Comparative studies on exchange reactions of hexafluoroacetylacetonate in bis(hexafluoroacetylacetonato)(dimethyl sulfoxide)dioxouranium(VI) in nonaqueous solvent and supercritical CO(2)

Exchange reactions of hexafluoroacetylacetonate (hfacac) in UO2(hfacac)2DMSO (DMSO = dimethyl sulfoxide) in o-C6D4Cl2 and supercritical CO2 (sc-CO2) have been studied using the NMR line-broadening method to compare reactivity in a nonaqueous solvent with that in sc-CO2. It was found that the exchange rates of hfacac in both systems are dependent on the concentration of the enol isomer ([Henol]) of hexafluoroacetylacetone and become slow with an increase in the concentration of free DMSO ([DMSO]). The exchange reaction between free and coordinated DMSO in UO2(hfacac)2DMSO has been also examined in o-C6D4Cl2 and sc-CO2. As a result, the exchange rate of DMSO was found to depend on [DMSO]. From these results, the hfacac exchange reactions in UO2(hfacac)2DMSO in o-C6D4Cl2 and sc-CO2 were proposed to proceed through the mechanism that the ring-opening for one of two coordinated hfacac in UO2(hfacac)2DMSO is the rate-determining step, and the resulting vacant site is coordinated by the incoming Henol, followed by the proton transfer from Henol to hfacac and the ring closure of unidentate hfacac. The rate constants at 60 degrees C and the activation parameters (DeltaH and DeltaS) for the ring-opening path are 35.8 +/- 3.2 s(-1), 57.8 +/- 2.7 kJ.mol(-1), and -42.9 +/- 7.7 J.mol(-1).K(-1) for the o-C6D4Cl2 system, and 518 +/- 50 s(-1), 18.9 +/- 1.8 kJ.mol(-1), and -138 +/- 5 J.mol(-1).K(-1) for the sc-CO2 system, respectively. Differences in kinetic parameters between sc-CO2 and o-C6D4Cl2 systems were proposed to be attributed to the solute-solvent interactions such as Lewis acid-Lewis base interactions and hydrogen bondings between sc-CO2 and beta-diketones.     

Stability of pyrrolidone derivatives against γ-ray irradiation

To evaluate the stability of N-alkylated pyrrolidone derivatives(NRPs),which are supposed to be used as precipitants for U(VI) and Pu(IV,VI) species in HNO 3 media,under irradiation environment,some candidate NRPs were irradiated by γ-ray.Irradiation to HNO 3 solutions up to 6 mol dm 3(= M) containing 2 M N-n-butyl-2-pyrrolidone(NBP),one of NRPs with lower hydrophobicity,has revealed that the residual ratios of NBP in the samples of HNO 3 up to 3 M decreased identically and linearly.Approximately 20% of NBP was found to be degraded after the irradiation at 1 MGy.It was also found that the decrease in the precipitation ratio of UO 2 2+(P.R.,%) was gentle and that the P.R.values were relatively in accordance with the residual ratios of NBP.On the other hand,the degradation of the samples irradiated in 6 M HNO 3 was found more distinguished.It was proposed from the analyses of degraded compounds that the degradation of NBP in HNO 3 by γ-ray irradiation started from the cleavage of the pyrrolidone ring by the addition of oxygen atom originating from HNO 3,followed by the formation of chain compounds by the successive addition of oxygen,leading to the generation of oxalic acid and acetic acid.The stability of other NRPs in 3 M HNO 3 was evaluated to be nearly identical with that of NBP except lower P.R.values of the samples containing NRPs with higher hydrophobicity irradiated at more than 0.5 MGy.     

Fast swelling/deswelling kinetics of comb-type grafted poly(N-isopropylacrylamide) hydrogels

The synthesis and characterization of comb-type grafted thermo-sensitive hydrogels is presented. These hydrogels were synthesized by polymerization of N-isopropylacrylamide (IPAAm) with a PIPAAm macromonomer. This process leads to a crosslinked IPAAm backbone polymer, copolymerized with highly mobile comb-type PIPAAm chains. These new thermo-responsive copolymers displayed higher equilibrium swellings at lower temperatures and rapid deswelling kinetics at elevated temperatures. The swelling/deswelling for comb-type gels is dependent on the graft chain lengths, in contrast to normal PIPAAm gel lacking the graft chains. As the temperature is increased above the critical temperature, the dehydrated graft chains aggregated due to hydrophobic attraction. Rapid and reversible kinetics of the graft-type gel were observed in response to stepwise temperature changes within short time cycles: phenomena not observed in normal crosslinked thermo-sensitive gels. The influence of freely mobile graft chains on both the equilibrium and dynamic properties of comb-type PIPAAm gel is demonstrated. Possible application of graft-type gel is discussed for actuator systems.