betadex and hexafluorobenzene

In this study, the effect of monopotassium phosphate (MKP) on the reduction in mobility and bioavailability of 2,4,6-trinitrotoluene (TNT) was tested. In the test soil, collected from an active firing range, of which cation binding sites were mostly exchanged with H(+) or Al(3+), potassium ions in MKP exchanged the existing cations and hence significantly increased TNT sorption. In addition, a competitive sorption experiment with hexafluorobenzene and 2,4-dinitrotoluene suggests that TNT was specifically sorbed through cation-polar interaction in the test soil. The unit-equivalent Freundlich sorption coefficient of TNT in MKP-amended soil (1370.96 mg-TNT/kg-soil) was about 13 times higher than that in untreated soil (106.23 mg-TNT/kg-soil). Finally, modified synthetic precipitation leaching procedure and hydroxypropyl-β-cyclodextrin extraction result revealed that MKP application could reduce both the leachability and bioavailability of soil TNT. The leachable and extractable fraction of TNT in untreated soil were 87.63% and 94.47% of the initial TNT, respectively, whereas these fractions decreased to 49.15% and 54.85% of the initial TNT in the presence of MKP, respectively. MKP application can be a benign technology which can reduce both mobility and bioavailability of TNT in soil.

Topics: 2-Hydroxypropyl-beta-cyclodextrin; Adsorption; beta-Cyclodextrins; Calcium; Dinitrobenzenes; Fluorocarbons; Phosphates; Potassium Compounds; Soil Pollutants; Trinitrotoluene

The effect of benzene fluorination on C-H...pi interactions is studied using a number of computational methods applied to a range of intermolecular complexes. High level wavefunction methods (CCSD(T)) predict a slightly greater interaction energy for complexes of benzene with methane or fucose, compared to corresponding complexes involving hexafluorobenzene. A number of more approximate treatments, DFT with the M06-2X functional, PM3-D* and MM methods, give interaction energies within 1 kcal mol(-1) of the high level values, and also correctly predict that the interaction energy is slightly greater for benzene compared to hexafluorobenzene. However, the DFT-D model used here predicts that the interaction energy is slightly greater for hexafluorobenzene. Molecular dynamics simulations, employing the GLYCAM-06 force field, validated here, are used to model the complexes of benzene and hexafluorobenzene with beta-cyclodextrin in aqueous solution. We predict the binding free energies of the complexes to be within 0.5 kcal mol(-1), and suggest that the different chemical shifts of the H5 protons observed in the two complexes arise from their slightly different structures, rather than from different binding energies.

Topics: Benzene; beta-Cyclodextrins; Fluorocarbons; Fucose; Molecular Dynamics Simulation; Quantum Theory; Thermodynamics