Electrochemical Tip-Enhanced Raman Spectroscopy for the Elucidation of Complex Electrochemical Reactions.

Tip-enhanced Raman spectroscopy (TERS) is an emerging nanospectroscopy technique whose implementation in situ/operando, namely, in the liquid phase and under electrochemical polarization (EC-TERS), remains challenging. The investigation of electrochemical processes at the nanoscale, in real time and over wide potential windows can be of particular interest but tedious when using EC-STM-TERS. This approach was successfully applied to the investigation of a well-established but yet complex system (a thiolated nitrobenzene derivative 4-NBM) whose reduction mechanism involves various multistep reaction paths, most likely pH-dependent. In light of the EC-TERS analysis carried out under specific conditions limiting the full (6 e-/6 H+) electrochemical reduction of 4-NBM and its photocoupling, a bimolecular electrochemical reaction path, difficult to evidence from the electrochemical response only, is proposed.

Confining calcium oxalate crystal growth in a carbonated apatite-coated microfluidic channel to better understand the role of Randall's plaque in kidney stone formation.

Effective prevention of recurrent kidney stone disease requires the understanding of the mechanisms of its formation. Numerous in vivo observations have demonstrated that a large number of pathological calcium oxalate kidney stones develop on an apatitic calcium phosphate deposit, known as Randall's plaque. In an attempt to understand the role of the inorganic hydroxyapatite phase in the formation and habits of calcium oxalates, we confined their growth under dynamic physicochemical and flow conditions in a reversible microfluidic channel coated with hydroxyapatite. Using multi-scale characterization techniques including scanning electron and Raman microscopy, we showed the successful formation of carbonated hydroxyapatite as found in Randall's plaque. This was possible due to a new two-step flow seed-mediated growth strategy which allowed us to coat the channel with carbonated hydroxyapatite. Precipitation of calcium oxalates under laminar flow from supersaturated solutions of oxalate and calcium ions showed that the formation of crystals is a substrate and time dependent complex process where diffusion of oxalate ions to the surface of carbonated hydroxyapatite and the solubility of the latter are among the most important steps for the formation of calcium oxalate crystals. Indeed when an oxalate solution was flushed for 24 h, dissolution of the apatite layer and formation of calcium carbonate calcite crystals occurred which seems to promote calcium oxalate crystal formation. Such a growth route has never been observed in vivo in the context of kidney stones. Under our experimental conditions, our results do not show any direct promoting role of carbonated hydroxyapatite in the formation of calcium oxalate crystals, consolidating therefore the important role that macromolecules can play in the process of nucleation and growth of calcium oxalate crystals on Randall's plaque.

Chemical characterization of inks in skin reactions to tattoo.

Skin reactions are well described complications of tattooing, usually provoked by red inks. Chemical characterizations of these inks are usually based on limited subjects and techniques. This study aimed to determine the organic and inorganic composition of inks using X-ray fluorescence spectroscopy (XRF), X-ray absorption spectroscopy (XANES) and Raman spectroscopy, in a cohort of patients with cutaneous hypersensitivity reactions to tattoo. A retrospective multicenter study was performed, including 15 patients diagnosed with skin reactions to tattoos. Almost half of these patients developed skin reactions on black inks. XRF identified known allergenic metals - titanium, chromium, manganese, nickel and copper - in almost all cases. XANES spectroscopy distinguished zinc and iron present in ink from these elements in endogenous biomolecules. Raman spectroscopy showed the presence of both reported (azo pigments, quinacridone) and unreported (carbon black, phtalocyanine) putative organic sensitizer compounds, and also defined the phase in which Ti was engaged. To the best of the authors' knowledge, this paper reports the largest cohort of skin hypersensitivity reactions analyzed by multiple complementary techniques. With almost half the patients presenting skin reaction on black tattoo, the study suggests that black modern inks should also be considered to provoke skin reactions, probably because of the common association of carbon black with potential allergenic metals within these inks. Analysis of more skin reactions to tattoos is needed to identify the relevant chemical compounds and help render tattoo ink composition safer.

Crystalline structures of L-cysteine and L-cystine: a combined theoretical and experimental characterization.

It is assumed that genetic diseases affecting the metabolism of cysteine and the kidney function lead to two different kinds of pathologies, namely cystinuria and cystinosis whereby generate L-cystine crystals. Recently, the presence of L-cysteine crystal has been underlined in the case of cystinosis. Interestingly, it can be strikingly seen that cystine ([-S-CH2-CH-(NH2)-COOH]2) consists of two cysteine (C3H7NO2S) molecules connected by a disulfide (S-S) bond. Therefore, the study of cystine and cysteine is important for providing a better understanding of cystinuria and cystinosis. In this paper, we elucidate the discrepancy between L-cystine and L-cysteine by investigating the theoretical and experimental infrared spectra (IR), X-ray diffraction (XRD) as well as Raman spectra aiming to obtain a better characterization of abnormal deposits related to these two genetic pathologies.

Advances in the identification of calcium carbonate urinary crystals.

The examination of the urinary sediment of a 64-year-old woman showed the presence of three different types of crystals, all with unusual morphology, which could not be identified with bright field microscopy, polarized light, and the knowledge of urine pH (7.5). The use of microscopic infrared spectroscopy, Raman spectroscopy and energy dispersive X-ray spectroscopy led to the identification of the three types of crystals as calcite, vaterite and aragonite, which are all variants of calcium carbonate crystals. This paper confirms the complex morphology and nature that urinary crystals may at times have and the utility of advanced infrared spectroscopy techniques for their identification.

Two-photon optical imaging, spectral and fluorescence lifetime analysis to discriminate urothelial carcinoma grades.

In the framework of urologic oncology, mini-invasive procedures have increased in the last few decades particularly for urothelial carcinoma. One of the essential elements in the management of this disease is still the diagnosis, which strongly influences the choice of treatment. The histopathologic evaluation of the tumor grade is a keystone of diagnosis, and tumor characterization is not possible with just a macroscopic evaluation. Even today intraoperative evaluation remains difficult despite the emergence of new technologies which use exogenous fluorophore. This study assessed an optical multimodal technique based on endogenous fluorescence, combining qualitative and quantitative analysis, for the diagnostic of urothelial carcinoma. It was found that the combination of two-photon fluorescence, second harmonic generation microscopy, spectral analysis and fluorescence lifetime imaging were all able to discriminate tumor from healthy tissue, and to determine the grade of tumors. Spectral analysis of fluorescence intensity and the redox ratio used as quantitative evaluations showed statistical differences between low-grade and high-grade tumors. These results showed that multimodal optical analysis is a promising technology for the development of an optical fiber setup designed for an intraoperative diagnosis of urothelial carcinoma in the area of endo-urology.

A Rotaxane Scaffold Bearing Multiple Redox Centers: Synthesis, Surface Modification and Electrochemical Properties.

A rotaxane scaffold incorporating two dithiolane anchoring units for the modification of gold surfaces has been functionalized with multiple copies of a redox unit, namely ferrocene. Surface modification has been first assessed at the single molecule level by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) imaging, while tip enhanced Raman spectroscopy (TERS) provided the local vibrational signature of the ferrocenyl subunits of the rotaxanes grafted onto the gold surface. Finally, oxidation of the redox moieties within a rotaxane scaffold grafted onto gold microelectrodes has been investigated by ultrafast cyclic voltammetry. Intramolecular electron hopping is indeed extremely fast in this system. Moreover, the kinetics of charge injection depends on the molecular coverage due to the influence of intermolecular contacts on molecular motions.

Tunable SERS Platforms from Small Nanoparticle 3D Superlattices: A Comparison between Gold, Silver, and Copper.

Herein we present new substrates for surface-enhanced Raman spectroscopy (SERS). The synthesis of colloidal nanoparticles through an organometallic route allowed us to obtain gold, silver, or copper nanoparticles with well-controlled shapes and sizes (5-12 nm in diameter). The organization of these nanoparticles into large-scale 3D superlattices produces a very large number of "hot spots" at the origin of the signal enhancement. Each superlattice was studied individually to correlate its optical and SERS properties to the thickness, the nanoparticle sizes, and the interparticle distance. This experimental and theoretical study provides insights for the optimization and tuning of the SERS activity. Indeed, significant SERS amplification could be observed regardless of the nature of the metal. In addition, the SERS signal was homogeneous at the surface of the superlattices, which opens the route for a new approach in analytical SERS detection.

Complex Electron Transfer Pathway at a Microelectrode Captured by in Situ Nanospectroscopy.

In the quest for analytical tools which enable the characterization of materials at the nanoscale and under the condition of their operation (in situ, operando), the emerging tip-enhanced Raman spectroscopy (TERS) now enters the spotlight. We demonstrate in this work that a TERS tip can be functionalized and partially insulated to be used as a microelectrode enabling electrochemical substrate enhanced Raman sectroscopy (EC-SERS) at a single hotspot. This "SERS at a tip" experiment enables one to capture the electrochemical transformation of a molecular layer self-assembled on a tapered gold microelectrode. The proposed setup and protocol open new perspectives in the characterization and development of complex redox architectures for molecular devices.

A Dendritic Nanostructured Copper Oxide Electrocatalyst for the Oxygen Evolution Reaction.

To use water as the source of electrons for proton or CO2 reduction within electrocatalytic devices, catalysts are required for facilitating the proton-coupled multi-electron oxygen evolution reaction (OER, 2 H2 O→O2 +4 H+ +4 e- ). These catalysts, ideally based on cheap and earth abundant metals, have to display high activity at low overpotential and good stability and selectivity. While numerous examples of Co, Mn, and Ni catalysts were recently reported for water oxidation, only few examples were reported using copper, despite promising efficiencies. A rationally designed nanostructured copper/copper oxide electrocatalyst for OER is presented. This material derives from conductive copper foam passivated by a copper oxide layer and further nanostructured by electrodeposition of CuO nanoparticles. The generated electrodes are highly efficient for catalyzing selective water oxidation to dioxygen with an overpotential of 290 mV at 10 mA cm-2 in 1 m NaOH solution.

Facile and Green Reduction of Graphene Oxide by a Reduced Polyoxometalate and Formation of a Nanohybrid.

An ecofriendly chemical reduction of graphene oxide (GO) in water is reported. The reducing agent is an electrochemically reduced Keggin-type polyoxometalate (SiW12 O40 5- ). Moreover, this process leads to the fabrication of SiW12 @rGO nanocomposite. This nanohybrid exhibits an electrochemical response which combines high faradic and capacitive currents due to high coverage of polyoxometalates on the rGO sheets. Therefore this material has strong potentiality for energy storage.

Correlating humidity-dependent ionically conductive surface area with transport phenomena in proton-exchange membranes.

The objective of this effort was to correlate the local surface ionic conductance of a Nafion 212 proton-exchange membrane with its bulk and interfacial transport properties as a function of water content. Both macroscopic and microscopic proton conductivities were investigated at different relative humidity levels, using direct-current voltammetry and current-sensing atomic force microscopy (CSAFM). We were able to identify small ion-conducting domains that grew with humidity at the surface of the membrane. Numerical analysis of the surface ionic conductance images recorded at various relative humidity levels helped determine the fractional area of ion-conducting active sites. A simple square-root relationship between the fractional conducting area and observed interfacial mass-transport resistance was established. Furthermore, the relationship between the bulk ionic conductivity and surface ionic conductance pattern of the Nafion membrane was examined.

The interaction of Li+ with single-layer and few-layer graphene.

The interaction of Li(+) with single and few layer graphene is reported. In situ Raman spectra were collected during the electrochemical lithiation of the single- and few-layer graphene. While the interaction of lithium with few layer graphene seems to resemble that of graphite, single layer graphene behaves very differently. The amount of lithium absorbed on single layer graphene seems to be greatly reduced due to repulsion forces between Li(+) at both sides of the graphene layer.