A rapidly-reversible absorptive and emissive vapochromic Pt(II) pincer-based chemical sensor.

Selective, robust and cost-effective chemical sensors for detecting small volatile-organic compounds (VOCs) have widespread applications in industry, healthcare and environmental monitoring. Here we design a Pt(II) pincer-type material with selective absorptive and emissive responses to methanol and water. The yellow anhydrous form converts reversibly on a subsecond timescale to a red hydrate in the presence of parts-per-thousand levels of atmospheric water vapour. Exposure to methanol induces a similarly-rapid and reversible colour change to a blue methanol solvate. Stable smart coatings on glass demonstrate robust switching over 104 cycles, and flexible microporous polymer membranes incorporating microcrystals of the complex show identical vapochromic behaviour. The rapid vapochromic response can be rationalised from the crystal structure, and in combination with quantum-chemical modelling, we provide a complete microscopic picture of the switching mechanism. We discuss how this multiscale design approach can be used to obtain new compounds with tailored VOC selectivity and spectral responses.

Fabrication of shuttle-junctions for nanomechanical transfer of electrons.

We report on the fabrication of nanomechanical devices for shuttling of electrons from one electrode to another. Each device consists of a 20 nm diameter gold nanoparticle embedded within the gap between two gold electrodes. In two different kinds of shuttle-junctions the nanoparticle is attached to the electrodes through either (i) a single layer of 1,8-octanedithiol or (ii) a multilayer of 1-octanethiol molecules. The thiol layers play the role of 'damped springs', such that when a sufficient voltage bias is applied to the junction, the nanoparticle is expected to start oscillating and thereby transferring electrons from one electrode to the other. For both kinds of shuttle-junctions we observed an abrupt increase in the transmitted current above a threshold voltage, which can be attributed to a transition from the stationary to the oscillating regime. The threshold voltage was found to be lower for single-layer shuttle-junctions.

Nanocomposite electrodes made of carbon nanofibers and black wax. Anodic stripping voltammetry of zinc and lead.

Nanocomposite electrodes offer exciting new possibilities in electroanalytical chemistry. In this preliminary study, nanocomposite electrodes made of carbon nanofibers and black wax were characterized and investigated as novel substrates for metal deposition and stripping processes. Carbon nanofibers were grown from ethylene-hydrogen gas mixtures over Fe-Ni-Cu (85:10:5) nanoparticle catalysts at 600 degrees C and then embedded in Apiezon black wax under vacuum at 140 degrees C. The resulting nanocomposite electrodes showed (i) good conductivity, (ii) a wide potential window in aqueous solutions, (iii) low background currents, (iv) near steady state voltammetric responses with substantial Faradaic currents and (v) sharply peaked fast scan metal stripping responses. Zinc is a notoriously difficult metal to determine in aqueous solutions, because its deposition and stripping are accompanied by hydrogen evolution at extreme negative potentials. It therefore provided a challenging test for our new nanocomposite electrode. Although numerous complications associated with the hydrogen evolution process could not be eliminated, remarkably clear voltammograms could be obtained even at scan rates of 40 V s(-1).

Directed assembly of multilayers--the case of Prussian blue.

We introduce the concept of 'directed assembly' of multilayers on surfaces: the overall process involves the exposure of a surface to a series of solutions containing, alternately, adsorbable cations and adsorbable anions, and these are gradually built up into well-defined multilayer structures.

Laser activation voltammetry: selective removal of reduced forms of methyl viologen deposited on glassy carbon and boron-doped diamond electrodes

The effect of high-intensity laser pulses on the reduction of methyl viologen at glassy carbon electrodes in aqueous solution is investigated using laser activation voltammetry (LAV) under both channel flow and no-flow conditions and compared with the effect of conventional variable-temperature voltammetry. The reduction proceeds in two consecutive one-electron steps, and the neutral two-electron-reduction product of methyl viologen is shown by voltammetry and in situ optical microscopy to form two types of deposits, amorphous and crystalline, on the electrode surface. Laser activation voltammetry using a 10 Hz pulsed Nd-YAG 532 nm laser is shown to remove the deposits from the electrode surface at different laser intensities: the amorphous material is more easily ablated than the crystalline deposit. By conventional variable-temperature voltammetry, it is shown that the two stripping peaks disappear as the temperature is increased. However, with conventional heating, the opposite ease of removal is detected compared to the case of laser activation voltammetry: the stripping response associated with the crystalline material disappears at lower temperatures compared to that for the amorphous material. In the presence of high-intensity laser pulses (>0.17 W cm(-2)), glassy carbon surfaces are damaged and the voltammetric characteristics become poor. It is shown that, by the employment of a thin-film boron-doped diamond electrode grown using a chemical vapor deposition procedure on a tungsten substrate, much higher laser intensities can be applied and well-defined LAV signals can be obtained without deactivation of the electrode.

Sonoelectrochemical and sonochemical effects of cavitation: correlation with interfacial cavitation induced by 20 kHz ultrasound.

Sonoelectrochemical measurements at macro-electrodes under extreme conditions with a very short distance between ultrasonic horn tip and electrode and different ultrasound intensity levels are shown to result in violent cavitation detected in form of current peaks superimposed on the average limiting current. Analysis of the current data obtained for the oxidation of ferrocene in dimethylformamide (0.1 M NBu4PF6) at a 4 mm diameter Pt disc electrode and for the reduction of Ru(NH3)6(3+) in aqueous 0.1 M KCl at a 6 mm diameter Pt disc electrode consistently indicate a change of the physicochemical nature of sonoelectrochemical processes under extreme conditions. The sonoelectrochemical measurement of the rate constant for the carbon bromide bond cleavage of a 3-bromobenzophenone radical anion electrogenerated at a glassy carbon electrode in dimethylformamide solution in the presence of power ultrasound is shown to yield evidence for a breakdown of the conventional mass transport model of a planar diffusion layer under extreme conditions. The change can be correlated to the number of current data points deviating more than 10% from the mean of the current due to violent cavitation processes superimposed onto the average limiting current. Further, a study of the sonochemical destruction of aqueous dilute cyanide solution (in 0.1 M NaOH) demonstrates a correlation between the electrochemically detected cavitation violence and the sonochemical activity. Factors that govern the violence of interfacial cavitation appear to be directly proportional to the factors that make cavitation in the bulk solution chemically efficient.

Sonoelectrochemical investigation of silver analysis at a highly boron-doped diamond electrode.

A study into the sonoelectroanalysis of silver at a highly boron-doped diamond electrode is presented, exploring the benefits of the introduction of power ultrasound and new electrode materials into classical electrochemical techniques. Both cathodic and anodic stripping voltammetry have been investigated in terms of their analytical suitability towards silver detection. Cathodic stripping voltammetry, via electrodeposited silver oxide, was affected by the unusual chemistry of the highly oxidising Ag(2+) species and the characterisation of this system is discussed in detail. Anodic stripping, via deposition of metallic silver on the bare boron-doped diamond electrode surface under ultrasound, coupled with square-wave voltammetry, was successfully employed in the development of a sensitive technique for the analysis of trace silver ions. A detection limit for Ag(+) of 10(-9) M for a 300-s deposition, with a linear range of at least two orders of magnitude, and the beneficial effects of controlling the speciation of Ag(+) via complexation with chloride ions are reported.

Ultrasound in photoelectrochemistry: a new approach to the enhancement of the efficiency of semiconductor electrode processes.

A novel photoelectrochemical experiment which simultaneously allows the illumination of a TiO2 semiconductor electrode surface and the application of power ultrasound emission is described. The horn probe of an immersion horn transducer is modified by an oxide coated titanium tip and placed in a conventional three electrode electrochemical cell which allows light from a monochromated source to be focussed onto the electrode surface. Well-defined photocurrents are observed in aqueous media and for the photoinduced oxidation of water in acetonitrile and of 2.4-dichlorophenol in acetonitrile. The effect of ultrasound is to shift the observed photocurrent responses to more negative potentials and therefore to enhance the observed processes. Several possible interpretations associated with the complex effects induced by ultrasound are considered and a model based mainly on the extreme change of mass transport at the semiconductor/solution interface is suggested. Considerably enhanced performance for non-Nernstian processes, such as those observed in photoelectrochemical reactions at semiconductor electrodes, can be achieved in the presence of ultrasound.

A novel approach for the quantitative kinetic study of reactions at solid/liquid interfaces in the presence of power ultrasound.

A novel cell and procedure is described which permits the quantitative mechanistic study of ultrasonically enhanced reactions which occur at solid/liquid interfaces. A model of a controlled and calculable time-average rate of mass transport to and from the interface is used in order to compare experimental results with theoretical predictions based on mechanistic reaction schemes. In this way concentrations of mechanistically significant species near the interface can be related to those in bulk solution and hence the sonochemical effects of ultrasound dissected from those arising purely from mass transport. The effect of ultrasound is demonstrated for the reaction dissolution of p-chloranil in the presence of aqueous base and for the reaction of the same substrate with the aromatic amine, N,N-dimethyl-phenylenediamine, both systems which have been studied previously in the absence of ultrasound. Complementary atomic force microscopy images are also reported.