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International audience; The synthesis of five light absorbing triazolobithiophenic thiols, which were utilized for producing self-assembled monolayers (SAMs) on gold surfaces, is presented. The monolayer formation was monitored by cyclic voltammetry, indicating excellent surface coverage. The new triazolobithiophenic compounds exhibited an absorption maximum around 340 nm, which is close to the emission wavelength of a standard nitrogen laser. Consequently these compounds could be used to aid ionization in laser desorption mass spectrometry (MS).

Within the last 25 years, matrix-assisted laser desorption ionization (MALDI) has become a powerful analytical tool in mass spectrometry (MS). While the method has been successfully applied to characterize large organic molecules such as proteins, sugars and polymers, its utilization for small molecules (≤ 600 Da) is significantly impaired by the coformation of matrix ions. Reducing or eliminating matrix-related signals has been subject of many studies. Some of which propose the enhancement of so-called matrix suppression effects, while others suggest the replacement of matrix molecules by materials such as microporous silicon. Alternatively, the immobilization of matrix molecules by utilizing them as self-assembled monolayers (SAMs) has been discussed. In continuation of this research, the current manuscript focuses on the elucidation of ion formation processes occurring on the surface of light absorbing SAMs. Ion yields obtained by free and immobilized matrix molecules as well as those generated by matrix-free gold film-assisted laser desorption ionization (GF-LDI) were compared. Experiments showed that the formation of strong analyte signals essentially required the presence of free matrix molecules, while the immobilization of the latter severely impaired ionization. The observed effect inversely correlated with the surface coverage of SAMs determined by cyclic voltammetry (CV). Based on these findings, the MS signal generated on light absorbing SAMs could be used supplementary to CV for determining the surface coverage of light absorbing SAMs. Copyright © 2011 John Wiley & Sons, Ltd.

The Laviron's interaction model, dedicated to randomly distributed electroactive adsorbed species, was extended to a non-random distribution in order to extract the current–voltage characteristics from any surface distribution of electroactive centers on self-assembled monolayer (SAM). Confronted to electrochemical behaviour of nitroxyl radical SAMs, the agreement observed between theory and experiments provides evidence of a distribution independence of the interaction parameters. Keywords: Tempo, Self-assembled monolayers, Cyclic voltammetry, Interaction model

International audience; A series of diazonium salts bearing different para substituents was used to functionalize glassy carbon (GC) and pyrolyzed photoresist film (PPF) under electrografting conditions in the absence and presence of the radical scavenger diphenyl-1-picrylhydrazyl (DPPH). Depositions were monitored by electrochemical quartz crystal microbalance (EQCM) and the grafted layers were analyzed by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). DPPH was used to selectively suppress film growth by radical coupling and thereby to reveal the existence of secondary mechanisms involved in the polymerization. Differences in grafting behaviors between various diazonium ion derivatives can be explained by the influence of the para substituent’s electronic properties on the electrophilic aromatic substitutions of diazonium ions on already grafted aromatic groups.

Two ferrocene-containing iron(III) chelators were synthesized from desferrioxamine B and kojic acid and their electronic absorption and electrochemical properties were studied in acetonitrile in the absence and presence of ferric ions. The results show a complex behavior arising from the occurrence of competing redox and complexation processes. Such systems are a first step toward the generation of chemosensors for the electrochemical detection of iron(III) in a solution.

The synthesis of tetrakis(tetrathiafulvalene)-annulated metal-free and metallophthalocyanines 5-8 via the tetramerization of the phthalonitrile derivative 4 is reported. All of them have been fully characterized by electronic absorption spectroscopy, thin-layer cyclic voltammetry, mass spectrometry, and elemental analysis. Their solution electrochemical data show two reversible four-electron oxidation waves, indicating that these fused systems are strong pi-electron donors, which give rise to tetra- or octaradical cation species. For the metal-free phthalocyanine 5, additionally a reversible one-electron wave was found in the negative direction arising from the reduction of the macrocycle. Moreover, the tetrathiafulvalene unit acts as an efficient reductive electron-transfer quencher for the phthalocyanine emission, but upon its oxidation, an intense luminescence is switched on.

The 3,5,3′,5′-3H4-2,2′-diphenyleneiodonium cation [3H]-1 was synthesized in three steps from cold 2,2′-diaminodiphenyl. The nitration of [3H]-1 gave easily the 4-nitro derivative [3H]-2. These two compounds which contain four tritium labels were obtained with a high specific activity, and are proposed as tools to study the interaction of 2,2′-diphenyleneiodonium cations with redox enzymes, especially flavoproteins. Copyright © 2000 John Wiley & Sons, Ltd.

Protoporphyrinogen oxidase, the last enzyme of the common branch of the heme and chlorophyll pathways in plants, is the molecular target of diphenyl ether-type herbicides. These compounds inhibit the enzyme competitively with respect to the tetrapyrrole substrate, protoporphyrinogen IX. We used the flavinic nature of protoporphyrinogen oxidase to investigate the reactivity of the enzyme toward the 2,2'-diphenyleneiodonium cation, a known inhibitor of several flavoproteins. Diphenyleneiodonium inhibited the membrane-bound yeast protoporphyrinogen oxidase competitively with molecular oxygen. The typical slow-binding kinetics suggested that the enzyme with a reduced flavin rapidly combined with the inhibitor to form an initial complex which then slowly isomerized to a modified enzyme-inhibitor complex (Ki = 6.75 x 10(-8) M, Ki* = 4.1 x 10(-9) M). This inhibition was strongly pH-dependent and was maximal at pH 8. Substituted diphenyleneiodoniums were synthesized and shown to be even better inhibitors than 2,2'-diphenyleneiodonium: Ki = 4.4 x 10(-8) M and Ki* = 1.3 x 10(-9) M for 4-methyl-2,2'-diphenyleneiodonium, Ki = 2.2 x 10(-8) M and Ki * = 1.1 x 10(-9) M for 6-methyl-2,2'-diphenyleneiodonium, and Ki = 6.4 x 10(-9) M and Ki* = 1.2 x 10(-1)2 M for 4-nitro-2,2'-diphenyleneiodonium. The 4-nitro-2,2'-diphenyleneiodonium was a quasi irreversible inhibitor (k5/k6 > 5000). Diphenyleneiodoniums are a new class of protoporphyrinogen oxidase inhibitors that act via a mechanism very different from that of diphenyl ether-type herbicides and appear to be promising tools for studies on the structure-function relationships of this agronomically important enzyme.

International audience; 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.

The photolysis of l-(2-azido-6-chloropyrid-4-yl)-3-phenylurea (1) was studied under various conditions. In alcohols or in hexane, complex mixtures of products were obtained. Methoxide anions or diethylamine gave rise in high yield to 1,3-diazepines resulting from ring enlargement of the intermediate nitrene with addition of one molecule of the nucleophile, and nucleophilic substitution of the chlorine atom. A similar reaction was observed in water, when Pyrex filtered light was used. However, with unfiltered light produced by a powerful lamp, the main reaction was photodechlorination. The reagent 1 is expected to bind covalently to cytokinin-binding proteins through different ways upon photolysis.

The mass spectra of 1,3-dithiole-2-thione- and tetrathiafulvalene-fused thiophenes have been studied. Isomer differentiation was achieved by electron impact, metastable ion and collision-induced dissociation spectra.

International audience; 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.

International audience; This article appeared in a journal published by Elsevier. The attached copy is furnished to the author for internal non-commercial research and education use, including for instruction at the authors institution and sharing with colleagues. Other uses, including reproduction and distribution, or selling or licensing copies, or posting to personal, institutional or third party websites are prohibited. In most cases authors are permitted to post their version of the article (e.g. in Word or Tex form) to their personal website or institutional repository. Authors requiring further information regarding Elsevier's archiving and manuscript policies are encouraged to visit: This work establishes an experimental estimation of the full steady-state coverage of redox centers on self-assembled monolayers. The results demonstrate that the assessment of the full surface coverage and the adsorption kinetic from a Langmuir model impose drastic experimental conditions.

International audience; The current manuscript presents 3-[5′-(methylthio)-2,2′-bithiophen-5-ylthio]propanenitrile (MT3P), as a novel matrix molecule, which facilitates the selective ionization of alkaloids in matrix-assisted laser desorption/ionization mass spectrometry. Exhibiting strong ionizing properties at low levels of laser energy, MT3P was evaluated on 55 compounds belonging to various chemical families. The observed molecular ion yields induced by MT3P were compared with those obtained by commercially available matrices such as 1,8-dihydroxy-9,10-dihydroanthracen-9-one, α-cyano-4-hydroxycinnamic acid, 2,2′:5′,2″-terthiophene and 2,5-dihydroxybenzoic acid. In conclusion, MT3P displayed excellent ionization properties for 23 out of 25 investigated alkaloids, while showing little to no interaction with compounds from different chemical origin. Further, in comparison to other tested matrices, MT3P generally facilitated better ionization of alkaloids. Eventually, levels of laser energy were adjusted to obtain spectra with significantly reduced matrix noise.

International audience; This work reports the first example of electrochemical cation binding transductionvianitroxyl groups. It shows the possibility to transduce a complexation without a π-conjugated bridge between the redox and the host moieties. As expected, we confirm that the host/redox probe distance is a key point for transduction.

International audience; Original article : The current manuscript presents 3-[5′-(methylthio)-2,2′-bithiophen-5-ylthio]propanenitrile (MT3P), as a novel matrix molecule, which facilitates the selective ionization of alkaloids in matrix-assisted laser desorption/ionization mass spectrometry. Exhibiting strong ionizing properties at low levels of laser energy, MT3P was evaluated on 55 compounds belonging to various chemical families. The observed molecular ion yields induced by MT3P were compared with those obtained by commercially available matrices such as 1,8-dihydroxy-9,10-dihydroanthracen-9-one, α-cyano-4-hydroxycinnamic acid, 2,2′:5′,2″-terthiophene and 2,5-dihydroxybenzoic acid. In conclusion, MT3P displayed excellent ionization properties for 23 out of 25 investigated alkaloids, while showing little to no interaction with compounds from different chemical origin. Further, in comparison to other tested matrices, MT3P generally facilitated better ionization of alkaloids. Eventually, levels of laser energy were adjusted to obtain spectra with significantly reduced matrix noise.

International audience; Electrocatalysis: The molecular distribution of redox centers on mixed nitroxyl SAMs strongly influences the electrocatalytic reactivity.

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.

Self assembled monolayers (SAMs) formed from TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) derivative thiols have been studied by electrochemical quartz crystal microbalance (EQCM) in both aqueous and non-aqueous solvents. The in situ study of the mass transport occurring during the oxidation of TEMPO provides evidence of a ion pair formation without incorporation of solvent in densely packed nitroxyl radical SAMs. For SAMs having a low nitroxyl radical surface coverage, the effect of mixed SAMs is evidenced and seems to avoid the solvent incorporation. Keywords: Tempo, Self assembled monolayers, Cyclic voltammetry, Ion pairing

An efficient and easy new method for the conversion of amino-esters into amino-amides is described. In a one pot reaction between dialkyllithium amide and some amino-esters of thiophene and benzene, the corresponding amino-N-dialkylamides have been synthesized in high yields. The method was extended to malonic and phenylacetic esters. The reaction mechanism involves an anionic intermediate characterized by germylation.

Mixed SAMs of nitroxyl radical derivative and alkanethiol have been studied by cyclic voltammetry in both aqueous and non-aqueous solvents. Cyclic voltammograms exhibit shapes as a function of surface coverage deviating from an “ideal system”. Confronted to Laviron’s interaction model, the agreement observed between theory and experiments provides evidence of a random distribution of electroactive centers on surface and indicates that the local ionic environment of charged redox centers plays a major role in the electrochemical behaviour of SAMs. Keywords: Tempo, Self assembled monolayers, Cyclic voltammetry, Interaction model

International audience; Nitroxyl radical SAMs on gold afford a noteworthy electrochemical stability in both aqueous and organic media (see figure). The control of the redox center accessibility using mixed SAMs is illustrated by the electrocatalytic activities towards benzyl-alcohol oxidation in CH2Cl2 and H2O.

International audience; Plants are one of the major sources for the biologically active organic compounds and play a key role in medicinal chemistry for the treatment of various diseases [1]. DIAMS method is able to determine the secondary metabolites of complex vegetal extracts. The high throughput analyses of vegetal extracts are relatively difficult to perform in MALDI mass spectrometry, since the preparation of the sample involves the co-crystallization of the matrix with the analyte. Moreover irradiation of the matrix ion produces many low-m/z vs high-intensity ions preventing the detection of low molecular weight molecules such as secondary metabolites. We have developed a matrix-free alternative to MALDI analyses by the means of an original desorption/ionization on self-assembled monolayers surfaces (DIAMS) technique [2]. Monolayers were formed by using novel thiophene and coumarin-triazole analogues that absorbs the laser beam at 337nm. We herein disclose our findings with respect to the DIAMS method which is well suitable for the detection and quantification of the low molecular weight compounds that are present in plant extracts. Some of the isoquinoline alkaloids from the root extracts of Thalictrum flavum have been detected by the DIAMS method. Indeed, this technique would be promising suitable for the qualitative and quantitative analysis of polar and non-polar organic components that are widely distributed in the plants, without any preliminary chromatographic resolution [3].

International audience; This work demonstrates that the desorption/ionization on self-assembled monolayer surface (DIAMS) mass spectrometry, a recent matrix-free laser desorption/ionization (LDI) method based on an organic target plate, is as statistically repeatable and reproducible as matrix assisted laser desorption ionization (MALDI) and thin gold film-assisted laser desorption/ionization (TGFA-LDI) mass spectrometries. On lipophilic DIAMS of target plates with a mixture of glycerides, repeatability/reproducibility has been estimated at 15 and 30% and the relative detection limit has been evaluated at 0.3 and 3 pmol, with and without NaI respectively. Salicylic acid and its d6-isomer analysis confirm the applicability of the DIAMS method in the detection of compounds of low molecular weight.

International audience; We have studied the intracellular trafficking of Sit1 [ferrioxamine B (FOB) transporter] and Enb1 (enterobactin transporter) in Saccharomyces cerevisiae using green fluorescent protein (GFP) fusion proteins. Enb1 was constitutively targeted to the plasma membrane. Sit1 was essentially targeted to the vacuolar degradation pathway when synthesized in the absence of substrate. Massive plasma membrane sorting of Sit1 was induced by various siderophore substrates of Sit1, and by coprogen, which is not a substrate of Sit1. Thus, different siderophore transporters use different regulated trafficking processes. We also studied the fate of Sit1-mediated internalized siderophores. Ferrioxamine B was recovered in isolated vacuolar fractions, where it could be detected spectrophotometrically. Ferrioxamine B coupled to an inhibitor of mitochondrial protoporphyrinogen oxidase (acifluorfen) could not reach its target unless the cells were disrupted, confirming the tight compartmentalization of siderophores within cells. Ferrioxamine B coupled to a fluorescent moiety, FOB-nitrobenz-2-oxa-1,3-diazole, used as a Sit1-dependent iron source, accumulated in the vacuolar lumen even in mutants displaying a steady-state accumulation of Sit1 at the plasma membrane or in endosomal compartments. Thus, the fates of siderophore transporters and siderophores diverge early in the trafficking process.

Quaterthiophenes containing a median 3,3'-dimethoxybithiophene (4MTZ) or bis(3,4-ethylenedioxythiophene) (4ETZ) block and an azobenzene group attached at two internal beta-positions of the end thiophene rings have been synthesized. The analysis of the crystal structure of the two compounds by X-ray diffraction shows that, for 4MTZ, the quaterthiophene chain adopts a syn-anti-syn conformation similar to the parent system based on unsubstituted quaterthiophene. In contrast, 4ETZ presents an all-anti conformation stabilized by noncovalent intramolecular interactions between oxygen atoms and thiophenic sulfur atoms. The effect of the photoisomerization of the azobenzene group on the electronic properties of the attached pi-conjugated quaterthiophene chain has been analyzed by UV-vis spectroscopy and cyclic voltammetry. The results obtained for 4MTZ suggest very limited geometrical changes due to the restricted rotation around the central interannular single bond caused by steric interactions between the methoxy groups. In contrast, upon trans to cis photoisomerization of the attached azobenzene group of 4ETZ, the quaterthiophene chain undergoes a reversible conformational switch to a final state with a lower HOMO level and a larger HOMO-LUMO gap than the initial state.

A fluorescent labelled artificial siderophore 1 was synthesized by coupling a 7-nitrobenz-2-oxa-1,3-diazole (NBD) derivative to the terminal amino group of a new trihydroxamate-containing amine 2, a ferrichrome-type siderophore that was obtained from tris(hydroxymethyl) amino methane. Compound I was shown to be a suitable tool for experiments on siderophore transport and uptake processes in various organisms cells and particularly in Candida albicans cells.

WOS: 000189124800019, The efficiency and versatility of a spectroelectrochemical cell was used in order to couple electrochemistry and fluorescence spectroscopy. This new tool was tested and validated through the study of the reduction steps of a soluble perylene derivative. Besides the establishment of the method, the efficiency of UV-Vis spectroelectrochemistry and fluorescence spectroelectrochemistry were compared

Analogs of N6-isopentenyladenine bearing one or two fluorine atoms at the allylic position were synthesized from simple fluorinated ketones. The monofluoro analog was found to be more active than N6-isopentenyladenine and equivalent to the more potent zeatin, another natural plant growth hormone. The difluoro analog was even more powerful than zeatin.

Radical-anions formed by one electron attachment to aryl halides undergo cleavage of the carbon-halogen bond in a unimolecular process to give an aryl σ-radical and halide ion. Aryl σ-radicals are highly reactive intermediates and the objective of our work is to find conditions under which they can be trapped in an intramolecular reaction by an adjacent phenyl or alkene substituent. Further steps lead to a stable cyclised product and the process is of interest in synthesis. The corresponding intermolecular reactions between phenyl radicals and either benzene or an alkene have been shown to have bimolecular rate constants1 in the range 105 to 108 M−1s−1 so that the related intramolecular and unimolecular processes are expected to be very fast. Alternative reactions for the aryl σ-radical intermediates include abstraction of a hydrogen atom from the solvent and further electron transfer at the electrode surface to form a carbanion which undergoes protonation.

1-(2-Azido-6-chloropyrid-4-yl)-3-phenylurea was synthesized using known methods. Azido-tetrazole equilibrium for this compound was studied in various solvents, and the azide tautomer was found to be largely predominant. However, in water solution, it is suspected to exist in the tetrazole form in a significant amount. Like other 2,6-disubstituted pyridylurea analogs, it exhibits high cytokinin activity, and it is easily photolysable. Thus it appears to be a good candidate as a photoaffinity labeling reagent for cytokinin-binding proteins, receptors in particular. In the absence of the 6-chloro substituent, the tetrazole form was the only existing tautomer. The corresponding compound does not exhibit cytokinin activity and is not photolysable.

A general method for the synthesis of [35S]phosphorothionates is proposed, based on the example of [35S]fenthion. This consists of reacting molecular 35S with the corresponding phosphites which are easily prepared from commercial precursors.