An innovative method for controlled synthesis of bicomponent monolayer films obtained by reduction of diazonium.

This study presents a novel method based on the electrochemical co-reduction of two aryldiazonium salts, enabling the synthesis of controlled two-component monolayer thin films on carbon in a single step. By introducing a 12-carbon alkyl chain as a spacer between the aryldiazonium function and the functional group, precise control over film thickness and composition was achieved. The alkyl chain effectively standardizes the reduction potential, enabling the equalization of reactivity and precise stoichiometric control. Experimental results from spectroscopic, electrochemical, and X-ray photoelectron spectroscopy analyses validate the effectiveness of the method in controlling the composition of the mixed layers.

Microorganisms that produce enzymes active on biodegradable polyesters are ubiquitous.

Biodegradability standards measure ultimate biodegradation of polymers by exposing the material under test to a natural microbial inoculum. Available tests developed by the International Organization for Standardization (ISO) use inoculums sampled from different environments e.g. soil, marine sediments, seawater. Understanding whether each inoculum is to be considered as microbially unique or not can be relevant for the interpretation of tests results. In this review, we address this question by consideration of the following: (i) the chemical nature of biodegradable plastics (virtually all biodegradable plastics are polyesters) (ii) the diffusion of ester bonds in nature both in simple molecules and in polymers (ubiquitous); (iii) the diffusion of decomposers capable of producing enzymes, called esterases, which accelerate the hydrolysis of esters, including polyesters (ubiquitous); (iv) the evidence showing that synthetic polyesters can be depolymerized by esterases (large and growing); (v) the evidence showing that these esterases are ubiquitous (growing and confirmed by bioinformatics studies). By combining the relevant available facts it can be concluded that if a certain polyester shows ultimate biodegradation when exposed to a natural inoculum, it can be considered biodegradable and need not be retested using other inoculums. Obviously, if the polymer does not show ultimate biodegradation it must be considered recalcitrant, until proven otherwise.

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.

No more compromise: a facile route towards functionalized surfaces with stable monolayers.

The results reported in this study clearly show that it is possible to easily control the formation of a functional monolayer by spontaneous reduction of an aryldiazonium salt on gold in a single step, mimicking the SAM technique.

Use of Selective Redox Cross-Inhibitors for the Control of Organic Layer Formation Obtained via Diazonium Salt Reduction.

The controlled electrochemical deposition of a series of four diazonium salts (4-bromobenzene, 4-iodobenzene, 4-methoxybenzene, and 4-diethylaminobenzene diazonium) on carbon surfaces has been achieved by exploiting the use of three redox mediators: 2,2-diphenyl-1-picrylhydrazyl, chloranil, and dichlone. The efficiency of the method rests on a fast redox cross-reaction in the diffusion layer between the diazonium compound and the reduced form of the selected inhibitor, characterized by an outer-sphere electron transfer. The effect of the inhibitor addition in the deposition solution was characterized using electrochemical techniques, X-ray photoelectron spectroscopy, and atomic force microscopy. Near-monolayers are obtained when the potential of the redox mediator is at least 100 mV lower than the reduction potential of the diazonium salt concerned. A judicious choice of the redox entity can allow, via a fine control of the experimental conditions, to modulate the thickness of organic layers by varying the grafting potential.

Supramolecular chemistry of helical foldamers at the solid-liquid interface: self-assembled monolayers and anion recognition.

The synthesis of a redox-active helical foldamer and its immobilization onto a gold electrode are described. These large molecular architectures are grafted in a reproducible manner and provide foldamer-based self-assembled monolayers displaying recognition properties.

Controlled diazonium electrografting driven by overpotential reduction: a general strategy to prepare ultrathin layers.

A global and extremely simple strategy to prepare a covalently attached monolayered organic film on a carbon surface is presented. The approach is centered on the strict control of the radical polymerization traditionally observed when aryldiazonium salts are reduced. By exploiting the reductive properties of superoxide ions generated from atmospheric dioxygen at the grafting potential, the diazonium concentration is drastically lowered at the substrate/solution interface, resulting in the formation of ultrathin films. As the presented approach does not require any specific synthesis or any redox mediator addition, and is only diffusion controlled by the dissolved dioxygen, it is suitable for the preparation of a large range of functional surfaces on the nanometric scale.

Click Chemistry: A Versatile Method for Tuning the Composition of Mixed Organic Layers Obtained by Reduction of Diazonium Cations.

Postfunctionalization of glassy carbon electrodes previously modified by reduction of 4-azidobenzenediazonium was exploited to conveniently synthesize controlled mixed organic layers. Huisgen 1,3-dipolar cycloaddition was used to anchor functional entities to azide platform. By this way, ((4-ethynylphenyl)carbamoyl)ferrocene (ϕ-Fc) was coimmobilized with a set of acetylene derivatives: 1-ethynyl-4-nitrobenzene (ϕ-NO2), 4-ethynylaniline (ϕ-NH2) or ethylnylbenzene (ϕ). The composition of the resulting organic layers was tuned by adjusting the acetylene derivatives ratio in the postfunctionalization binary solution. Electronic properties of the substituents beared by the aromatic rings were found to have a strong impact on the cycloaddition kinetics toward the confined azide moieties. From this study, rules to prepare finely tuned bifunctional organic layers can be anticipated.

Very Strong Binding for a Neutral Calix[4]pyrrole Receptor Displaying Positive Allosteric Binding.

The dual-analyte responsive behavior of tetraTTF-calix[4]pyrrole receptor 1 has been shown to complex electron-deficient planar guests in a 2:1 fashion by adopting a so-called 1,3-alternate conformation. However, stronger 1:1 complexes have been demonstrated with tetraalkylammonium halide salts that defer receptor 1 to its cone conformation. Herein, we report the complexation of an electron-deficient planar guest, 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA, 2) that champions the complexation with 1, resulting in a high association constant Ka = 3 × 1010 M-2. The tetrathiafulvalene (TTF) subunits in the tetraTTF-calix[4]pyrrole receptor 1 present a near perfect shape and electronic complementarity to the NTCDA guest, which was confirmed by X-ray crystal structure analysis, DFT calculations, and electron density surface mapping. Moreover, the complexation of these species results in the formation of a charge transfer complex (22⊂1) as visualized by a readily apparent color change from yellow to brown.

Spontaneous assembly of silylethane-thiol derivatives on Au(111): a chemically robust thiol protecting group as the precursor for the direct formation of aromatic gold thiolate monolayers.

Self-assembled monolayers (SAMs) on gold were obtained by the direct absorption of a fully conjugated phenylenethienylene derivative () presenting robust silylethane-thiol protecting groups as anchoring agents. The thiol deprotection and SAM formation have been evidenced by quartz crystal microbalance (QCM) measurements and X-ray photoelectron spectroscopy (XPS), and have been compared to the SAM obtained from its thioacetate analog (5). The chemically robust silylethane-thiol protecting group appeared as a surprisingly effective anchoring agent for the preparation of aromatic SAMs on Au(111), suitable for subsequent post-functionalization.

Spontaneous grafting of nitrophenyl groups on carbon: effect of radical scavenger on organic layer formation.

The effect of a radical scavenger (DPPH: 2,2-diphenyl-1-picrylhydrazyl) on the spontaneous covalent grafting of nitrophenyl functionalities on a vitreous carbon substrate using the 4-nitrobenzene diazonium cation has been studied by electrochemical measurements and X-ray photoelectron spectroscopy. The addition of micromolar concentrations of DPPH to the diazonium solution efficiently limits the multilayer formation and leads to monolayer surface coverage. Control of polyaryl layer formation via the capture of the reactive nitrophenyl radical was also found to increase the proportion of nitrophenyl groups grafted to the surface via azo bridges. This work validates the recently reported strategy using a radical scavenger to prevent the formation of a polyaryl layer without interfering with direct surface grafting.

A facile route to steady redox-modulated nitroxide spin-labeled surfaces based on diazonium chemistry.

A TEMPO derivative was covalently grafted onto carbon and gold surfaces via the diazonium chemistry. The acid-dependent redox properties of the nitroxyl group were exploited to elaborate electro-switchable magnetic surfaces. ESR characterization demonstrated the reversible and permanent magnetic character of the material.

TEMPO mixed SAMs: electrocatalytic efficiency versus surface coverage.

Electrocatalytic behavior of TEMPO derivative SAMs on gold has been studied in the presence of benzyl alcohol. The results demonstrate that interfacial activity of the SAMs can be enhanced by diluting the TEMPO moiety with an alkyl passive matrix. The absolute catalytic activity exhibits a maximum for an intermediate value of the surface coverage of catalytic centers. The most significant feature is the monotonic increase of the turnover (relative activity) until a limit value reached for low TEMPO surface concentrations. The electrocatalytic performances seem to be governed by a combination of two factors: the physical accessibility (by alcohol molecules in solution) and the regeneration (via the comproportionation of oxoammonium and hydroxylamine before electrochemical reoxidation) of the catalytic centers.

Electrochemical transduction on self-assembled monolayers: are covalent links essential?

Electrochemical transduction without covalent links between redox and complexant units in a complexing self-assembled monolayer has been established. The results demonstrate that transduction depends on the crown ether/ferrocene ratio and appears to be tunable.

Intermolecular interactions in self-assembled monolayers of tetrathiafulvalene derivatives.

The elaboration of mixed self-assembled monolayers (SAMs) of tetrathiafulvalene derivatives allows the modulation of intermolecular interactions and provides evidence of segregated distribution of redox centers.

Phase segregation on electroactive self-assembled monolayers: a numerical approach for describing lateral interactions between redox centers.

A numerical method is proposed in order to differentiate a random distribution from a phase segregation of redox centers on (mixed) SAMs. This approach is compared to Laviron's interactions model and voltammetric data of nitroxylalkanethiolate SAMs.

Modification of carbon electrode with aryl groups having an aliphatic amine by electrochemical reduction of in situ generated diazonium cations.

The electrochemically induced functionalization of glassy carbon electrode by aryl groups having an aliphatic amine group was achieved by reduction of in situ generated diazonium cations in aqueous media. The corresponding diazonium cations of 4-aminobenzylamine, 2-aminobenzylamine, 4-(2-aminoethyl)aniline, N-methyl-1,2-phenylenediamine, and N, N-dimethyl- p-phenylenediamine were generated in situ with sodium nitrite in aqueous HCl. The kinetics of electrochemical grafting were investigated with electrochemical impedance spectroscopy and electrochemical quartz crystal microbalance measurements (with carbon-coated quartz crystal), and the barrier properties of the grafted layers were evaluated by cyclic voltammetry in the presence of electroactive redox probes such as Fe(CN)6 3-/4- and Ru(NH 3)6 (3+). The grafting efficiency of aryl groups was found to depend on the nature of the amine (primary, secondary, and tertiary), the chain length of the alkyl substituent, and the substitution position on the aromatic ring. The nitrosation of the "aliphatic" amine, in the case of secondary and tertiary amines, was also evidenced by X-ray photoelectron spectroscopy.