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31.
The deposition of PbO2 on platinum and glassy carbon electrodes was investigated experimentally. The comparison of the different behaviour on the two types of electrodes is presented. The effects of variation of temperature, potential, nucleation order and induction time-lags on the electrocrystallisation process are discussed.The present investigations have confirmed that electrocrystallisation of PbO2 occurs through 3-D nucleation and growth on glassy carbon and most probably also on platinum. The data on platinum contains considerable noise from simultaneous chemical processes and is not amenable for analysis in a simple way. The steady state behaviour is unusual because it has generally been assumed that charge transfer is rate determining under most conditions. However, as shown here, if lattice incorporation is slow even at the steady state, it provides a method for separating the activation energies associated with the nucleation and growth rate constants. Finally, the dissolution of PbO2 into the platinum substrate and its implication on transient rates merits more attention. In this context the Pt-PbO2 system is probably not a good choice because of the large contribution of substrate oxidation to the measured transient rates.  相似文献   
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Photoluminescence studies on porous silicon show that there are luminescence centers present in the surface states. By taking photoluminescence spectra of porous silicon with respect to temperature, a distinct peak can be observed in the temperature range 100–150 K. Both linear and nonlinear relationships were observed between excitation laser power and the photoluminescence intensity within this temperature range. In addition, there was a tendency for the photoluminescence peak to red shift at low temperature as well as at low excitation power. This is interpreted as indicating that the lower energy transition becomes dominant at low temperature and excitation power. The presence of these luminescence centers can be explained in terms of porous silicon as a mixture of silicon clusters and wires in which quantum confinement along with surface passivation would cause a mixing of andX band structure between the surface states and the bulk. This mixing would allow the formation of luminescence centers.  相似文献   
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The limit of detection for the 4,6 dinitro-orthocresol (DNOC) pesticide, including small latex particles as light scattering samples in water as suspending medium, has been determined for the transversal photothermal deflection technique. The results where compared to conventional spectrophotometry. In the photothermal deflection experiments performed with a continuous Ar+-excitation beam (=363.8 nm) a LOD of 0.8 g/l is achieved for the DNOC in water.Awarded poster prize  相似文献   
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Li QG  Xu JG  Huang XZ  Chen GZ 《Talanta》1994,41(12):2049-2054
The effects of media properties including buffers, acidity, solvents and surfactant on horseradish peroxidase-catalyzed fluorogenic reaction were investigated. The results showed that the so-called non-fluorescent hydrogen donors were in fact fluorescent. There existed an acid—base equilibrium in the fluorescent dimer product. For p -hydroxyphenylpropionic acid, a pKa value of 8.0 for the product was obtained from its titration curve. The product fluorescence increased with higher pH, however, a longer time was needed to reach the reaction equilibrium due to the pH mismatch problem. Cationic micelles cetyltrimethylammonium bromide and cetyltrimethylammonium chloride could reduce the pH mismatch and offered a way to further increase the determination sensitivity. Finally, a micelle-enhanced flow-injection analysis of horseradish peroxidase is suggested.  相似文献   
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