemically assisted self-assembly co-condensation of tetraethoxysilane and (3-cyanopropyl)triethoxysilane in the presence of cetyltrimethylammonium bromide as a surfactant, the subsequent hydrolysis of cyano groups into carboxylate ones, followed by their complexation with silver ions. The output materials have been electrochemically characterized with regard to the synthesis effectiveness in order to confirm and quantify the presence of the silver ions in the material. The mesostructure has been observed by transmission electron microscopy. We have pointed out that it is possible to finely tune the functionalization level by controlling the co-condensation procedure, notably the concentration of (3-cyanopropyl)triethoxysilane in the synthesis medium.

Scanning Gel Electrochemical Microscopy (SGECM): Lateral Physical Resolution by Current and Shear Force Feedback.

Scanning gel electrochemical microscopy (SGECM) is a novel technique measuring local electrochemistry based on a gel probe. The gel probe, which is fabricated by electrodeposition of hydrogel on a microdisk electrode, immobilizes the electrolyte, and constitutes a two-electrode system upon contact with the sample. The contact area determines the lateral physical resolution of the measurement, and considering the soft nature of the gel it is essential to be well analyzed. In this work, the lateral physical resolution of SGECM is quantitatively studied from two aspects: (1) marking single sampling points by locally oxidizing Ag to AgCl and measuring their size; (2) line scan over reference samples with periodic topography and composition. The gel probe is approached to the sample by either current or shear force feedback, and the physical resolution of them is compared. For the optimal gel probe based on 25 µm diameter Pt disk electrode of Rg ≈ 2, the lateral physical resolution of SGECM at contact position is ca. 50 µm for current feedback and ca. 63 µm for shear force feedback. More importantly, the lateral physical resolution of SGECM can be flexibly tuned in the range of 14-78 µm by pulling or pressing the gel probe after touching the sample. In general, current feedback is more sensitive to gel-sample contact than shear force feedback. But the latter is more versatile, which is also applicable to nonconductive samples.

Moxifloxacin Hydrochloride Electrochemical Detection at Gold Nanoparticles Modified Screen-Printed Electrode.

It appeared that either the carbon paste or the screen-printed carbon electrodes that were modified with gold nanoparticles (AuNPs) gave rise to the largest current responses after a rapid screening of various nanomaterials as modifiers of carbon composite electrodes in view of designing an electrochemical sensor for Moxifloxacin Hydrochloride (Moxi). The screen-printed electrode (SPE) support was preferred over the carbon paste one for its ability to be used as disposable single-use sensor enabling the circumvention of the problems of surface fouling encountered in the determination of Moxi. The response of AuNPs modified SPE to Moxi was investigated by cyclic voltammetry (CV) (including the effect of the potential scan rate and the pH of the medium), chronoamperometry, and differential pulse voltammetry (DPV) after morphological and physico-chemical characterization. DPV was finally applied to Moxi detection in phosphate buffer at pH 7, giving rise to an accessible concentration window ranging between 8 µM and 0.48 mM, and the detection and quantification limits were established to be 11.6 µM and 38.6 µM, correspondingly. In order to estimate the applicability of Moxi identification scheme in actual trials, it was practiced in a human baby urine sample with excellent recoveries between 99.8 % and 101.6 % and RSDs of 1.1-3.4%, without noticeable interference.

Mesoporous Silica-Based Materials for Electronics-Oriented Applications.

Electronics, and nanoelectronics in particular, represent one of the most promising branches of technology. The search for novel and more efficient materials seems to be natural here. Thus far, silicon-based devices have been monopolizing this domain. Indeed, it is justified since it allows for significant miniaturization of electronic elements by their densification in integrated circuits. Nevertheless, silicon has some restrictions. Since this material is applied in the bulk form, the miniaturization limit seems to be already reached. Moreover, smaller silicon-based elements (mainly processors) need much more energy and generate significantly more heat than their larger counterparts. In our opinion, the future belongs to nanostructured materials where a proper structure is obtained by means of bottom-up nanotechnology. A great example of a material utilizing nanostructuring is mesoporous silica, which, due to its outstanding properties, can find numerous applications in electronic devices. This focused review is devoted to the application of porous silica-based materials in electronics. We guide the reader through the development and most crucial findings of porous silica from its first synthesis in 1992 to the present. The article describes constant struggle of researchers to find better solutions to supercapacitors, lower the k value or redox-active hybrids while maintaining robust mechanical properties. Finally, the last section refers to ultra-modern applications of silica such as molecular artificial neural networks or super-dense magnetic memory storage.

Scanning Gel Electrochemical Microscopy for Topography and Electrochemical Imaging.

Scanning electrochemical probe techniques have been widely applied for analyzing the local electrochemical activity of surfaces and interfaces. In this work, we develop a new concept of carrying out local electrochemical measurements by localizing both the electrode and the electrolyte. This is achieved through a gel probe, which is prepared by electrodepositing chitosan-gelatin gel on a microdisk electrode. It is positioned in contact with the sample surface by shear force feedback. The preliminary results indicate that the topography of the sample can be mapped by tapping the probe and recording the coordinates at a given normalized shear force signal, while the local electrochemical activity can be retrieved from local measurements with the probe touching the sample surface. The technique is denoted as scanning gel electrochemical microscopy. As compared with existing techniques, it has a major advantage of operating in air with the electrolyte immobilized in gel. This would prevent the spreading and leakage of solution on the sample surface and may lead to field applications.

MS2 and Qß bacteriophages reveal the contribution of surface hydrophobicity on the mobility of non-enveloped icosahedral viruses in SDS-based capillary zone electrophoresis.

SDS is commonly employed as BGE additive in CZE analysis of non-enveloped icosahedral viruses. But the way by which SDS interacts with the surface of such viruses remains to date poorly known, making complicate to understand their behavior during a run. In this article, two related bacteriophages, MS2 and Qß, are used as model to investigate the migration mechanism of non-enveloped icosahedral viruses in SDS-based CZE. Both phages are characterized by similar size and surface charge but significantly different surface hydrophobicity (Qß > MS2, where '>' means 'more hydrophobic than'). By comparing their electrophoretic mobility in the presence or not of SDS on both sides of the CMC, we show that surface hydrophobicity of phages is a key factor influencing their mobility and that SDS-virus association is driven by hydrophobic interactions at the surface of virions. The CZE analyses of heated MS2 particles, which over-express hydrophobic domains at their surface, confirm this finding. The correlations between the present results and others from the literature suggest that the proposed mechanism might not be exclusive to the bacteriophages examined here.

Vertically Aligned and Ordered One-Dimensional Mesoscale Polyaniline.

The growth of vertically aligned and ordered polyaniline nanofilaments is controlled by potentiostatic polymerization through hexagonally packed and oriented mesoporous silica films. In such small pore template (2 nm in diameter), quasi-single PANI chains are likely to be produced. From chronoamperometric experiments and using films of various thicknesses (100-200 nm) it is possible to evidence the electropolymerization transients, wherein each stage of polymerization (induction period, growth, and overgrowth of polyaniline on mesoporous silica films) is clearly identified. The advantageous effect of mesostructured silica thin films as hard templates for the generation of isolated polyaniline nanofilaments is demonstrated from enhancement of the reversibility between the conductive and the nonconductive states of polyaniline and the higher electroactive surface areas displayed for all mesoporous silica/PANI composites. The possibility to control and tailor the growth of conducting polymer nanofilaments offers numerous opportunities for applications in various fields including energy, sensors and biosensors, photovoltaics, nanophotonics, or nanoelectronics.

Kinetics of the electrochemically-assisted deposition of sol-gel films.

Electrochemically-assisted deposition is now becoming a widespread method for preparing sol-gel films. It is based on the electrochemical generation of OH- ions, which can then catalyze the sol-gel condensation reactions. It has a key advantage of selectively facilitating the film deposition on electrochemically active surfaces while not affecting the stability of the bulk precursor solution. Experimental studies have clearly shown that the thickness of the electrochemically-assisted deposited films is influenced by the deposition parameters such as the potential and time. However, there is still a lack of quantitative description of the kinetics of film growth due to the complexity of the process. In this preliminary study, we derived quantitative analytical expressions for describing the kinetics associated with the growth of sol-gel films generated by electrochemically assisted deposition. Both heterogeneous and homogeneous condensation reactions were considered. The key strategy was to simplify the process by separating the electrochemical step of generating OH- ions with the condensation steps of film formation under approximation. Furthermore, numerical simulation was carried out to examine the validity and any errors in the analytical expressions in the cases when the required approximations were not fulfilled. The analytical expressions could well explain the trends observed in the experimental studies and could also be used for fitting the experimental results from the literature. This study provides a deeper understanding of the mechanism and quantitative guidance for manipulating electrochemically-assisted deposition processes at a large scale in industry. It may also be referred to in regard to other indirect electrodeposition systems in which the deposition is not an electrochemical step but is instead driven by electrochemically-generated catalysts.