Electrowetting measurements with mercury showing mercury/mica interfacial energy depends on charging

We demonstrate that the interfacial energy between mercury and mica is a function of charge on the mercury surface, decreasing with increasing positive charge. The contact angle of mercury on mica has been measured as a function of potential applied to the mercury, which forms the working electrode of a cell containing either KC1 or NaF electrolyte solution. At high negative applied potentials, a stable aqueous film exists between the mercury and mica surface. As potential is made less negative, the film collapses and mercury partial1 wets the mica at a critical potential, close to the electrocapillary maximum. Upon increasing the potential further (making the Hg surface more and more positive), the contact angle measured within the mercury continually decreases. Electrowetting with mercury is not unexpected since its interfacial tension with the aqueous phase is known to be a function of applied potential. However, the observed decrease goes against the trend expected from the Young equation if only this effect is considered. To explain the data we must allow the mercury/mica interfacial tension also to vary with applied potential. This variation indicates that the mercury surface is positively charged by contact with mica, consistent with known contact electrification between these two materials. The inherent charges at the mercury interfaces with mica and electrolyte solution result in contact angle changes of some tens of degrees with a change in applied potential of half a volt orders of magnitude less than the potentials required to effect comparable changes in other electrowetting systems.

Adsorptive potentiometric stripping analysis of nucleic acids at mercury electrodes

The application of adsorptive stripping potentiometry to the reductive detection of nucleic acids at mercury electrodes is reported. Compared to analogous voltammetric stripping modes, constant current potentiometric stripping analysis (PSA) effectively addresses the hydrogen discharge background problem, and hence greatly improves the characteristics of the superimposed cytosine/adenine (CA) reduction peak. Compared to earlier schemes for trace measurements of nucleic acids at mercury or carbon electrodes that rely on anodic signals arising from the guanine residue, convenient quantitation can now be carried out in connection with the cytosine and adenine residues. Variables influencing the adsorptive PSA response are explored and optimized. With five minute accumulation, the detection limits for tRNA, ssDNA and dsDNA are 30 mu g l(-1), 60 mu g l(-1) and 2 mg l(-1), respectively. Such different values reflect the strong dependence of the PSA CA signal upon the nucleic-acid structure. This allows the quantitation of ssDNA or tRNA in the presence of dsDNA, and offers new possibilities for electrochemical studies of DNA structure and interactions.

Modification of glassy carbon electrodes with a poly-L-lysine/glutaraldehyde film

A film of poly-L-lysine (PLL) adheres better to the surface of a glassy carbon electrode when the PLL is partially cross-linked by means of glutaraldehyde. A film composition of 97.5% PLL/2.5% glutaraldehyde gives good adhesion and retains the anionic exchange capability of the PLL. The performance of the film was tested with hexacyanoferrate(III) using electrochemical and nonelectrochemical accumulation.

Film formation and surface growth on tin electrodes in bicarbonate solutions: an impedance spectroscopy study

The electrochemical behaviour of potentiodynamically formed thin anodic films of polycrystalline tin in aqueous sodium bicarbonate solutions (pH approximate to 8.3) were studied using cyclic voltammetry and electrochemical impedance spectroscopy. Different equivalent circuits corresponding to various potential regions were employed to account for the electrochemical processes taking place under each condition. (C) 2004 Elsevier Ltd. All rights reserved.

Gold electrodes from recordable CDs for mercury quantification by flow injection analysis

The development of a new methodology for the construction of very efficient flow cells for mercury detection by potentiometric stripping analysis, employing the thin gold layer of recordable CDs as working electrode is reported. This new source of electrodes (CDtrodes) show very attractive performance, similar to that obtained with commercial gold electrodes, with superior versatility. The low cost of this new source of gold electrodes allows a frequent replacement of the electrode, avoiding cumbersome clean-up treatments. Various experimental parameters have been optimized to yield low detection limits (0.25 ng/mL of mercury for 5 min deposition at 0.3 V) and good precision (standard deviation of 1.9% was obtained for 15 repetitive measurements using 10 ng/mL of mercury). Standard curves were found to be linear over the range of 0.5-100 μg L-1 of mercury. The flow cells developed were used for the quantification of mercury in oceanic and tap water. © Springer-Verlag 2000.

Mercury determination in urine samples by gold nanostructured screen-printed carbon electrodes after vortex-assisted ionic liquid dispersive liquid–liquid microextraction

A novel approach is presented to determine mercury in urine samples, employing vortex-assisted ionic liquid dispersive liquid–liquid microextraction and microvolume back-extraction to prepare samples, and screen-printed electrodes modified with gold nanoparticles for voltammetric analysis. Mercury was extracted directly from non-digested urine samples in a water-immiscible ionic liquid, being back-extracted into an acidic aqueous solution. Subsequently, it was determined using gold nanoparticle-modified screen-printed electrodes. Under optimized microextraction conditions, standard addition calibration was applied to urine samples containing 5, 10 and 15 μg L−1 of mercury. Standard addition calibration curves using standards between 0 and 20 μg L−1 gave a high level of linearity with correlation coefficients ranging from 0.990 to 0.999 (N = 5). The limit of detection was empirical and statistically evaluated, obtaining values that ranged from 0.5 to 1.5 μg L−1, and from 1.1 to 1.3 μg L−1, respectively, which are significantly lower than the threshold level established by the World Health Organization for normal mercury content in urine (i.e., 10–20 μg L−1). A certified reference material (REC-8848/Level II) was analyzed to assess method accuracy finding 87% and 3 μg L−1 as the recovery (trueness) and standard deviation values, respectively. Finally, the method was used to analyze spiked urine samples, obtaining good agreement between spiked and found concentrations (recovery ranged from 97 to 100%).

Mercury vapor sorption and amalgamation with a thin gold film

Understanding the amalgamation mechanisms between mercury and gold is of fundamental interest and importance to many mercury sensing applications. However, there is only limited and piecemeal discussion in the literature of the mechanisms by which Au-Hg amalgams are formed on thin Au films. Here, we present a comprehensive description of a series of morphological changes occurring in a thin polycrystalline Au film during Au-Hg amalgamation investigated by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and atomic force microscopy (AFM). These microscopic investigations enable us to offer a coherent explanation for the features and the mechanisms of amalgamation of Hg with Au in the film. We also use an optical technique (fringes of equal chromatic order, FECO) to observe changes in optical thickness and reflectivity of the film. Amalgamation reactions in the film render it inhomogeneous, thus making optical techniques unsuitable as a method for quantitative monitoring of Hg vapor using Au films of this type.

Low temperature synthesis of carbon nanotubes on indium tin oxide electrodes for organic solar cells

The electrical performance of indium tin oxide (ITO) coated glass was improved by including a controlled layer of carbon nanotubes directly on top of the ITO film. Multi-wall carbon nanotubes (MWCNTs) were synthesized by chemical vapor deposition, using ultra-thin Fe layers as catalyst. The process parameters (temperature, gas flow and duration) were carefully refined to obtain the appropriate size and density of MWCNTs with a minimum decrease of the light harvesting in the cell. When used as anodes for organic solar cells based on poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM), the MWCNT-enhanced electrodes are found to improve the charge carrier extraction from the photoactive blend, thanks to the additional percolation paths provided by the CNTs. The work function of as-modified ITO surfaces was measured by the Kelvin probe method to be 4.95 eV, resulting in an improved matching to the highest occupied molecular orbital level of the P3HT. This is in turn expected to increase the hole transport and collection at the anode, contributing to the significant increase of current density and open circuit voltage observed in test cells created with such MWCNT-enhanced electrodes.

A high mobility P-type DPP-thieno[3,2-b]thiophene copolymer for organic thin-film transistors

A copolymer comprising 1,4-diketopyrrolo[3,4-c]pyrrole (DPP) and thieno[3,2-b]thiophene moieties, PDBT-co-TT, shows high hole mobility of up to 0.94 cm2 V-1 s-1 in organic thin-film transistors. The strong intermolecular interactions originated from π-π stacking and donor-acceptor interaction lead to the formation of interconnected polymer networks having an ordered lamellar structure, which have established highly efficient pathways for charge carrier transport.

Solution processable poly(2,5-dialkyl-2,5-dihydro-3,6-di-2-thienyl- pyrrolo[3,4-c]pyrrole-1,4-dione) for ambipolar organic thin film transistors

Solution processable diketopyrrolopyrrole (DPP)-bithiophene polymers (PDBT) with long branched alkyl side chains on the DPP unit are synthesized. These polymers have favourable highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels for the injection and transport of both holes and electrons. Organic thin film transistors (OTFTs) using these polymers as semiconductors and gold as source/drain electrodes show typical ambipolar characteristics with very well balanced high hole and electron mobilities (μ h = 0.024 cm 2 V -1 s -1 and μ e = 0.056 cm 2 V -1 s -1). These simple and high-performing polymers are promising materials for ambipolar organic thin film transistors for low-cost CMOS-like logic circuits.

Graphene-based supercapacitor with carbon nanotube film as highly efficient current collector

Flexible graphene-based thin film supercapacitors were made using carbon nanotube (CNT) films as current collectors and graphene films as electrodes. The graphene sheets were produced by simple electrochemical exfoliation, while the graphene films with controlled thickness were prepared by vacuum filtration. The solid-state supercapacitor was made by using two graphene/CNT films on plastic substrates to sandwich a thin layer of gelled electrolyte. We found that the thin graphene film with thickness <1 μm can greatly increase the capacitance. Using only CNT films as electrodes, the device exhibited a capacitance as low as ~0.4 mF cm−2, whereas by adding a 360 nm thick graphene film to the CNT electrodes led to a ~4.3 mF cm−2 capacitance. We experimentally demonstrated that the conductive CNT film is equivalent to gold as a current collector while it provides a stronger binding force to the graphene film. Combining the high capacitance of the thin graphene film and the high conductivity of the CNT film, our devices exhibited high energy density (8–14 Wh kg−1) and power density (250–450 kW kg−1).