Complexation of actinides and lanthanides with carboxylic organic ligands is known to facilitate migration of radionuclides from deep geological disposal systems of spent nuclear fuel. In order to examine the ligand-dependent structures of trivalent actinides and lanthanides, a series of Eu(III)-aliphatic dicarboxylate compounds, Eu2(oxalate)3(H2O)6, Eu2(malonate)3(H2O)6, and Eu2(succinate)3(H2O)2, were synthesized and characterized by using X-ray crystallography and time-resolved laser fluorescence spectroscopy. Powder X-ray diffraction results captured the transition of the coordination modes of aliphatic dicarboxylate ligands from side-on to end-on binding as the carbon chain length increases. This transition is illustrated in malonate bindings involving a combination of side-on and end-on modes. Strongly enhanced luminescence of these solid compounds, especially on the hypersensitive peak, indicates a low site symmetry of these solid compounds. Luminescence lifetimes of the compounds were measured to be increased, which is ascribed to the displacement of water molecules in the innersphere of Eu center upon bindings of the organic ligands. The numbers of remaining bound water molecules estimated from the increased luminescence lifetimes were in good agreement with crystal structures. The excitation-emission matrix spectra of these crystalline polymers suggest that oxalate ligands promote the sensitized luminescence of Eu(III), especially in the UV region. In the case of malonate and succinate ligands, charge transfer occurs in the opposite direction from Eu(III) to the ligands under UV excitation, resulting in weaker luminescence.
The pinewood nematode, Bursaphelenchus xylophilus is a serious forest pathogen in many countries including Japan, China and Korea. To minimize the environmental problems caused by synthetic chemicals broadly utilized in the control of B. xylophilus, we estimated the nematicidal potency of 63 aliphatic compounds against B. xylophilus by measuring their inhibition activity against acetylcholinesterases (ACE, EC 3.1.1.7) of B. xylophilus (BxACEs). In the primary inhibition assay using B. xylophilus crude protein, C6, C9, C10 2E-alkenal C12 alkanoic acid were observed the > 45% BxACE inhibition rate and they were subsequently estimated the inhibition rate against three recombinant BxACEs. Whole compounds showed the high inhibition rate against BxACE-1 and BxACE-2. Interestingly, C6 2E-alkenal and C12 alkanoic acid exhibited the high inhibition rate against BxACE-3 which would be insensitive to ACE inhibitors.
Nematicidal activity of aliphatic compounds was tested against pien wood nematode, Bursaphelenchus xylophilus. There was a significant difference in nematicidal activity among function groups. In a test with alkanols and 2-alkenols, compounds with C8-C11 chain length showed 100% nematicidal activity at 0.5 mg/mL concentration. C6-C10 2-alkenals exhibited >95% nematicidal activity, but the other compounds with C11-C14 chain length showed weak activity. Nematicidal activity of alkanoic acids with C7-C11 chain length was strong. Whole compounds belonging to hydrocarbons, alkanals and alkanoic acetate showed weak nematicidal activity at 0.5 mg/mL concentration. Nematicidal activity of compounds which showed strong nematicidal activity at 0.5 mg/mL concentration was tested at a lower concentration. At 0.25 mg/mL concentration, whole compounds except C8 alkanol, C8 2-alkenol and C7 alkanoic acid showed >80% nematicidal activity. C9-C11 alkanols, C10-C11 2-alkenols, C8-C9 2-alkenals and C9-C10 alkanoic acids showed >80% nematicidal activity at 0.125 mg/mL concentration. Only C11 alkanol exhibited strong nematicidal activity at 0.0625 mg/mL concentration
This study was performed : 1) to establish the experimental analysis conditions for the sorption and desorption of toxic organic contaminants to/from the activated sludge, sediment, and clay, and 2) to determine the sorption and desorption equilibrium coefficients of some representative halogenated aliphatic compounds. Through the preliminary sorption test using Azo dye, a setting of quantitative experimental conditions to determine the sorption and desorption characteristics was decided as follows; equilibration time of 180 minutes, centrifuge for 15 minutes at 5000×g, and 500㎎/ℓ of TOC concentration. The sorption and desorption characteristics of halogenated aliphatic compounds onto activated sludge, sediment and clay could be described very well using the Freundlich isotherm. The preference of the average sorption capacity of the overall compounds showed in the sequence sediment 0.26㎎/g, clay 0.23㎎/g, and activated sludge 0.11㎎/g. The desorption rate of the sorbed compounds onto activated sludge, sediment and clay was approximately 89.8%, 35.3%, and 66.4%, respectively.
Sorption and desorption is an important phenomenon to determine the fate of halogenated aliphatic hydrocarbons in the aqueous phase. This study was conducted to develope a predictive equation capable of estimating the sorption and desorption potentials of halogenated aliphatic hydrocarbons onto the sludge from activated process, sediment, and clay. It has shown that the sorption and desorption parameters can be accurately estimated using Quantitative Structural Activity Relationship(QSAR) models based on molecular connectivity indexes of test compounds. The QSAR model could be applied to predict the sorption and desorption capacity of the other halogenated aliphatic hydrocarbons. The QSAR modeling would provide a useful tool to predict the sorption and desorption capacity without time-consuming experiments.