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A new coupling reaction, the para-fluoro-thiol (PFT) reaction, activated by base at room temperature, is reported for carbon surface functionalization. 4-Nitrothiophenol (4-NTP) and (3-nitrobenzyl)mercaptan (3-NBM) were coupled to pentafluorophenyl (F5-Ph) anchor layers grafted from the aryldiazonium ion formed in situ. The relative yields of the PFT reactions, estimated from the electrochemical responses of coupled nitrophenyl (NP) and nitrobenzyl (NB) groups, depended on the nucleophilicity of the thiolate and the strength of the base. The highest surface concentration (4.6 × 10-10 mol cm-2) was obtained using 3-NBM in the presence of [Bu4N]OH; this concentration corresponds to the maximum that is typically achieved for other high-yielding coupling reactions at aryldiazonium ion anchor layers. The PFT reaction is expected to be applicable to the numerous thiol derivatives commonly restricted to self-assembled monolayer (SAM) formation at gold and other noble metals, thereby opening a simple new approach for interface design on carbon substrates. The strategy may also have advantages for modification of gold surfaces: the layer prepared by coupling 3-NBM to F5-Ph films on gold was found to be more stable to storage under ambient conditions than self-assembled monolayers of 3-NBM.

ZnO is a strong candidate for transparent electronic devices due to its wide band gap and earth-abundance, yet its practical use is limited by its surface metallicity arising from a surface electron accumulation layer (SEAL). The SEAL forms by hydroxylation of the surface under normal atmospheric conditions, and is present at all crystal faces of ZnO, although with differing hydroxyl structures. Multilayer aryl films grafted from aryldiazonium salts have previously been shown to decrease the downward bending at O-polar ZnO thin films, with Zn-O-C bonds anchoring the aryl films to the substrate. Herein we show that the Zn-polar (0001), O-polar (000 1‾ ), and non-polar m-plane (10 1‾ 0) faces of ZnO single crystals, can also be successfully electrografted with nitrophenyl (NP) films. In all cases, X-ray photoelectron spectroscopy (XPS) measurements reveal that the downward surface band bending decreases after modification. XPS provides strong evidence for Zn-O-C bonding at each face. Electrochemical reduction of NP films on O-polar ZnO single crystals converts the film to a mainly aminophenyl layer, although with negligible further change in band bending. This contrasts with the large upward shifts in band bending caused by X-ray induced reduction.

Aryldiazonium ions are widely used reagents for surface modification. Attractive aspects of their use include wide substrate compatibility (ranging from plastics to carbons to metals and metal oxides), formation of stable covalent bonding to the substrate, simplicity of modification methods that are compatible with organic and aqueous solvents, and the commercial availability of many aniline precursors with a straightforward conversion to the active reagent. Importantly, the strong bonding of the modifying layer to the surface makes the method ideally suited to further on-surface (postfunctionalization) chemistry. After an initial grafting from a suitable aryldiazonium ion to give an anchor layer, a target species can be coupled to the layer, hugely expanding the range of species that can be immobilized. This strategy has been widely employed to prepare materials for numerous applications including chemical sensors, biosensors, catalysis, optoelectronics, composite materials, and energy conversion and storage. In this Review our goal is first to summarize how a target species with a particular functional group may be covalently coupled to an appropriate anchor layer. We then review applications of the resulting materials.

Synchrotron x-ray photoelectron spectroscopy was used to explore the relationship between the hydroxyl termination and band bending at the $(\overline{2}01)$ surface of $\ensuremath{\beta}\text{\ensuremath{-}}\mathrm{G}{\mathrm{a}}_{2}{\mathrm{O}}_{3}$ bulk single crystals. All as-received $(\overline{2}01)$ surfaces were terminated with OH groups, with H/OH binding to surface ${\mathrm{O}}_{\mathrm{s}}/\mathrm{G}{\mathrm{a}}_{\mathrm{s}}$ atoms. Removal of this native OH termination produced a large upward shift in band bending of up to 1.0 eV, consistent with strong electron depletion and a semiconductor to insulator-like transition in the near-surface region. Simple surface treatments were used to control the size and stability of the band bending of as-received $(\overline{2}01)$ surfaces by modifying the nature of the OH termination. NaOH (${\mathrm{H}}_{2}\mathrm{S}{\mathrm{O}}_{4}$) treatment consistently produced upward (downward) shifts in band bending and a significant increase (decrease) in the thermal stability of the OH termination that was associated with an increase in the relative density of $\mathrm{G}{\mathrm{a}}_{\mathrm{s}}\text{\ensuremath{-}}\mathrm{OH}$ (${\mathrm{O}}_{\mathrm{s}}\text{\ensuremath{-}}\mathrm{H}$) species. Annealing in wet ${\mathrm{O}}_{2}$ (at 600 \ifmmode^\circ\else\textdegree\fi{}C) produced an extremely stable OH termination and the strongest downward shift in band bending. These effects, combined with the relatively slow dissociation of ${\mathrm{H}}_{2}\mathrm{O}$ on bare $(\overline{2}01)$ surfaces, allowed the preparation of surfaces with significant variations in band bending that may prove useful in optimizing the properties of $\ensuremath{\beta}\text{\ensuremath{-}}\mathrm{G}{\mathrm{a}}_{2}{\mathrm{O}}_{3}$ metal-semiconductor contacts and heterojunctions. A comparison of two methods used to determine the absolute band bending at semiconductor surfaces confirmed that bare $\ensuremath{\beta}\text{\ensuremath{-}}\mathrm{G}{\mathrm{a}}_{2}{\mathrm{O}}_{3}(\overline{2}01)$ surfaces are characterized by strong upward band bending (\ensuremath{\sim}0.5 to 1.0 eV) and an electron depletion layer that can be completely removed by the hydroxylation of the surface.

Tin(IV) dioxide (SnO2) is a technologically important transparent conducting oxide with high chemical stability. In air, the SnO2 surface is terminated with hydroxyl groups which cause the electronic bands to bend downward at the surface capturing a two-dimensional surface electron accumulation layer (SEAL). The SEAL promotes adsorption at the surface, giving environmentally-sensitive electronic properties; this sensitivity is a barrier to some potential applications of the material. This work investigates surface modification of SnO2via reaction with an aryldiazonium salt as a route to controlling the surface band bending. We compare the surface layers formed by reaction at open-circuit potential and under potential control of 4-(trifluoromethyl)benzene diazonium ions with moderately- and highly-doped (101) SnO2 thin films grown by plasma-assisted molecular beam epitaxy. Atomic force microscopy and synchrotron X-ray photoelectron spectroscopy (XPS) measurements demonstrate that both reaction conditions lead to covalently-attached 4-(trifluoromethyl)phenyl groups, with grafting at open-circuit potential giving thinner layers ( 3 nm). Valence band investigations show that for all samples the 4-(trifluoromethyl)phenyl layers decrease the surface downward band bending with the greatest effect observed for the electrografted sample. In the latter case, a +0.29 eV shift in band bending relative to that of the unmodified material indicates the success in turning the surface electron accumulation layer into a depletion layer.

ZnO is a member of a small class of semiconductors that includes In2O3, SnO2, CdO, and InN, whose surfaces are highly unusual because their electronic bands bend downward to form a quantized potential well in which a two-dimensional electron gas is confined. At the O-polar ZnO(0001) surface, this effect arises from the adsorption of H adatoms which produces a hydroxyl-terminated surface. In this work, we investigate the effect of covalently anchored organic layers on the band bending at ZnO(0001) surfaces. We use aryldiazonium salt electrochemistry to deposit 4–5 nm thick layers of 4-nitrophenyl (NP) and 4-(trifluoromethyl)phenyl (TFMP) groups. Synchrotron X-ray photoelectron spectroscopy (XPS) showed that both NP and TFMP modifications permanently removed the downward band bending at the ZnO surface. This behavior can be explained by the direct covalent bonding of the aryl groups to the surface, also revealed by XPS analysis, and the electron-withdrawing character of both modifiers. Surprisingly, the i...

The differential capacitance of 1–2 layered and 6–7 layered graphene (LG) was measured in aqueous 0.01, 0.1, 1.0, and 3 M perchloric and sulfuric acid solutions. The total measured capacitance was evaluated for approx. ±500 mV either side of the potential of zero charge to observe the contribution from the quantum capacitance and shielding effects on the measured capacitance. The experimental results were compared to the recent theoretical evaluations of similar electrode–electrolyte interfaces for supercapacitor applications. At 6–7 LG electrodes, the measured differential capacitance was dependent on the solution and electrical double layer structures, and although the 1–2 layered electrode showed far fewer differences upon changing solution conditions, it was not strictly independent. The concept of shielding effects within the graphene electrode and a dielectric capacitance as proposed by theory would account for these observations.

Preventing graphene sheet aggregation while retaining full accessibility to the total graphene surface area is key to optimizing the performance of graphene supercapacitors. Spacer species can be added to graphene assemblies to prevent aggregation, but typical methodologies do not allow accurate assessment of the extent of sheet separation nor whether spacing groups block some of the surface area. In this work we have grafted sub-10 nm films of aryl spacer groups to chemical vapor deposition-grown few layer graphene (FLG) sheets using aryldiazonium salts. Using a layer-by-layer strategy that relies on individually handling each FLG sheet, 3-sheet stacks were prepared and electrochemically interrogated. By comparing the differential and integral capacitances of modified and unmodified single FLG sheets and 3-sheet stacks, we show that in the 3-sheet stacks of modified FLG, the grafted spacer groups fully separate the FLG sheets and allow complete double layer formation at all FLG-solution interfaces. The s...

Graphene-Au hybrid materials show promise for applications ranging from biosensing to field emission devices. Electrodeposition is an inexpensive, fast and technically simple method for controlled deposition of nanoparticles but its use with graphene prepared by chemical vapor deposition (CVD) presents some problems. Cu foil is commonly used to catalyze the CVD process and the resulting graphene is most conveniently handled while retained on the Cu support. However Cu is able to spontaneously reduce Au salts in aqueous solution and hence deposition of nanoparticles via galvanic displacement occurs simultaneously with electrodeposition, and control of the growth process is lost. We show here that Au nanoparticles can be controllably electrodeposited onto Cu-supported few layer graphene (FLG) from N,N -dimethylformamide (DMF) solutions of a [AuCl 4 ] − salt because spontaneous deposition of Au nanoparticles does not occur in this medium. Deposition occurs by the instantaneous nucleation mechanism when driven by an applied potential enabling the Au nanoparticle density to be controlled by the deposition conditions, predominantly the deposition potential. Following nucleation, nanoparticle growth is diffusion controlled. Our results demonstrate that the growth rate is similar in the presence and absence of an applied potential and control of growth time is key to controlling nanoparticle size.

Tin(iv) dioxide (SnO

We have recently reported that reversible electrowetting can be observed on the basal plane of graphite, without the presence of a dielectric layer, in both liquid/air and liquid/liquid configurations. The influence of carbon structure on the wetting phenomenon is investigated in more detail here. Specifically, it is shown that the adsorption of adventitious impurities on the graphite surface markedly suppresses the electrowetting response. Similarly, the use of pyrolysed carbon films, although exhibiting a roughness below the threshold previously identified as the barrier to wetting on basal plane graphite, does not give a noticeable electrowetting response, which leads us to conclude that specific interactions at the water–graphite interface as well as graphite crystallinity are responsible for the reversible response seen in the latter case. Preliminary experiments on mechanically exfoliated and chemical vapour deposition grown graphene are also reported.

ZnO is a prime candidate for future use in transparent electronics; however, development of practical materials requires attention to factors including control of its unusual surface band bending and surface reactivity. In this work, we have modified the O-polar (0001), Zn-polar (0001), and m-plane (1010) surfaces of ZnO with phosphonic acid (PA) derivatives and measured the effect on the surface band bending and surface sensitivity to atmospheric oxygen. Core level and valence band synchrotron X-ray photoemission spectroscopy was used to measure the surface band bending introduced by PA modifiers with substituents of opposite polarity dipole moment: octadecylphosphonic acid (ODPA) and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylphosphonic acid (F13OPA). Both PAs act as surface electron donors, increasing the downward band bending and the strength of the two-dimensional surface electron accumulation layer on all of the ZnO surfaces investigated. On the O-polar (0001) and m-plane (1010) surfaces, the O...

Methods that reliably yield monolayers of covalently anchored modifiers on graphene and other planar graphitic materials are in demand. Covalently bonded groups can add functionality to graphitic carbon for applications ranging from sensing to supercapacitors and can tune the electronic and optical properties of graphene. Limiting modification to a monolayer gives a layer with well-defined concentration and thickness providing a minimum barrier to charge transfer. Here we investigate the use of anthranilic acid derivatives for grafting aryl groups to few layer graphene and pyrolyzed photoresist film (PPF). Under mild conditions, anthranilic acids generate arynes, which undergo Diels-Alder cycloadditions. Using spectroscopy, electrochemistry, and atomic force microscopy, we demonstrate that the reaction yields monolayers of aryl groups on graphene and PPF with maximum surface coverages consistent with densely packed layers. Our study confirms that anthranilic acids offer a convenient route to covalent modification of planar graphitic carbons (both basal and edge plane materials).

The surface concentration of nitrophenyl (NP) films is commonly calculated from the charge associated with its redox reactions in aqueous solution. Reduction is usually carried out in acidic or basic solution and is assumed to proceed by either four electrons, or a mixed four and six electron process. Here we reproducibly graft NP films of different thicknesses to glassy carbon electrodes from the corresponding diazonium ion and examine the reduction of the films in strongly acidic and basic solutions. We demonstrate that in all cases, assumption of a four electron reduction of NP groups coupled with use of the redox reaction of the hydroxylamine product will lead to an underestimation of the surface concentration of NP groups. Use of acidic media with the assumption of a mixed four and six electron reduction of NP groups is shown to be an electrochemically and chemically sensible approach to estimating surface concentrations of NP groups.

Free-floating, and copper-supported, few-layer graphene sheets were spontaneously modified from an aqueous solution containing nitrobenzenediazonium ions. The infrared spectra of the chemically modified (copper etched) free-floating graphene were measured in transmission mode by manipulating the sheets onto a KBr disc. The major advantage to this method is the ability to release the graphene sheets off the disc to refloat on a water bath, allowing the graphene to be further modified or deposited onto a new substrate suitable for other analysis. In this study, graphene sheets were then mounted onto highly ordered pyrolytic graphite (HOPG) for atomic force microscopy imaging and electrochemical measurements. The results show there are at least two reaction pathways for spontaneous film grafting to graphene: the commonly accepted aryl radical leading to films containing −C–C– linkages and a direct reaction of the diazonium cation with graphene to give films containing −N═N– linkages. The ability to manipulat...

International audience; Cyclic voltammograms for the reduction of aryldiazonium ions at glassy carbon electrodes are often, but not always, reported to show two peaks. The origin of this intriguing behavior remains controversial. Using 4-nitrobenzenediazonium ion (NBD), the most widely studied aryldiazonium salt, we make a detailed examination of the electroreduction processes in acetonitrile solution. We confirm that deposition of film can occur during both reduction processes. Film thickness measurements using atomic force microscopy reveal that multilayer films of very similar thickness are formed when reduction is carried out at either peak, even though the film formed at the more negative potential is significantly more blocking to solution redox probes. These and other aspects of the electrochemistry are consistent with the operation of a surface-catalyzed reduction step (proceeding at a clean surface only) followed by an uncatalyzed reduction at a more negative potential. The catalyzed reduction proceeds at both edge-plane and basal-plane graphite materials, suggesting that particular carbon surface sites are not required. The unusual aspect of aryldiazonium ion electrochemistry is that unlike other surface-catalyzed reactions, both processes are seen in a single voltammetric scan at an initially clean electrode because the conditions for observing the uncatalyzed reaction are produced by film deposition during the first catalyzed reduction step.[on SciFinder (R)]

The quantum capacitance from large area, 6- to 7-layered graphene, and chemically modified graphene, was determined using electrochemical impedance spectroscopy measured at 100 Hz in a three-electrode electrochemical cell and aqueous acidic solution. Aryldiazonium chemistry was used to modify one side of the few-layered graphene sheets with methoxy- and iodo-phenyl groups. The graphene sheets were then mounted via an aqueous transfer method onto an epoxy substrate. It was found that both sides of the graphene sheets could be accessed by the electrolyte and thus the sheets were in a pseudo free-floating arrangement. The results show a complex quantum capacitance behavior with applied electrode potential, and that behavior was not stable with potential cycling. Chemically modified samples have similar quantum capacitance minimum to unmodified graphene, and all samples have a shallow U-shaped relationship with respect to applied electrode potential. The results show chemically modifying one side of few-layer...

Herein, we report a highly sensitive electrocatalytic sensor-cell construct that can electrochemically communicate with the internal environment of immune cells (e.g., macrophages) via the selective monitoring of a particular reactive oxygen species (ROS), hydrogen peroxide. The sensor, which is based on vertically aligned single-walled carbon nanotubes functionalized with an osmium electrocatalyst, enabled the unprecedented detection of a local intracellular “pulse” of ROS on a short second time scale in response to bacterial endotoxin (lipopolysaccharide-LPS) stimulation. Our studies have shown that this initial pulse of ROS is dependent on NADPH oxidase (NOX) and toll like receptor 4 (TLR4). The results suggest that bacteria can induce a rapid intracellular pulse of ROS in macrophages that initiates the classical innate immune response of these cells to infection.

Use of porous anodic alumina (PAA) membranes prevents sintering of metal catalyst particles during growth of carbon nanotubes (CNTs) by chemical vapour deposition (CVD). When a metal catalyst fills the base of the pores, the diameters of the resulting CNTs match those of the pores. This approach is generally limited to PAA membranes with pores ≥50 nm in diameter presumably due to difficulties associated with metal deposition in very narrow pores and with mass transport of gases during CVD. However, PAA membranes offer the opportunity to grow CNTs using catalyst particles with diameters that are significantly smaller than the pores. Here we investigate the electrodeposition of small amounts of Co into the pores of shallow PAA membranes. Using alternating voltage deposition with membranes that have intact, but thinned, barrier layers we demonstrate that CNTs with a diameter of 25 ± 3 nm can be grown from pores with diameters of 60 ± 4 nm.

Monolayers and sub-monolayers of ferrocene (Fc) groups were immobilised on glassy carbon by direct reactions of primary amine and carboxylic acid derivatives of Fc. Reaction of FcCH2NH2 with polished GC in acetonitrile at open circuit potential yielded grafted layers with surface coverages up to ∼70 % of a close-packed monolayer. The influence of the solvent and applied potential during the reaction was consistent with a Michael-like addition mechanism at the surface. When FcCH2NH2 was reacted with GC under conditions that promote amide bond formation, sub-monolayers of Fc groups were attached; however, the participation of the Michael-like addition reaction as the major immobilisation pathway could not be discounted. Activation of FcCOOH and FcCH2COOH with oxalyl chloride and reaction with polished GC gave surface coverages of Fc corresponding to ∼25 % of a close-packed monolayer. Ester bonds are assumed to form in these reactions. The modification methods investigated here are experimentally simple and are very suitable for use with high surface area carbons. Furthermore, they may be the method of choice for applications where multilayer coatings must be avoided.

Patterned nanoscale molecular films will be a key componentof advanced devices such as novel chemical and biologicalsensors and nanoelectronic systems. For long-establishedsurface modification strategies such as the use of self-assembledmonolayers ofalkanethiolsat noblemetal surfacesandreactionsofsilanesatoxidesurfaces,patterningstrategieshave reached a high level of sophistication.

International audience; Surface modification by grafting from aryldiazonium salts has been widely studied and applied to many substrates as a simple and versatile method for preparing strongly adherent organic coatings. Unless special precautions or conditions are used, the usual film structure is a loosely packed disordered multilayer; however, over the past decade, attention has been paid to establishing strategies for grafting just a monolayer of modifiers to the surface. To date, four general approaches to monolayer preparation have emerged: use of aryldiazonium ions with cleavable protection groups; use of aryldiazonium ions with steric constraints; grafting in the presence of a radical scavenger; and grafting from ionic liquids. This review describes these approaches, illustrates some of their applications, and highlights the advantages and disadvantages of each.

A simple method for producing patterned forests of multiwalled carbon nanotubes (MWCNTs) is described. An aqueous metal salt solution is spin-coated onto a substrate patterned with photoresist by standard methods. The photoresist is removed by acetone washing leaving the acetone-insoluble catalyst pattern on the substrate. Dense forests of vertically aligned (VA) MWCNTs are grown on the patterned catalyst layers by chemical vapour deposition. The procedures have been demonstrated by growing MWCNT forests on two substrates: silicon and conducting graphitic carbon films. The forests adhere strongly to the substrates and when grown directly on carbon film, offer a simple method of preparing MWCNT electrodes.

Candida albicans and some other yeast species are known to have an oestrogen binding protein (EBP), which oxidises NAD(P)H to NAD(P) + . 17β-oestradiol, when present, binds to the NAD(P)H oxidation site which leads to an accumulation of NAD(P)H. Our previous research has shown that oestrogens can be quantified using Saccharomyces cerevisiae cells as the detection element and a double mediator electrochemical system to measure NAD(P)H. In a modification to the whole cell method, C. albicans cell lysate and a single hydrophilic mediator was used to quantify 17β-oestradiol. This paper employs the mediated electrochemical systems to investigate the influence of growth phase on EBP production in C. albicans and the response of cells of different ages to different concentrations of oestrogen. A cell not known to possess EBP ( Arxula adeninivorans ) was also investigated for its response to 17β-oestradiol. As expected, A. adeninivorans did not show a detectable response to 17β-oestradiol, but surprisingly, its catabolism was inhibited.

We describe the reproducible fabrication of robust, vertically aligned multiwalled carbon nanotube (VACNT)/epoxy composite electrodes. The electrodes are characterized by cyclic voltammetry, impedance spectroscopy, and scanning electron and atomic force microscopies. Low background currents are obtained at the electrodes, and common redox probe molecules and NADH show excellent voltammetric behavior. When electrode performance deteriorates due to fouling, the electrode surfaces can be reproducibly renewed by mechanical polishing followed by O(2) plasma treatment. The electrochemical performance of the electrodes is maintained after more than 100 cycles of use and renewal.

An investigation of the kinetics of electron transfer though a self-assembled monolayer containing long chain alkanethiol and β-peptide components and a terminating ferrocene group has been carried out at a polycrystalline gold electrode. Cyclic voltammetry and electrochemical impedance spectroscopy in aqueous and mixed aqueous−methanol solutions showed the rate of electron transfer varied from approximately 5 in water to 29 s−1 in methanol. This difference is attributed to a change in the alkanethiol tilt angle in the film in response to hydrogen bonding disruption of the peptide to allow greater molecular motion during electron transfer.

The covalent grafting of nitrophenyl functionalities to planar carbon substrates by reaction with 4-nitrobenezene diazonium salt at open circuit potential has been studied in aqueous acid and acetonitrile solutions. Atomic force microscopy and electrochemical measurements reveal that the reaction proceeds through two distinct mechanisms. Rapid film growth occurs via reduction of the 4-nitrobenezene diazonium cation by the substrate, giving an aryl radical that couples to the surface. Film growth by this mechanism ceases once the film has reached a thickness at which electron transfer through the passivating film is no longer possible. Slow film growth via a secondary, potential-independent mechanism continues even after the substrate-dependent reaction has ceased. We tentatively propose that slow film growth involves grafting of an aryl cation originating from thermal heterolytic decomposition of the diazonium cation.

Size-controlled ZnO nanowires were grown by eclipse pulsed laser deposition using Au colloids and ultra-small (sub 2 nm) Au101 and Au9 clusters as catalysts, tethered to c-plane sapphire substrates using aminopropyltrimethoxysilane (APTMS). A strong correlation was observed between ZnO nanowire tip diameter and Au catalyst size, with no apparent lower limit to the size of Au nanoparticles able to catalyze nanowire growth. All ZnO nanowires produced intense ultraviolet photoluminescence with almost no visible defect band emission that is commonly observed in ZnO-based materials, including nanowires. A correlation was also observed between the quality of the ultraviolet photoluminescence (in terms of decreasing exciton line widths and surface-related emission) and decreasing ZnO nanowire diameter, with the highest quality emission obtained using Au9 atomically precise cluster catalysts, used here as catalysts for ZnO growth for the first time.

International audience; A simple, time-and cost-effective procedure is described for regenerating film-modified or deactivated pyrolyzed photoresist film (PPF) surfaces. Heating for 30 min at 545 ± 25 °C in argon at a flow rate of 1 L min-1 removes covalently bound thin organic films, attached via electrografting from aryldiazonium salt solutions. The heat-treated surfaces exhibit improved electrochemical characteristics compared to those prior to modification and can be re-used for solution-based electrochemical measurements and for electrografting. The same treatment reactivates PPF electrodes that have been deactivated by exposure to adsorbates from air or solution. X-ray photoelectron spectroscopy (XPS), atomic force microscopy and water contact angle measurements establish that the regeneration procedure does not lead to significant changes in oxygen content, roughness or hydrophobicity of PPF surfaces. XPS measurements also confirm the complete removal of covalently attached organic films after heat treatment, but reveal a specific interaction between grafted nitrophenyl films and PPF which results in a small amount of N incorporation in the surface.

Osmium bipyridine complexes were directly grafted to carbon electrodes through electroreduction of the diazonium salts [Os(bpy-ph-N 2 + ) 3 ](PF 6 ) 5 ( 1 ) and [Os(bpy-ph-N 2 + ) 2 Cl 2 ](PF 6 ) 2 ( 2 ). Growth of the films was not self-limiting as is usually found for grafting from diazonium salts. It appears that electron hopping through the bipyridine ligands of the immobilised complexes enables film growth to continue at a constant rate during grafting by potential cycling. The surface concentrations of deposited films were measured electrochemically and the film thicknesses were measured by depth-profiling using the atomic force microscope. Films up to 42 nm thick were prepared with no evidence for slowing of film growth. The grafted films exhibited high stability when repetitively cycled through the Os 2+/3+ couple and electron transfer rate constants of 11.4 s −1 and 35.4 s −1 were measured in ACN and PBS, respectively, for the Os 2+/3+ couple of the film grafted from 1 .

A multiwalled carbon nanotube/chitosan modified glassy carbon electrode (MWCNTs-CHT/GCE) has been used for simultaneous determination of paracetamol (PAR) and uric acid (UA). The measurements were carried out using differential pulse voltammetry (DPV), cyclic voltammetry (CV) and chronoamperometry (CA). DPV measurements showed a linear relationship between oxidation peak current and concentration of PAR and UA in phosphate buffer (pH 7) over the concentration range 2 µM to 250 µM, and 10 µM to 400 µM, respectively. The analytical performance of this sensor has been evaluated for detection of PAR and UA in human serum and human urine with satisfactory results.

Diazonium ion chemistry has been used to electrochemically graft aminophenyl layers onto p-type silicon (1 0 0) substrates. A condensation reaction was used to immobilise single-walled carbon nanotubes with high carboxylic acid functionality directly to this layer. Electrochemical monitoring of the aminophenyl groups confirmed the formation of an amide linkage between the single-walled carbon nanotubes and the aminophenyl layer. The carbon nanotube electrode showed high stability and good electrochemical performance in aqueous solution. At moderate scan rates the Ru(NH3)6+3/+2 couple exhibited quasi-reversible electron transfer kinetics with a standard heterogenous rate constant of 1.2 × 10−3 cm s−1 at the covalently-linked carbon nanotube surface. The electrode thus combines the advantages of a silicon substrate for easy integration into sophisticated electrical and electronic devices, carbon nanotubes for desirable electrochemical properties, and stability in aqueous medium for future applications in environmental sensing.

The electrochemistry of self-assembled monolayers (SAMs) on gold containing a lipoic acid linker, the beta-peptide sequence (beta(3)Val-beta(3)Ala-beta(3)Leu)(n) for n = 1, 2, and a terminal ferrocenyl group has been described for the first time. Circular dichroism (CD), NMR, and molecular modeling were used to evaluate the beta-peptide structure in solution, while the monolayer film organization and electron-transfer kinetics were evaluated by cyclic voltammetry, chronoamperometry (CA), and ellipsometry. The peptides were assembled from trifluoroethanol solutions, where they are linear (n = 1) or helical (n = 2) based on CD, NMR, ellipsometry, and modeling evidence. The structure of the SAMs is less well understood. There is evidence for noncompact layers that allow electrolyte ions to approach the interface. Electron-transfer rates for n = 1, 2 were found to be 2500 and 1200 s(-1), respectively, and CA evidence indicated that the transfer is based on the hopping mechanism.

Forests of vertically aligned carbon nanotubes (VACNTs) have been chemically assembled on carbon surfaces. The structures show excellent stability over a wide potential range and are resistant to degradation from sonication in acid, base, and organic solvent. Acid-treated single-walled carbon nanotubes (SWCNTs) were assembled on amine-terminated tether layers covalently attached to pyrolyzed photoresist films. Tether layers were electrografted to the carbon substrate by reduction of the p-aminobenzenediazonium cation and oxidation of ethylenediamine. The amine-modified surfaces were incubated with cut SWCNTs in the presence of N,N'-dicyclohexylcarbodiimide (DCC), giving forests of vertically aligned carbon nanotubes (VACNTs). The SWCNT assemblies were characterized by scanning electron microscopy, atomic force microscopy, and electrochemistry. Under conditions where the tether layers slow electron transfer between solution-based redox probes and the underlying electrode, the assembly of VACNTs on the tether layer dramatically increases the electron-transfer rate at the surface. The grafting procedure, and hence the preparation of VACNTs, is applicable to a wide range of materials including metals and semiconductors.

The reaction of gold substrates with p-nitrobenzene diazonium tetrafluoroborate (NBD) in 0.1 M H(2)SO(4) at open-circuit potential (OCP) is demonstrated to proceed by electron transfer from gold to the NBD cation. Electrochemical, atomic force microscopy, and X-ray photoelectron spectroscopy analyses reveal the formation of multilayer films with the same composition as electrografted films. The film growth characteristics (surface concentration and film thickness vs time) also follow those observed during electrografting, consistent with electron transfer from the substrate to the diazonium cation. The OCP of the gold substrate increases during the period of film growth ( approximately 60 min) and then decreases to close to its initial value. The increase corresponds to accumulation of positive charge as electrons are transferred to NBD; the discharge process is tentatively attributed to slow oxidation of adventitious impurities in the reaction solution. Films formed at OCP or by electrografting from aqueous acid solution are markedly less stable to sonication in acetonitrile than are those electrografted from acetonitrile. Increased amounts of physisorbed material in films prepared in aqueous media or bonding of aryl groups to different gold sites in the two media are tentatively proposed to account for the different stabilities.

Uniform, vertically aligned multiwalled carbon nanotube arrays (VACNTs) were grown on glassy carbon-like thin films by thermal chemical vapour deposition (CVD). Thin (5 nm) aluminum and iron catalyst layers were pre-deposited by evaporation on the carbon substrates and VACNTs were grown at 750 °C by water-assisted CVD using ethylene as the carbon source. The aluminum layer was shown to be essential for aligned nanotube growth. VACNT arrays adhered strongly to the carbon film with low contact resistance between the VACNTs and the substrate. The VACNT arrays grown directly on the planar conducting carbon substrate have attractive properties for use as electrodes. Excellent voltammetric characteristics are demonstrated after insulating the arrays with a dielectric material.

A straightforward procedure is described for preparation of arrays of microdisk electrodes comprising bundles of vertically aligned carbon nanotubes (VACNTs). The arrays are fabricated by thermal chemical vapor deposition synthesis directly on a planar carbon film support. Use of standard micro- and nanolithography procedures for patterning the bilayer catalyst spots enables arrays to be grown with controlled electrode diameters and spacings. The minimum accessible VACNT bundle diameter, and hence microelectrode diameter, is 2 microm. After insulating the arrays with SU-8 epoxy and exposing the VACNT ends by polishing or treating with O2 plasma, the microdisk electrodes exhibit attractive electrochemical properties.

The increased use of pyrolysed photoresist films (PPF) as electrode material intensifies the need to know what fabrication variables are important in the pyrolysis process. The main factor effects of seven variables (three time/temperature heating levels plus the position in the furnace tube) in the fabrication of PPF were investigated by a Plackett and Burman, eight-run, experimental design. In the three-step pyrolysis programme, gas flow had a large effect on the surface cleanliness and roughness. It was also observed that the position in the furnace affected the resistivity of the PPF. Fabrication parameters that give rapid electron transfer to redox species in solution, that provide low surface oxide and that lead to low surface roughness were identified. The guidelines on what fabrication conditions to employ to give a variety of different electrode characteristics are presented.

A new strategy for preparation of robust multifunctional low nanometer thickness monolayers on carbon substrates is presented. Beginning with protected aryldiazonium salts, sparse monolayers of ethynyl-, amino-, and carboxy-terminated tethers are covalently anchored to the surface. The layers are then backfilled with a second modifier via the nucleophilic addition of an amine derivative to the surface. Through use of electroactive moieties coupled to the tethers, and an electroactive amine for backfilling, electrochemical measurements reveal that backfilling approximately doubles the surface concentration of the monolayer. Cyclic voltammetry of solution-based redox probes at the modified surfaces is consistent with the expected blocking properties at various stages of surface preparation. Fractional surface coverages of the layers are estimated using electrochemically determined surface concentrations of modifiers and computationally derived modifier footprints. Assuming free rotation of the coupled ferrocenyl or nitrophenyl groups leads to physically unreasonable fractional surface coverages, indicating that these larger modifiers must be rotationally restricted. Using a conformationally constrained model produces lower bound estimates of the total fractional surface coverage close to 0.4, with tether-only coverages close to 0.2. The backfilled tether layers constitute practical platforms for controlled construction of complex interfaces with many potential applications including sensing, molecular electronics, and catalysis.

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.

The electrochemical response of solution-based redox probes is commonly used to detect and monitor the formation and stability of films grafted to conducting substrates. In this work we examine redox probe responses at films grafted to glassy carbon (GC) and pyrolysed photoresist film (PPF) by electrooxidation of aliphatic primary amines. Cyclic voltammograms are obtained before and after soaking the modified surfaces in phosphate buffer and acetonitrile. For conditions where films exhibit large changes in electrochemical blocking properties, AFM measurements of film thickness and surface roughness, and XPS measurements of surface composition, are used to monitor the stability of the films. No changes in film structure or composition can be detected, demonstrating that electrochemical loss of blocking properties cannot be equated with large-scale loss of surface film. The origin of changes in probe response is discussed. Keywords: Amine oxidation, Surface modification, AFM depth profiling, Film permeability

The structure and properties of thin organic films electrografted to conducting surfaces by reduction of the corresponding diazonium salts are not well understood. In this work we used electrochemistry and contact angle measurements to characterize multilayer carboxyphenyl and methylphenyl films grafted to Au surfaces. Freshly grafted films contain material that can be readily removed during potential cycling and sonication. Observation of Au oxide surface electrochemistry confirms a porous bulk film structure as previously found for films electrografted to carbon surfaces. The charge associated with Au oxide reduction was used to estimate the upper limit for surface concentration of modifiers directly attached to the surface after careful preparation of the Au surface prior to and after grafting. Values for the surface concentration of the modifier in the range of 3−4 × 10-10 mol cm-2 indicate that the first layer of the films is loosely packed. The close correspondence of surface concentration with that...

Natural fibres represent a readily available source of ecologically friendly and inexpensive reinforcement in composites with degradable thermoplastics, however chemical treatments of fibres are required to prepare feasible composites. It is desirable to characterize the surface wettability of fibres after chemical treatment as the polarity of cellulose-based fibres influences compatibility with a polymer matrix. Assessment of the surface wettability of natural fibres using conventional methods presents a challenge as the surfaces are morphologically and chemically heterogeneous, rough, and can be strongly wicking. In this work it is shown that under atmospheric conditions the adhesion force between an atomic force microscopy (AFM) tip and the fibre surface can estimate the water contact angle and surface wettability of the fibre. AFM adhesion force measurements are suitable for the more difficult surfaces of natural fibres and in addition allow for correlations between microstructural features and surface wettability characteristics.

Aminophenyl and aminomethylphenyl monolayers have been electrografted to glassy carbon and pyrolyzed photoresist film from the corresponding diazonium ions using a protection–deprotection strategy based on Boc (tert-butyloxycarbonyl) and Fmoc (fluorenylmethyloxycarbonyl) groups. After grafting and then deprotecting films of Boc-NH-Ar, Fmoc-NH-Ar, and Fmoc-NH-CH2-Ar, depth profiling by atomic force microscopy confirmed that the resulting amine-terminated films were monolayers. In contrast, after deprotection, Boc-NH-CH2-Ar gave a multilayer film. Electroactive carboxylic acid derivatives were coupled to the monolayers through amide linkages. Electrochemical measurements revealed that the deprotected Fmoc-NH-CH2-Ar monolayer gave the highest surface concentration of coupled nitrophenyl and ferrocenyl groups and DFT calculations established that this monolayer has the highest theoretical surface concentration of those examined.

We have demonstrated three simple strategies employing poly(dimethylsiloxane) (PDMS) molds for patterning carbon surfaces with two different modifiers in an 18 microm line pattern. The PDMS molds are patterned with microfluidic channels (approximately 22 microm wide and 49 microm deep) and form a reversible, conformal seal to the pyrolyzed photoresist film (PPF) and modified PPF surfaces. Modifiers are electrochemically grafted to the PPF surface by the reduction of aryl diazonium salts and the oxidation of primary amines. For the fill-in patterning approach, the first modifier is electrografted to the PPF surface exposed within the microchannels, and in a second grafting step after removal of the PDMS mold, the second modifier fills in the remaining surface. The selective conversion strategy involves electrografting a continuous film of the modifier to the PPF surface, sealing the PDMS mold to the modified surface and carrying out an irreversible electrochemical reaction of the modifier exposed within the microchannels. In the build-up patterning approach, the PDMS mold is sealed to the modified PPF surface, and a chemical coupling reaction is effected in the microchannels to build up the pattern. The patterns are characterized using SEM, optical microscopy, the formation of condensation figures, and SEM imaging after the assembly of Au nanoparticles.

Arylmethyl films have been grafted to glassy carbon surfaces and to pyrolyzed photoresist films (PPFs) by electrochemical oxidation of 1-naphthylmethylcarboxylate and 4-methoxybenzylcarboxylate. Atomic force microscopy (AFM) and electrochemistry were used to characterize the as-prepared films and to monitor changes induced by post-preparation treatments. Film thickness was measured by depth profiling using an AFM tip to remove film from the PPF surface. Surface coverage of electroactive modifiers was estimated from cyclic voltammetry, and monitoring the response of a solution-based redox probe at grafted surfaces gave a qualitative indication of changes in film properties. For preparation of the films, the maximum film thickness increased with the potential applied during grafting, and all films were of multilayer thickness. The apparent rate of electron transfer for the Fe(CN)(6)3-/Fe(CN)(6)4- couple was very low at as-prepared films. After film-grafted electrodes were transferred to pure acetonitrile-electrolyte solution and subjected to negative potential excursions, the response of the Fe(CN)(6)3-/Fe(CN)(6)4- couple changed and was consistent with faster electron-transfer kinetics, the film thickness decreased and the surface roughness increased substantially. Applying a positive potential to the treated film reversed changes in film thickness, but the voltammetric response of the Fe(CN)(6)3-/Fe(CN)(6)4- couple remained kinetically fast. After as-prepared films were subjected to positive applied potentials in acetonitrile-electrolyte solution, the apparent rate of electron transfer for the Fe(CN)(6)3-/Fe(CN)(6)4- couple remained very slow and the measured film thickness was the same or greater than that before treatment at positive potentials. Mechanisms are considered to explain the observed effects of applied potential on film characteristics.

Nitroazobenzene films have been grafted to pyrolyzed photoresist films by electrochemical reduction of the corresponding diazonium salt in acetonitrile solution. Two component films were also prepared by electrochemically grafting methylbenzene layers to preformed NAB films. Voltammetric investigation of the films in aqueous acid medium and the measurement of film thickness using atomic force microscopy (AFM) lead to new insights into film structure. In aqueous acid solution, the azobenzene groups have no detectable electroactivity and not all nitro groups in the films can be reduced. These findings point to a compact film structure in which proton diffusion is limited. There may also be spatial inhibition of the conformational changes that accompany azobenzene reduction. For increasingly thick NAB films, the peak for reduction of the nitro groups moves to more negative potentials and the peaks become more asymmetric in shape. These changes are interpreted in terms of the dielectric properties and the rate of proton diffusion in the films. Film thickness was measured by ploughing through the film with an AFM tip. When an NAB film prepared in acetonitrile solution is reduced in aqueous acid, the film thickness decreases by more than 50%. The changes can be partially reversed by treatment in acetonitrile-electrolyte solution and hence are attributed to ion-solvent induced swelling and shrinking. Thus, the large decrease in thickness detected by AFM after treatment of the film in aqueous acid is consistent with the compact film structure revealed by electrochemistry.