The development of redox-modified electrodes as charge-accumulating devices for use in higher sensitivity detection systems

Electrochemical methods can be applied in a number of ways as detection systems for competitive immunoassays, especially through the use of redox-labelled antigens. To overcome the problem of detection of such conjugates at low concentration, a system is described in which a poly(vinylferrocene)-modified glassy carbon electrode is used to accumulate charge from solution glucose/glucose oxidase via the intermediacy of a redox-labelled antigen, cycled repeatedly between the enzyme and the electrode. The charge accumulated by the electrode is measured electrochemically by returning the electrode to its original potential and integrating the resulting current-time transient. The charge is proportional to the concentration of redox-labelled antigen in solution and to the charge-accumulation time. In this way 1,1'-dimethylferrocene-ethan-1-ol-2-amine was reproducibly detected to 0.9 nM, with a 10 min incubation period. The 8-ferrocenyl conjugate of theophylline was characterised as a model system for possible application in a higher sensitivity electrochemical immunoassay.     

The Hamiltonian structure of general relativistic perfect fluids

We show that the evolution equations for a perfect fluid coupled to general relativity in a general lapse and shift, are Hamiltonian relative to a certain Poisson structure. For the fluid variables, a Lie-Poisson structure associated to the dual of a semi-direct product Lie algebra is used, while the bracket for the gravitational variables has the usual canonical symplectic structure. The evolution is governed by a Hamiltonian which is equivalent to that obtained from a canonical analysis. The relationship of our Hamiltonian structure with other approaches in the literature, such as Clebsch potentials, Lagrangian to Eulerian transformations, and its use in clarifying linearization stability, are discussed.Research supported in part by NSF grant MCS 81-08814(A02)Research supported in part by NSF grant MCS 81-07086     

Seasonality in estuarine sources of methylated arsenic

The effect of seasonal temperature change on the release of methylated arsenic from macroalgae, phytoplankton and sediment porewaters has been investigated by a series of controlled laboratory experiments. The appearance of dissolved arsenic species in the overlying waters was monitored using a coupled hydride generation/GC AA analytical technique. The liberation of dissolved arsenic species by the macroalgae Ascophyllum nodosum was examined under estuarine conditions at 5 °C and 15 °C. At the lower temperature the release rates were 0.2 μg kg^?1 h^?1 (wet weight of material) for monomethylarsenic (MMA) and 0.5 μg kg^?1 h^?1 for dimethylarsenic (DMA), whereas at 15 °C the rates were 0.4 μg kg^?1 h^?1 and 3.2 μg kg^?1h^?1, respectively. Incubation experiments were also carried out at 15 °C using the diatom Skeletonema costatum. During the log growth phase, when chlorophyll a concentrations were in the range 1-5 μg dm^?3, the rate of appearance of DMA in the water was ～3 ng dm^?3 h^?1. Sediment samples from the freshwater and seawater end-members of the Tamar Estuary, UK, were incubated under natural conditions at 5 °C and 15 °C. The freshwater sediments released DMA in preference to MMA; the concentrations of both species increased exponentially and reached a steady state in the overlying water after 250 h. Considerably more DMA was produced at 15 °C than at 5 °C, whilst the amount of MMA produced appeared to be insensitive to the temperature increase. In contrast, the seawater sediments always produced more MMA than DMA and the increase in temperature had little effect on the production of either MMA or DMA. The results of the laboratory experiments were compared with field observations in temperate estuaries, including the Tamar Estuary. The implications of changes of water temperature on the fate of arsenic in estuaries is discussed and modifications to the estuarine arsenic cycle are proposed.     

Methylation of inorganic lead by Tamar Estuary (UK) sediments

Tetramethyllead (TML) has been produced from inorganic lead salts using biologically active sediments and waters from the Tamar Estuary, S. W. England. The TML production was a two-stage process involving an initial lag phase of about 100 hours followed by the exponential appearance of TML, which amounted to about 0.03% of total added lead. The methylation process is discussed in the context of lead transport in estuaries.     

Observation of a free radical during the photolysis of phenyliodoacetylene

An ESR spectrum observed during the photolysis of phenyliodoacetylene indicates the formation of a π-radical. It is suggested that a crossing of α- and π-levels occurs in the phenylethynyl radical.     

Photomechanically induced ferroelectricity in smectic liquid crystals

We report new photomechanical effects in the ferroelectric liquid crystal SCE13 doped with a photoisomerizing guest azo dye. Low concentrations of dye (∼5 per cent wt:wt) are shown to cause an isothermal, reversible disruption of smectic phases when the system is illuminated with low power density (∼ 1 mW cm^-2) UV light. In the case of a sample initially in the S*_c phase, this results in a fall in the magnitude of spontaneous electrical polarization (P_s) and changes in electro-optic switching characteristics. If the sample is illuminated in the S_A phase, the electroclinic switching decreases. In contrast to this, when systems containing higher concentrations of dye (≥ 10 per cent wt: wt) are UV illuminated in the S_A phase, a reversible, isothermal transition to a biphasic S*_c/isotropic state occurs. In this case, the P_s is seen to rise from zero in the S_A phase to a finite value(∼2 nC cm^-2) in the biphasic mixture and hysteresis occurs in the electro-optic switching. When these higher dye concentration mixtures are held initially in the S*_c phase and UV illuminated, a more complicated variation of P_s occurs with the sample again undergoing a transition to a biphasic S*_c/isotropic state. Possible mechanisms for the transition are discussed.     

On the Onset of Rayleigh-Bénard Convection in a Fluid Layer of Slowly Increasing Depth

A two-scaling approach is used to investigate the onset of convection in a fluid layer whose depth is a slowly increasing function of horizontal distance. It is shown that whatever the value of the imposed temperature difference between the boundaries (provided, of course, that the lower one is hotter) there are regions which are stable and regions which are unstable to small perturbations. As the depth increases the amplitude of steady solutions increases from exponentially small values to take on the familiar square-root behavior of weakly nonlinear solutions. The solution in this narrow transition region is described in terms of the second Painlevé transcendent. In the exceptional case when the perturbation takes the form of longitudinal rolls, this equation needs some modification in that the second derivative is replaced by the fourth. The flow in a horizontal layer when the temperature difference between the boundaries increases slowly may be treated in exactly the same way. The necessary modifications to theory and results are given in an Appendix.     

The nucleation of sparingly soluble salts from solution

The relationship between heterogeneous and homogeneous nucleation of sallts from solution has been examined. These concepts enable both new and older published data to be interpreted in terms of the Volmer-Becker-Döring theory. The results and some of their implications in surface chemistry and crystallization processes are discussed.