A New Antibacterial N-Halamine Coating Based on Polydopamine.

To prevent the formation of biofilms on material surfaces, the latter must have antibacterial properties. The aim of this study is to investigate the synthesis and the antibacterial effect of a new N-halamine coating based on polydopamine (PDA). The benefits of this coating are multiple, notably the green process used to prepare it and the wide variety of organic or inorganic materials that can be functionalized. First, the formation of the PDA coating by oxidative polymerization of dopamine in weak alkaline aqueous solution was studied and characterized. Then, these PDA films were exposed to a NaOCl solution in order to form chloramine functions into the coating, i.e., to immobilize oxidative chlorine on and into the coating. The PDA film chlorination was notably followed in situ by a quartz crystal microbalance (QCM). The influence of the NaOCl solution pH and concentration on chlorination kinetics and on PDA film degradation was evidenced. Finally, the antibacterial properties of the modified PDA coatings were highlighted by testing their antiadhesion and bactericidal properties toward the Escherichia coli bacterial strain.

Tuning Charge Storage Properties of Supercapacitive Electrodes Evidenced by In Situ Gravimetric and Viscoelastic Explorations.

Revealed by an integrated electrogravimetric and viscoelastic method, slightly electrochemically reduced graphene oxide (ERGO) presents an anion preference for charge storage and delivery, while with the progressive removal of oxygen functionalities on its basal planes, cations begin to predominate in charge compensation. This "anion-to-cation" evolution in neutral aqueous media can not only affect the electrochemical charge storage, but also play an important role in electrode's viscoelasticity. It was demonstrated that oxygen functionalities could modify the interactions between graphene layers and even contribute to pseudocapacitances. However, the role of oxygen functionalities in species transfer and viscoelastic variations still remains poorly understood. Herein, a combined methodology of electrochemical quartz crystal microbalance (EQCM), ac-electrogravimetry and electroacoustic impedance measurements was proposed for characterizing the electrochemical and viscoelastic responses of graphene oxides with various degree of electrochemical reduction. With the removal of oxygen containing functional groups, ERGO electrode exhibits ( i) a gradually enhanced specific capacitance ( Cs) with increased flexibility (decreased storage moduli, G'); ( ii) a dehydration process of cations (i.e., from Na+·2H2O to Na+·H2O); and ( iii) a potential-dependent "stiffened-softened" behavior. These results open the door for a suitable design of GO-based materials for electrochemical energy storage and shed light on electronic devices where ion-selective behavior plays a key role.

Ion intercalation dynamics of electrosynthesized mesoporous WO3 thin films studied by multi-scale coupled electrogravimetric methods.

Mesoporous WO3 thin films were prepared electrochemically by using an ionic surfactant during the synthesis, and the electrochemical properties are investigated in comparison with their dense analogues. This report specifically highlights the suitability of a time resolved coupled electrogravimetric method to follow meticulously the ion intercalation/extraction phenomena which revealed the enhanced ion intercalation/extraction behavior of electrodeposited mesoporous WO3 thin films for diverse applications in energy storage and electrochromism. This methodology (electrochemical impedance spectroscopy (EIS) and its coupling with a fast quartz crystal microbalance (QCM)) has the ability to detect the contribution of the charged or uncharged species during the electrochemical processes, and to deconvolute the global EQCM responses into the anionic, cationic, and the free solvent contributions. Our study identifies the involvement of several charged species (Li(+), Li(+)·H2O) in the compensation of charge, and H2O molecules indirectly contribute to the process in both dense and mesoporous WO3 thin films. Even a slight contribution of ClO4(-) ions was detected in the case of mesoporous analogues. The results of the study indicate that the transfer resistances of Li(+) and Li(+)·H2O are decreased when the WO3 films are mesoporous. A more significant difference is observed for the larger and partially dehydrated Li(+)·H2O ions, suggesting that increased surface area and pore volume created by mesoporous morphology facilitate the transfer of larger charged species. The relative concentration changes of cations are also magnified in the mesoporous films. The final concentration variations are higher in mesoporous films than that in the dense analogues; ∼4 times and ∼10 times higher for Li(+) and for Li(+)·H2O, respectively. To the best of our knowledge, an unambiguous identification of species other than desolvated cations (e.g. Li(+) ions), the information on their transfer dynamics and quantification of the transferred species have never been reported in the literature to describe the charge compensation process in WO3 based electrodes.

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.

Determination of the diffusion coefficient of protons in Nafion thin films by ac-electrogravimetry.

This letter deals with an adaptation of the ac-electrogravimetry technique to extract separately the dynamic properties of H(+) and water in Nafion nanometric thin films (average thickness of 400 nm). An original theoretical approach was developed to extract the representative parameters from ac-electrogravimetry data. The concentration change of the exchanged species and the diffusion coefficient of the protons in a Nafion nanometric thin film (D = 0.5 × 10(-6) cm(2) s(-1) at 0.3 V vs SCE) were estimated for the first time according to the applied potential. The conductivity value of Nafion thin films was calculated from the Nernst-Einstein equation using diffusion coefficients and concentration values extracted from ac-electrogravimetry data. The calculated conductivity results agree well with the experimental proton conductivity values of Nafion thin films.

Antimicrobial N-halamine polymers and coatings: a review of their synthesis, characterization, and applications.

Antimicrobial N-halamine polymers and coatings have been studied extensively over the past decade thanks to their numerous qualities such as effectiveness toward a broad spectrum of microorganisms, long-term stability, regenerability, safety to humans and environment and low cost. In this review, recent developments are described by emphasizing the synthesis of polymers and/or coatings having N-halamine moieties. Actually, three main approaches of preparation are given in detail: polymerization, generation by electrochemical route with proteins as monomers and grafting with precursor monomers. Identification and characterization of the formation of the N-halamine bonds (>N-X with X = Cl or Br or I) by physical techniques such as Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), and by chemical reactions are described. In order to check the antimicrobial activity of the N-halamine compounds, bacterial tests are also described. Finally, some examples of application of these N-halamines in the water treatment, paints, healthcare equipment, and textile industries are presented and discussed.

Tuning Redox State and Ionic Transfers of Mg/Fe-Layered Double Hydroxide Nanosheets by Electrochemical and Electrogravimetric Methods.

Studying the electrogravimetric behavior of Mg/Fe-layered double hydroxide (LDH) nanoparticles with an electrochemical quartz crystal microbalance demonstrates its pseudocapacitance properties of mix cation and anion exchanger. The electrochemical control of the oxidation state of iron constituting the layered sheets allowed anion intercalation/deintercalation into the LDH interlayer space. Concomitantly, in agreement with the pH of zero point of net charge of the Mg/Fe-LDH, the interfacial pH increase via catalyzed hydrogen evolution reaction allows cation electroadsorption onto the external surfaces of the nanoplatelets.

Charge Storage Properties of Nanostructured Poly (3,4-ethylenedioxythiophene) Electrodes Revealed by Advanced Electrogravimetry.

PEDOT nanowires (NWs) directly grown on the conducting electrode of quartz resonators enable an advanced electrogravimetric analysis of their charge storage behavior. Electrochemical quartz crystal microbalance (EQCM) and its coupling with electrochemical impedance spectroscopy (ac-electrogravimetry or AC-EG) were used complementarily and reveal that TBA+, BF4- and ACN participate in the charge compensation process with different kinetics and quantity. BF4- anions were dominant in terms of concentration over TBA+ cations and the anion transfer results in the exclusion of the solvent molecules. TBA+ concentration variation in the electrode was small compared to that of the BF4- counterpart. However, Mw of TBA+ is much higher than BF4- (242.3 vs. 86.6 g·mol-1). Thus, TBA+ cations' gravimetric contribution to the EQCM response was more significant than that of BF4-. Additional contribution of ACN with an opposite flux direction compared with BF4-, led to a net mass gain/lost during a negative/positive potential scan, masking partially the anion response. Such subtleties of the interfacial ion transfer processes were disentangled due to the complementarity of the EQCM and AC-EG methodologies, which were applied here for the characterization of electrochemical processes at the PEDOT NW electrode/organic electrolyte interface.

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.

Amorphous carbon nitride as an alternative electrode material in electroanalysis: simultaneous determination of dopamine and ascorbic acid.

Boron-doped diamond (BDD) films are excellent electrode materials, whose electrochemical activity for some analytes can be tuned by controlling their surface termination, most commonly either to predominantly hydrogen or oxygen. This tuning can be accomplished by e.g. suitable cathodic or anodic electrochemical pretreatments. Recently, it has been shown that amorphous carbon nitride (a-CNx) films may present electrochemical characteristics similar to those of BDD, including the influence of surface termination on their electrochemical activity toward some analytes. In this work, we report for the first time a complete electroanalytical method using an a-CNx electrode. Thus, an a-CNx film deposited on a stainless steel foil by DC magnetron sputtering is proposed as an alternative electrode for the simultaneous determination of dopamine (DA) and ascorbic acid (AA) in synthetic biological samples by square-wave voltammetry. The obtained results are compared with those attained using a BDD electrode. For both electrodes, a same anodic pretreatment in 0.1 mol L(-1) KOH was necessary to attain an adequate and equivalent separation of the DA and AA oxidation potential peaks of about 330 mV. The detection limits obtained for the simultaneous determination of these analytes using the a-CNx electrode were 0.0656 µmol L(-1) for DA and 1.05 µmol L(-1) for AA, whereas with the BDD electrode these values were 0.283 µmol L(-1) and 0.968 µmol L(-1), respectively. Furthermore, the results obtained in the analysis of the analytes in synthetic biological samples were satisfactory, attesting the potential application of the a-CNx electrode in electroanalysis.

Photocurrent generation in carbon nitride and carbon nitride/conjugated polymer composites.

The semiconductor and photovoltaic properties of carbon nitride (CNx) thin films prepared using a reactive magnetron cathodic sputtering technique were investigated both individually and as composites with an organic conjugated polymer, poly(2,2'-bithiophene) (PBT). The CNx films showed an increasing thickness as the deposition power and/or nitrogen content in the gas mixture increase. At low nitrogen content and low deposition power (25-50 W), the film structure was dominated by the abundance of the graphitic sp(2) regions, whereas at higher nitrogen contents and magnetron power CNx films started to demonstrate semiconductor properties, as evidenced by the occurrence of photoconductivity and the development of a space charge region. However, CNx films alone did not show any reproducible photovoltaic properties. The situation changed, however, when CNx was deposited onto conjugated PBT substrates. In this configuration, CNx was found to function as an acceptor material improving the photocurrent generation both in solution and in solid state photovoltaic devices, with the external quantum efficiencies reaching 1% at high nitrogen contents. The occurrence of the donor-acceptor charge transfer was further evidenced by suppression of the n-doping of the PBT polymer by CNx. Nanoscale atomic force microscopy (AFM) and current-sensing AFM data suggested that CNx may form a bulk heterojunction with PBT.

A very thin overoxidized polypyrrole membrane as coating for fast time response and selective H2O2 amperometric sensor.

Pyrrole electrooxidation in the presence of weak-acidic anions allows one to locally, rapidly and in single step form on the electrode a pinhole-free very thin layer of overoxidized polypyrrole (OPPy). This membrane could be really useful for the design of amperometric biosensor based on oxidation of H(2)O(2) generated by an oxidase. Indeed, using rotation disk electrode, the apparent diffusion coefficient of H(2)O(2) within this OPPy film was found to be 10(-8)cm(2)s(-1), which corresponds to a fast response time of 0.1 ms. Moreover, it is shown that with this system, platinum electrode coated with the very thin OPPy membrane, the H(2)O(2) sensitivity is excellent (700 nA microM(-1)cm(-2)) and the H(2)O(2) selectivity relative to potentially interfering species present in biological fluids, such as ascorbate and dopamine, is very good. Thus, this OPPy membrane which can be locally electrodeposited is ideal for the construction of oxidase-based microbiosensors.

An original route to immobilize an organic biocide onto a transparent tin dioxide electrode.

Prevention of biofilm growth on surfaces immersed in an aqueous environment could be obtained either by the release of an antifouling biocide or by the presence of such compounds on the surface. In this paper it is shown, for the first time, that an electrochemical treatment performed in the presence of chlorides and proteins allows the immobilization of an organic biocide (chloramine) on the electrode. This electrode is a stable transparent conductive tin dioxide film coated on glass. It is polarized to oxidize chloride ions into hypochlorous acid, which reacts with the organic matter (bovine serum albumin) present at the electrode/solution interface, leading on one hand to the chlorination of the proteins with in particular the chloramine formation and on the other hand to the protein aggregation on the surface.

A reduced polyoxomolybdenum borophosphate anion related to the Wells-Dawson clusters.

The new compound (C3N2H5)8[MoV5MoVI7O22(BO4)2(PO4)5(HPO4)3].nH2O is the first molybdenum borophosphate. It contains clusters of twelve molybdenum, eight phosphorus and two boron atoms, [Mo12O22(BO4)2(PO4)5(HPO4)3]8- similar to the Wells-Dawson clusters. Five molybdenum atoms are MoV while the others are MoVI, and the five electrons are delocalized. According to the temperature dependence of the magnetic susceptibility four of these electrons are paired.