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.

Clicked BODIPY-Fullerene-Peptide Assemblies: Studies of Electron Transfer Processes in Self-Assembled Monolayers on Gold Surfaces.

Two BODIPY-C60 -peptide assemblies were synthesized by CuAAC reactions of BODIPY-C60 dyads and a helical peptide functionalized with a terminal alkyne group and an azide group, respectively. The helical peptide within these assemblies was functionalized at its other end by a disulfide group, allowing formation of self-assembled monolayers (SAMs) on gold surfaces. Characterizations of these SAMs, as well as those of reference molecules (BODIPY-C60 -alkyl, C60 -peptide and BODIPY-peptide), were carried out by PM-IRRAS and cyclic voltammetry. BODIPY-C60 -peptide SAMs are more densely packed than BODIPY-C60 -alkyl and BODIPY-peptide based SAMs. These findings were attributed to the rigid peptide helical conformation along with peptide-peptide and C60 -C60 interactions within the monolayers. However, less dense monolayers were obtained with the target assemblies compared to the C60 -peptide, as the BODIPY entity likely disrupts organization within the monolayers. Finally, electron transfer kinetics measurements by ultra-fast electrochemistry experiments demonstrated that the helical peptide is a better electron mediator in comparison to alkyl chains. This property was exploited along with those of the BODIPY-C60 dyads in a photo-current generation experiment by converting the resulting excited and/or charge separated states from photo-illumination of the dyad into electrical energy.

Voltammetric techniques for low-cost on-site routine analysis of thymol in the medicinal plant Ocimum gratissimum.

The composition of essential oils varies according to culture conditions and climate, which induces a need for simple and inexpensive characterization methods close to the place of extraction. This appears particularly important for developing countries. Herein, we develop an analytical strategy to determine the thymol content in Ocimum Gratissimum, a medicinal plant from Benin. The protocol is based on electrochemical techniques (cyclic and square wave voltammetry) implemented with a low cost potentiostat. Thymol is a phenol derivative and was directly oxidized at the electrode surface. We had to resort to submillimolar concentrations (25-300 µM) in order to minimize production of phenol oligomers that passivate the electrode. We worked first on two essential oils and realized that in one of them the thymol concentration was below our detection method. These results were confirmed by gas chromatography - mass spectrometry. Furthermore, we optimized the detection protocol to analyze an infusion made directly from the leaves of the plant. Finally, we studied whether the cost of the electrochemical cell may also be minimized by using pencil lead as working and counter electrodes.

Highly Reactive Diazenyl Radical Species Evidenced during Aryldiazonium Electroreduction.

We report the experimental reassessment of the widely admitted concerted reduction mechanism for diazonium electroreduction. Ultrafast cyclic voltammetry was exploited to demonstrate the existence of a stepwise pathway, and real-time spectroelectrochemistry experiments allowed visualization of the spectral signature of an evolution product of the phenyldiazenyl radical intermediate. Unambiguous identification of the diazenyl species was achieved by radical trapping followed by X-ray structure resolution. The electrochemical generation of this transient under intermediate energetic conditions calls into question our comprehension of the layer structuration when surface modification is achieved via the diazonium electrografting technique as this azo-containing intermediate could be responsible for the systematic presence of azo bridges in nanometric films.

Enlightening the Alkali Ion Role in the Photomagnetic Effect of FeCo Prussian Blue Analogues.

FeCo Prussian blue analogues of general formula AxCoy[Fe(CN)6]z are responsive, non-stoichiometric materials whose magnetic and optical properties can be reversibly switched by light irradiation. However, elucidating the critical influence of the inserted alkali ion, A+, on the material's properties remains complicated due to their complex local structure. Here, by investigating soluble A ⊂ [Fe4-Co4] cyanido cubes (A = K, Rb, and Cs), both accurate structural and electronic information could be obtained. First, X-ray diffraction analyses reveal distinct interactions between the inserted A+ ions and the {Fe4-Co4} box, which impacts the structural distortion in the cubic framework. These distortions vanish, and a displacement of the small K+ ion from a corner toward the center is observed, as a cobalt corner CoIIHS is oxidized to CoIIILS. Second, cyclic voltammetry experiments performed at variable temperatures show distinct splitting of the CoIIHS ⇔ CoIIILS peak potentials for the different A+ cations, which can be qualitatively linked to different thermodynamic (standard potentials) and kinetic (energy barriers) parameters associated with the structural reorganization accompanying this redox-coupled spin state change. Moreover, for the first time, photomagnetism was investigated in frozen solution to avoid effects of intermolecular interactions. The results show that the metastable state is stabilized following the trend K > Rb > Cs. The outcome of these studies suggests that the interaction of the inserted alkali ions with the cyanide cage and the structural changes accompanying the electron transfer impact the stability of the photoinduced state and the relaxation temperature: the smaller the cation, the higher the structural reorganization and the associated energy barrier, and the more stable the metastable state.

PassStat, a simple but fast, precise and versatile open source potentiostat.

This work presents 4 open source potentiostat solutions for performing accurate measurements in cyclic voltammetry and square wave voltammetry at a low price. A very simple and easy to reproduce analogic board (c.a. 10 €) was driven either by a Teensy card from the company PJRC under an Arduino/Python software solution (39 €) or by an Analog Discovery 2 device from Digilent (less than 300 €). A smartphone Bluetooth Android interface was also created to circumvent the use of a computer. We demonstrated that our scheme is suitable for measurements in classical electrochemical conditions but also to carry out experiments with ultramicroelectrodes. We could thus reach a noise resolution of less than 1 pA. Scan rates of 8000 Vs-1 with ohmic drop compensation were also achieved. The device is suitable for teaching purposes but also for experiments in a participative science context on the ground, or countries with lower financial possibilities.

Janus-type homo-, hetero- and mixed valence-bimetallic complexes with one metal encapsulated in a cyclodextrin.

Bis-azolium salts with one azolium capping a perbenzylated α-cyclodextrin have been designed to generate Janus-type bimetallic complexes with various combinations of copper, silver, gold or palladium salts. Encapsulation of one metal center inside the cavity allowed (trans)metalation and oxidation reactions to be controlled at selected positions. In particular, it was possible to oxidize AuI into AuIII selectively on the position outside the cavity of the cyclodextrin on the bis-AuI Janus complex.

Embedding Collagen in Multilayers for Enzyme-Assisted Mineralization: A Promising Way to Direct Crystallization in Confinement.

The biogenic calcium phosphate (CaP) crystallization is a process that offers elegant materials design strategies to achieve bioactive and biomechanical challenges. Indeed, many biomimetic approaches have been developed for this process in order to produce mineralized structures with controlled crystallinity and shape. Herein, we propose an advanced biomimetic approach for the design of ordered hybrid mineralized nano-objects with highly anisotropic features. For this purpose, we explore the combination of three key concepts in biomineralization that provide a unique environment to control CaP nucleation and growth: (i) self-assembly and self-organization of biomacromolecules, (ii) enzymatic heterogeneous catalysis, and (iii) mineralization in confinement. We use track-etched templates that display a high density of aligned monodisperse pores so that each nanopore may serve as a miniaturized mineralization bioreactor. We enhance the control of the crystallization in these systems by coassembling type I collagen and enzymes within the nanopores, which allows us to tune the main characteristics of the mineralized nano-objects. Indeed, the synergy between the gradual release of one of the mineral ion precursors by the enzyme and the role of the collagen in the regulation of the mineralization allowed to control their morphology, chemical composition, crystal phase, and mechanical stability. Moreover, we provide clear insight into the prominent role of collagen in the mineralization process in confinement. In the absence of collagen, the fraction of crystalline nano-objects increases to the detriment of amorphous ones when increasing the degree of confinement. By contrast, the presence of collagen-based multilayers disturbs the influence of confinement on the mineralization: platelet-like crystalline hydroxyapatite form, independently of the degree of confinement. This suggests that the incorporation of collagen is an efficient way to supplement the lack of confinement while reinforcing mechanical stability to the highly anisotropic materials. From a bioengineering perspective, this biomineralization-inspired approach opens up new horizons for the design of anisotropic mineralized nano-objects that are highly sought after to develop biomaterials or tend to replicate the complex structure of native mineralized extracellular matrices.

The Fermi level as an energy reference in liquid jet X-ray photoelectron spectroscopy studies of aqueous solutions.

To advance the understanding of key electrochemical and photocatalytic processes that depend on the electronic structure of aqueous solutions, X-ray photoemission spectroscopy has become an invaluable tool, especially when practiced with liquid microjet setups. Determining vertical ionization energies referenced to the vacuum level, and binding energies referenced to the Fermi level, including the much-coveted reorganization energy of the oxidized species of a redox couple, requires that energy levels be properly defined. The present paper addresses specifically how the vacuum level "just outside the surface" can be known through the energy position of the rising edge of the secondary electrons, and how the Fermi level reference is uniquely determined via the introduction of a redox couple. Taking the case of the ferricyanide/ferrocyanide and ferric/ferrous couples, this study also tackles issues related to the electrokinetic effects inherent to the production of a liquid jet in a vacuum, which has become the standard water sample environment for photoemission experiments.

Hierarchical Collagen-Hydroxyapatite Nanostructures Designed through Layer-by-Layer Assembly of Crystal-Decorated Fibrils.

A comprehensive understanding of the mechanism by which type I collagen (Col) interacts with hydroxyapatite nanoparticles (Hap NPs) in aqueous solutions is a pivotal step for guiding the design of biologically relevant nanocomposites with controlled hierarchical structure. In this paper we use a variety of Hap NPs differing by their shape (rod vs platelet) and their size (∼30 vs ∼130 nm) and investigate their mechanism(s) of interaction with collagen. The addition of collagen to the Hap suspensions induces different effects that strongly depend on the nanoparticle type. Interestingly, the use of small rods, typically with ∼30 nm of length (R30), leads to the formation of assembled collagen fibrils decorated with Hap nanocrystals which, in turn, self-assemble progressively to form larger fibrillar Hap-Col composite. The crystals decorating collagen provide "intrinsic" negative charges to the fibrillar objects that allow their incorporation in three-dimensional structure using layer-by-layer (LbL) assembly. This offers a straightforward way to construct a collagen-based hybrid material with well-defined hierarchy under near-physiological conditions. In situ, QCM-D monitoring revealed the buildup of soft and highly hydrated hybrid (PAH/R30-Col)n multilayers for which the mechanism of growth was very different from that observed for polyelectrolytes and nanoparticles without collagen (PAH/R30). The LbL assembly of crystal-decorated collagen yields a hierarchical nanostructured film whose thickness and roughness can be modulated by the addition of salt and incorporate fibrillar objects of about 400 nm in width and few micrometers in length, as probed by AFM. The approach described in this work provides a relevant way to better control the (supra)molecular assembly of Col and Hap NPs with the perspective of developing hierarchical Hap-Col nanocomposites with tuned properties for various biomedical applications.

Light Driven Design of Dynamical Thermosensitive Plasmonic Superstructures: A Bottom-Up Approach Using Silver Supercrystals.

When narrowly distributed silver nanoparticles (NPs) are functionalized by dodecanethiol, they acquire the ability to self-organize in organic solvents into 3D supercrystals (SCs). The NP surface chemistry is shown to introduce a light-driven thermomigration effect, thermophoresis. Using a laser beam to heat the NPs and generate steep thermal gradients, the migration effect is triggered dynamically, leading to tailored structures with high density of plasmonic hot spots. This work describes how to manipulate the hot spots and monitor the effect by holography, thus providing a complete characterization of the migration process on a single object basis. Extensive single object tracking strategies are employed to measure the SCs trajectories, evaluate their size, drift velocity magnitude and direction, allowing the identification of the physical chemical origins of the migration. The phenomenon is shown to happen as a result of the combination of thermophoresis (at short length scales) and convection (long-range), and does not require a metallic substrate. This constitutes a fully optical method to dynamically generate plasmonic platforms in situ and on demand, without requiring substrate nanostructuration and with minimal interference on the chemistry of the system. The importance of the proof-of-concept herein described stems from the numerous potential applications, spanning over a variety of fields such as microfluidics and biosensing.

Twisted N-Doped Nano-Graphenes: Synthesis, Characterization, and Resolution.

Two diastereoisomeric N-doped nanographene derivatives have been efficiently prepared in two synthetic steps starting from an ethynylated hexaazatriphenylene building block. The first derivative adopts a D3 -symmetrical propeller-shaped structure with three equivalent nanographene foils. The structure of the second diastereoisomer is C2 -symmetrical and differs from the first one by the way two peripheral nanographene foils overlap. Owing to their intertwined structures, the two N-doped nanographenes are soluble in organic solvents and could be characterized by a combination of several analytical tools. Resolution of the D3 -symmetrical derivative has been achieved and CD measurements revealed extremely strong Cotton effects.

Photoactive Molecular Dyads [Ru(bpy)3-M(ttpy)2] n+ on Gold (M = Co(III), Zn(II)): Characterization, Intrawire Electron Transfer, and Photoelectric Conversion.

We propose in this work a stepwise approach to construct photoelectrodes. This takes advantage of the self-assembly interactions between thiol with a gold surface and terpyridine ligands with first-row transition metals. Here, a [Ru(bpy)3]2+ photosensitive center bearing a free terpyridine group has been used to construct two linear dyads on gold (Au/[ZnII-RuII]4+ and Au/[CoIII-RuII]5+). The stepwise construction was characterized by electrochemistry, quartz crystal microbalance, and atomic force microscopy imaging. The results show that the dyads behave as rigid layers and are inhomogeneously distributed on the surface. The surface coverages are estimated to be in the order of 10-11 mol cm-2. The kinetics of the heterogeneous electron transfer is determined on modified gold ball microelectrodes using Laviron's formula. The oxidation rates of the terminal Ru(II) subunits are estimated to be 700 and 2300 s-1 for Au/[ZnII-RuII]4+ and Au/[CoIII-RuII]5+, respectively. In the latter case, the rate is limited by the kinetics of electron transfer between an intermediate Co(II) center and the gold surface. For Au/[ZnII-RuII]4+, the Zn-bis-terpyridine center is not involved in the electron-transfer process and the oxidation of the Ru(II) subunit occurs through a superexchange process. In the presence of a tertiary amine in solution, the electrodes at a bias of 0.12 V behave as photoanodes when subjected to visible light irradiation. The magnitude of the photocurrent is around 10 µA cm-2 for Au/[CoIII-RuII]5+ and 5 µA cm-2 for Au/[ZnII-RuII]4+, proving the importance of an electron relay on the photon-to-current conversion. The results suggest an efficient conversion for Au/[CoIII-RuII]5+, since each bound dyad, once excited, injects an electron around 10 times per second.

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.

A Rotaxane Scaffold for the Construction of Multiporphyrinic Light-Harvesting Devices.

A sophisticated photoactive molecular device has been prepared by combining recent concepts for the preparation of multifunctional nanomolecules (click chemistry on multifunctional scaffolds) with supramolecular chemistry (self-assembly to prepare rotaxanes). Specifically, a clickable [2]rotaxane scaffold incorporating a free-base porphyrin stopper has been prepared and functionalized with ten peripheral Zn(II)-porphyrin moieties. Electrochemical investigations of the final compound revealed a peculiar behavior resulting from the intramolecular coordination of the Zn(II) porphyrin moieties to 1,2,3-triazole units. Finally, steady state investigations of the compound combining Zn(II) and free-base porphyrin moieties have shown that this compound is a light-harvesting device capable of channeling the light energy from the peripheral Zn(II)-porphyrin subunits to the core by singlet-singlet energy transfer.

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.

Coordination-Driven Folding in Multi-ZnII -Porphyrin Arrays Constructed on a Pillar[5]arene Scaffold.

Pillar[5]arene derivatives bearing peripheral porphyrin subunits have been efficiently prepared from a deca-azide pillar[5]arene building block (17) and ZnII -porphyrin derivatives bearing a terminal alkyne function (9 and 16). For the resulting deca-ZnII -porphyrin arrays (18 and 20), variable temperature NMR studies revealed an intramolecular complexation of the peripheral ZnII -porphyrin moieties by 1,2,3-triazole subunits. As a result, the molecules adopt a folded conformation. This was further confirmed by UV/Vis spectroscopy and cyclic voltammetry. In addition, we have also demonstrated that the coordination-driven unfolding of 18 and 20 can be controlled by an external chemical stimulus. Specifically, addition of an imidazole derivative (22) to solution of 18 or 20 breaks the intramolecular coordination at the origin of the folding. The resulting molecular motions triggered by the addition of the imidazole ligand mimic the blooming of a flower.

Determination of the isomeric forms proportion of fluorogenic naphthalene-2,3-dicarboxaldehyde in a binary mixture of water:methanol using electrochemical methods.

The electrochemical response of the fluorogenic label naphthalene-2,3-dicarboxyaldehyde (NDA) in a binary mixture of water/methanol was characterized with cyclic voltammetry (CV) and differential pulse voltammetry (DPV) electrochemical techniques. Naphthalene-2,3-dicarboxyaldehyde does exist in three isomeric forms in aqueous solution: the unhydrated dialdehyde (DA), the acyclic monohydrated (MA) and the cyclic hemiacetal (HAC). The study underlines that the proportion of each of them varies according to the working pH. At low and high pH, the dialdehyde form is in larger proportion than the acyclic monohydrated form. Conversely at intermediate pH, the concentration of the acyclic form is in greater proportion than the dialdehyde form. These results allowed us to determine the optimal pH of 9 for which the labeling of biomolecules could be more efficient due to the base catalyzed regeneration of the unhydrated form. At this pH, the data processing from the analysis of measured currents and estimation of diffusion coefficients of each form according to the semi-empirical models of Wilke-Chang, Scheibel, Reddy-Doraiswamy and Lusis-Ratcliff allowed us to obtain the concentration of dialdehyde (0.28 mM), acyclic monohydrated (0.57 mM) and cyclic hemiacetal monohydrated (0.15 mM) forms starting from 1mM naphthalene-2,3-dicarboxyaldehyde.

Copper nanoparticles of well-controlled size and shape: a new advance in synthesis and self-organization.

Here, we report a new synthetic route for spherical small copper nanoparticles (CuNPs) with size ranging from 3.5 nm to 11 nm and with an unprecedented associated monodispersity (<10%). This synthesis is based on the reduction of an organometallic precursor (CuCl(PPh3)3) by tert-butylamine borane in the presence of dodecylamine (DDA) at a moderate temperature (50 to 100 °C). Because of their narrow size distribution, the CuNPs form long-range 2D organizations (several µm(2)). The wide range of CuNPs sizes is obtained by controlling the reaction temperature and DDA-to-copper phosphine salt ratio during the synthesis process. The addition of oleic acid (OA) after the synthesis stabilizes the CuNPs (no coalescence) for several weeks under a nitrogen atmosphere. The nature and the reactivity of the ligands were studied by IR and UV-visible spectroscopy. We thus show that just after synthesis the nanoparticles are coated by phosphine and DDA. After adding OA, a clear exchange between phosphine and OA is evidenced. This exchange is possible thanks to an acid-base reaction between the free alkylamine in excess in the solution and OA. OA is then adsorbed on the NPs surface in the form of carboxylate. Furthermore, the use of oleylamine (OYA) instead of DDA as the capping agent allows one to obtain other NP shapes (nanorods, triangles and nanodisks). We get evidence that OYA allows the selective adsorption of chloride ions derived from the copper precursor on the different crystallographic faces during the growth of CuNPs that induces the formation of anisotropic shapes such nanorods or triangles.