Studies on the kinetics of soot-O3 reactions, at various soot and ozone concentrations, have been conducted under flow conditions with ozone ranging from 50 to 15,000 ppm and soot from 2 to 350 mg. At lower concentrations, the initial rates of CO2 and CO formation are found to be half order with respect to soot and first order with respect to ozone. At higher concentrations, CO2 formation exhibits a more complex pattern. The initial rate for the formation of CO2 for a first stage is half order with respect to soot and 1.5 order with respect to O3, while the second stage is zero order in both species. Differences between data at higher and lower concentrations are discussed, and mechanisms for the formation of CO2 CO, and carboxylics during ozonation are suggested. Mass balance calculations on low concentration data reveal that only a small portion of the ozone is used to produce CO2, CO, H2O, and carboxylic species, most of it being decomposed catalytically over soot. At higher concentrations of O3 the rate of formation of carboxylic functionalities during the hexane soot-ozone reaction under static conditions has been examined. The initial rate, as determined by the Elovich equation, suggests that the soot-ozone reaction is nearly 6 times faster under equivalent conditions than the sool-NO2/N2O4 reaction reported earlier from this laboratory.

We have investigated the interactions of a novel anionic ryanoid, 10-O-succinoylryanodol, with individual mammalian cardiac muscle ryanodine receptor channels under voltage clamp conditions. As is the case for all ryanoids so far examined, the interaction of 10-O-succinoylryanodol with an individual RyR channel produces profound alterations in both channel gating and rates of ion translocation. In the continued presence of the ryanoid the channel fluctuates between periods of normal and modified gating, indicating a reversible interaction of the ligand with its receptor. Unlike the majority of ryanoids, we observe a range of different fractional conductance states of RyR in the presence of 10-O-succinoylryanodol. We demonstrate that 10-O-succinoylryanodol is a very flexible molecule and propose that each fractional conductance state arises from the interaction of a different conformer of the ryanoid molecule with the RyR channel. The probability of channel modification by 10-O-succinoylryanodol is dependent on the transmembrane holding potential. Comparison of the voltage dependence of channel modification by this novel anionic ryanoid with previous data obtained with cationic and neutral ryanoids reveals that the major influence of transmembrane potential on the probability of RyR channel modification by ryanoids results from an alteration in receptor affinity. These investigations also demonstrate that the charge of the ryanoid has a major influence on the rate of association of the ligand with its receptor indicating that ionic interactions are likely to be involved in this reaction.

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The simultaneous evolution of CO, CO2, N2O, and NO, detected and estimated by both infrared spectroscopy and chemiluminescence during the reaction of soot and NO2/N2O4 over a range of temperatures, suggests that, in addition to the previously described chemisorption reaction, there also is a redox process occurring in the initial stages of the reaction. Estimations of these gases suggest that the redox reaction also includes reactive components other than the olefinic segment of soot, and occurs under all conditions examined. Infrared studies show that gaseous NO, produced immediately on the introduction of NO2/N2O4 into a reactor containing soot and water vapor, subsequently decreases with the accompanying formation of N2O.

Qualitative and quantitative studies of the reaction of black carbon with the oxides of nitrogen, including NO, NO2/N2O4, N2O, and N2O3, have been carried out with the use of Fourier transform infrared spectroscopy (FT-IR). The active reactant is shown to be NO2, whether it acts as a disproportionation product or as an impurity in the gas under study. FT-IR spectra of the surface species identify them as resulting from reaction of carbon with NO2. For paraffin candle soot which was exposed simultaneously to oxygen atoms, and nitric oxide at 298 K, the surface species also are due to NO2, formed by oxidative adsorption of NO on the soot surface.