Scintillator Species

The excited RH can be formed by the recombination of RH+ + e or directly through molecular excitation through secondary electrons. In the reaction scheme, S is a scintillator species, which can provide invaluable information about the distribution of the electron-hole distances and ion-pair singlet-triplet character (which itself is a function of the magnetic interactions and the applied field), by directly observing the time-dependence of the fluorescence. 

In the carbon-14 expts, HMX/RDX product was isolated qualitatively, separated Into its components, and each component assayed for carbon-14 beta radioactivity using a liquid scintillation counting technique (Ref 11). DPT-l4C was isolated as an intermediate product from the reaction mixt and similarly radioassayed. For the nitrogen-15 tagged AN expts, HMX and RDX were assayed mass spectrometrically for i5N/i4N ratios from which atom %1SN contents were calcd. In die course of these expts, each tagged species was added initially and also at subsequent stages of the reaction process. The important observations and results are summarized as ... 

SPA is based on bringing a radioactive species in close proximity to a bead of solid scintillant. The technique relies on the specific capture of the substrate or product onto the bead so that the radioactivity can be measured without the need for separation. 

Secondary isotope effects are small. In fact, most of the secondary deuterium KIEs that have been reported are less than 20% and many of them are only a few per cent. In spite of the small size, the same techniques that are used for other kinetic measurements are usually satisfactory for measuring these KIEs. Both competitive methods where both isotopic compounds are present in the same reaction mixture (Westaway and Ali, 1979) and absolute rate measurements, i.e. the separate determination of the rate constant for the single isotopic species (Fang and Westaway, 1991), are employed (Parkin, 1991). Most competitive methods (Melander and Saunders, 1980e) utilize isotope ratio measurements based on mass spectrometry (Shine et al., 1984) or radioactivity measurements by liquid scintillation (Ando et al., 1984 Axelsson et al., 1991). However, some special methods, which are particularly useful for the accurate determination of secondary KIEs, have been developed. These newer methods, which are based on polarimetry, nmr spectroscopy, chromatographic isotopic separation and liquid scintillation, respectively, are described in this section. The accurate measurement of small heavy-atom KIEs is discussed in a recent review by Paneth (1992). 

It should be noted here that the variable temperature data presented for Np02 in Fig. 6 are close to those reported by Glebov et al. (43) but that the relaxivities presented in this figure for PuOl are different from those published by these authors (44) (the concentration of the PuO is uncertain in this reference). It has already been mentioned that special care must be taken in the preparation of solutions of plutonyl salts to avoid the presence of lower oxidation states. UV-visible spectroscopy (27) and liquid scintillation detectors (50) are particularly useful to assess the concentration and the nature of Pu species in solution. The purity of the PuO can also be tested by liquid liquid extraction with thenoyltrifluoroacetone, an agent known to be able to extract Pu" " from acidic aqueous phases but unable to extract PuO + (51). 

Sampling and Measurements. The determination of dissolved actinide concentration was started a week after the preparation of solutions and continued periodically for several months until the solubility equilibrium in each solution was attained. Some solutions, in which the solubilities of americium or plutonium were relatively high, were spectrophotometrically analyzed to ascertain the chemical state of dissolved species. For each sample, 0.2 to 1.0 mL of solution was filtered with a Millex-22 syringe filter (0.22 pm pore size) and the actinide concentration determined in a liquid scintillation counter. After filtration with a Millex-22, randomly chosen sample solutions were further filtered with various ultrafilters of different pore sizes in order to determine if different types of filtration would affect the measured concentration. The chemical stability of dissolved species was examined with respect to sorption on surfaces of experimental vials and of filters. The experiment was performed as follows the solution filtered by a Millex-22 was put into a polyethylene vial, stored one day, filtered with a new filter of the same pore size and put into another polyethylene vial. This procedure was repeated twice with two new polyethylene vials and the activities of filtrates were compared. The ultrafiltration was carried out by centrifugation with an appropriate filter holder. The results show that the dissolved species in solution after filtration with Millex-22 (0.22 ym) do not sorb on surfaces of experimental materials and that the actinide concentration is not appreciably changed with decreasing pore size of ultrafilters. The pore size of a filter is estimated from its given Dalton number on the basis of a hardsphere model used in the previous work (20). 

Nonetheless, it has been shown to elute immediately after the PC peak. LysoPC, if present, would elute between the PAF and sphingomyelin (Sph) peak. The latter component often shows a double peak, and this can be attributed to the separation of distinct fatty acyl species. It is well to emphasize again that compounds such as PAF and lysoPC have very low levels of unsaturated bonds present, and hence a detector other than an ultraviolet monitor would have to be used. An alternate approach would be to use tritiated PAF or tritiated lysoPC as examples and assay the eluates by liquid scintillation counting. Since the labeled compounds are at tracer dose levels, one could still assay for biological activity associated with the compounds. 

While these methods both share the distinct advantage of looking directly at the active ingredient of the formulation they also share a number of disadvantages. Because of the small quantities released, sample preparation techniques, can frequently be elaborate and therefore very time consuming. Since each step in the preparation of a sample is a potential source of error, this increased complexity can also decrease the accuracy of the method. Considerations of this type led this laboratory to the use of labeled pheromones to decrease sample handling and to increase the quantitative accuracy, however, liquid scintillation counting does not provide qualitative information about the labeled species. 

The MIPs have also been utilized as the recognition elements in pseudoimmunoassays. " In this approach, MIPs are substituted for antibodies to quantify the amount of analyte in a biological sample, such as blood plasma. Most MIP immunoassays are competitive binding studies in which a radio- or fluorescent-labeled analyte is added to a mixture of the MIP and imlabeled analyte. After equilibrium is reached, some fraction of the labeled species is bound to the polymer surface and thus can be separated from the supernatant. The supernatant is then analyzed via scintillation or fluorescence techniques to determine the concentration of the original unlabeled analyte. Mosbach et al. have demonstrated that MIP-based immunoassays can rival the selectivity of antibody-based assays. Imprinted polymers for the opioid receptor ligands enkephalin and morphine were prepared and showed submicromolar (pM) level selectivity in a radioligand competition assay in aqueous buffers. The analysis... 

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