Self-assembly of nonionic surfactants into lyotropic liquid crystals in ethylammonium nitrate, a room-temperature ionic liquid

The stability of a variety of lyotropic liquid crystals formed by a number of polyoxyethylene nonionic surfactants in the room-temperature ionic liquid ethylammonium nitrate (EAN) is surveyed and reported. The pattern of self-assembly behaviour and mesophase formation is strikingly similar to that observed in water, even including the existence of a lower consolute boundary or cloud point. The only quantitative difference from water is that longer alkyl chains are necessary to drive the formation of liquid crystalline mesophases in EAN, suggesting that a rich pattern of "solvophobic" self-assembly should exist in this solvent.     

Formation of aquatic Th(IV) colloids and stabilization by interaction with Cm(III)/Eu(III)

The present investigation is to ascertain under what conditions actinide ions undergo aggregation via oxo-bridging to form stable colloidal species. Eu and Th are taken for this purpose as trivalent and tetravalent actinide homologue ions, respectively. For verification of the effects of impurities in chemicals on the actinide colloid generation, pH is adjusted either by a conventional acid-base titration or by coulometry without addition of NaOH. The colloid generation is monitored by highly sensitive laser-induced breakdown detection in varying pH from 3 to 7, first in dilute Eu and Th solutions separately and then in a mixture of both, all in 0.5 M HCl/NaCl. The formation of stable colloids is observed particularly in a mixed solution of Eu and Th, suggesting that aggregation via mutual oxo-bridging of trivalent and tetravalent metal ions results in surface polarization, leading to stable hydrophilic particles of 20-30 nm in diameter. When Eu is replaced by Cm in the mixed solution in favor of the high fluorescence intensity of the latter, the chemical speciation is determined on colloid-borne Cm by time-resolved laser fluorescence spectroscopy. Two different colloid-borne Cm species, oxo-bridged with Th, are identified: a minor amount at 598.0 nm (denoted as Cm-Th(1)) and a major amount at 604.8 nm (Cm-Th(2)). The former is found as a transitional state, which converts to the latter with increasing pH and prevails at pH > 5.5. Both colloid-borne species (Cm-Th) are distinctively different from hydrolyzed Cm or its carbonate complexes with respect to their fluorescence peak positions and lifetimes. In conclusion, a mixed oxo-bridging of trivalent and tetravalent actinides elicits the generation of stable colloids, whereas individual ions in their pure state form colloids under oversaturation at near neutral pH only as a transitional state for precipitation.     

Novel fluorescent main-chain liquid crystalline ionomers containing Eu(III) ions

Novel nematic fluorescent main-chain liquid crystalline ionomers containing Eu(III) ions (Eu-LCI) were synthesised by the use of bis(4-(chlorocarbonyl)phenyl) decanedioate (BD), 4,4-dihydroxybiphenyl (D), 2,5-dihydroxybenzoic acid (B) and anhydrous europium chloride. The chemical structures, liquid crystalline behaviours and fluorescence properties of Eu-LCI were characterised by various experimental techniques. The introduction of small amounts of europium ions endowed the LCI with excellent luminescence properties. POM results showed that europium ions did not change the liquid crystalline texture of the LCI. Fourier transform infrared imaging showed that europium ions were evenly distributed in the matrices of ionomers. A schematic diagram of nematic fluorescent LCI was established to demonstrate the interaction and distribution of the components. Eu-LCI showed reversible mesomorphic phase transitions, wide mesophase temperature ranges and high thermal stability. The thermogravimetric analysis (TGA) results showed that decomposition temperatures (5% weight loss) were greater than 308°C in all Eu-LCI. Eu-LCI can emit red light when excited. The luminescence intensity of Eu-LCI gradually increased with increase in Eu(III) ions from 0.3 to 1.5 mol%. The temperature dependence of luminescent intensity was studied in the liquid crystalline phase, where the fluorescence intensity of Eu-LCI decreased monotonically with increase in temperature.     

Ion exchange separation of Eu(III), Th(IV), U(VI) and Pu(IV) ions on Amberlyst A-15 in non-aqueous solutions

Distribution ratios of europium(III), thorium(IV), uranium(VI) and plutonium(IV) ions on Amberlyst A-15, a macroreticular polystyrene sulfonate resin, after extraction in HTTA-TBP-Shell Sol-T and HTTA-TOPO-benzene solutions have been determined as a function of the aqueous acidity. The affinity orders were EuPu>Th>U and Eu>Th>Pu>U in the former and the latter solutions, respectively. Separation factors were computed from the observed K_d values. A procedure for the separation of a mixture of Eu(III), Th(IV), and U(VI) ions in HTTA-TOPO-benzene solution in an ion-exchange column is described.     

Cyclic voltammetry of Th(IV) in the room-temperature ionic liquid [Me3NnBu][N(SO2CF3)2

A Th(IV) compound, [Th(TFSI)4(HTFSI)].2H2O [where TFSI = N(SO2CF3)2], has been synthesized and characterized using elemental analysis, thermogravimetric analysis, and vibrational spectroscopy. The analysis suggests that the TFSI anion coordinates to the metal center via the sulfonyl oxygens as well as provides evidence for the coordination of HTFSI. The voltammetric behavior of this compound has been studied in the room-temperature ionic liquid [Me3NnBu][TFSI], and results show that Th(IV) is reduced to Th(0) in this ionic liquid in a single reduction step. Analysis of cyclic voltammograms shows that an insoluble product is being formed at the electrode surface, which is attributed to the formation of ThO2 by reaction with water. The E0 value for the reduction of Th(IV) to Th(0) has been determined to be -2.20 V (vs Fc+/Fc; -1.80 V vs SHE). A comparison of this E0 value with those obtained for Th(IV) reduction in a LiCl-KCl eutectic (400 degrees C), water, and nonaqueous solvents shows that the reduction in [Me3NnBu][TFSI] is easier to accomplish than that in these other solvents.     

Investigation of U(VI), Th(IV), and Eu(III) ions’ sorption behavior onto silica gel modified with anhydride

Journal of Radioanalytical and Nuclear Chemistry - Modification of silica gel by butanedioic anhydride (SiO2–BDAH) results in efficient adsorbents for removal of U(VI), Th(IV), and Eu(III)...     

Ion flotation of lanthanum(III) and holmium(III) from nitrate and nitrate-chloride media

Ion flotation of lanthanum(III) and holmium(III) from nitrate and nitrate-chloride solutions with sodium dodecyl sulfate was studied. The distribution coefficients and their dependence on pH were determined.     

Electrochemical behaviour of poly(3,4-ethylenedioxythiophene) in a room-temperature ionic liquid

The cyclic voltammetry responses and the redox switching dynamics of poly(3,4-ethylenedioxythiophene) (PEDOT) in a room-temperature ionic liquid, 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)amide (EMImTf₂N), were investigated. The shape of the cyclic voltammograms showed two anodic and two cathodic peaks. These peak currents varied linearly with the scan rate indicating a thin-layer behaviour. No memory effects were observed during the cyclic voltammetry experiments in this ionic liquid. On the other hand, the redox switching dynamics of PEDOT were studied by means of potential step experiments. The analysis of chronocoulograms in term of RC-circuits indicated that the time dependence of the charge transferred during the potential step showed two time constants. These results were consistent with the postulated structure or morphology of the PEDOT film which contained two types of coexisting zones: a compact and an open structures.     

Effect of nitrate, perchlorate, and water on uranyl(VI) speciation in a room-temperature ionic liquid: a spectroscopic investigation

Room-temperature ionic liquids form potentially important solvents in novel nuclear waste reprocessing methods, and the solvation, speciation, and complexation behaviors of lanthanides and actinides in these solvents are of great current interest. In the study reported here, the coordination environment of uranyl(VI) in solutions of the room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][Tf(2)N]) containing perchlorate, tetrabutylammonium nitrate, and water was investigated using Raman, ATR-FTIR, and NMR spectroscopies in order to better understand the role played in uranyl(VI) solution chemistry in room-temperature ionic liquids by water and other small, weakly complexing ligands. The (2)H NMR chemical shift for water in a solution of uranyl perchlorate hexahydrate in [EMIM][Tf(2)N] appears at 6.52 ppm, indicating that water is coordinated to uranyl(VI). A broad ν(OH) stretching mode at 3370 cm(-1) in the ATR-FTIR spectrum shows that this coordinated water is engaged in hydrogen bonding with water molecules in a second coordination sphere. A significant upfield shift in the (2)H NMR signal for water and the appearance of distinct ν(as)(HOH) (at 3630 cm(-1)) and ν(s)(HOH) (at 3560 cm(-1)) vibrational bands in the ATR-FTIR spectra show that coordinated water is displaced by nitrate upon formation of the UO(2)(NO(3))(2) and UO(2)(NO(3))(3)(-) complexes. The Raman spectra indicate that perchlorate complexed to uranyl(VI) is also displaced by nitrate. Our results indicate that perchlorate and water, though weakly complexing ligands, do have a role in uranyl(VI) speciation in room-temperature ionic liquids and that Raman, infrared, and NMR spectroscopies are valuable additions to the suite of tools currently used to study the chemical behavior of uranyl(VI)-ligand complexes in these solvents.     

Formation of higher chloride complexes of Np(IV) and Pu(IV) in water-stable room-temperature ionic liquid [BuMeIm][Tf2N

A UV/vis/near-IR spectroscopic study shows that in [BuMeIm][(CF3SO2)2N] hydrophobic room-temperature ionic liquid solutions, [BuMeIm]2[AnCl6] complexes, where BuMeIm+ is 1-n-butyl-3-methylimidazolium and An(IV) is Np(IV) or Pu(IV), have an octahedral An(IV) environment similar to that observed in solid complexes. Water has no influence on the absorption spectra of AnCl6(2-) complexes, indicating their stability to hydrolysis in ionic liquid. Adding [BuMeIm]Cl modifies the UV/vis/near-IR absorption spectra of An(IV) in the ionic liquid and causes solids to precipitate. The solid-state reflectance spectra of the precipitates reveal considerable differences from the corresponding An(IV) hexachloro complexes. A voltammetric study indicates that AnCl6(2-) complexes are electrochemically inert in [BuMeIm][(CF3SO2)2N] at the glassy carbon working electrode. By contrast, quasi-reversible electrochemical reduction An(IV)/An(III) and An(IV) oxidation are observed in ionic liquids in the presence of [BuMeIm]Cl. The oxidation wave of noncoordinated chloride ions interferes with the An(IV) oxidation waves. The spectroscopic and voltammetric data clearly indicate the formation of nonoctahedral actinide(IV) chloride complexes with a Cl-/An(IV) ratio exceeding 6/1 in [BuMeIm][(CF3SO2)2N] in excess chloride ions.     

Sorption behaviour of nanocrystalline MOR type zeolite for Th(IV) and Eu(III) removal from aqueous waste by batch treatment

The nanocrystalline mordenite (MOR) type zeolite materials with initial chemical composition Na(2)O:Al(2)O(3):10SiO(2):48H(2)O have been synthesized under hydrothermal conditions. MOR1 and MOR2 are spherically shaped nanocrystals, whereas MOR3 and MOR4 have rod-like morphology. This paper reports the sorption characteristics of MOR analogues for Th(IV) and Eu(III) removal from aqueous nuclear waste. Sorption of Th(IV) and Eu(III) on MOR1, MOR2, MOR3 and MOR4 in a single component system with varying initial metal ion concentration, solution pH, contact times, sorbent dose and temperatures has also been investigated. Further, the Langmuir and Freundlich sorption models have been applied to describe equilibrium isotherms at different temperatures. The adsorption capacity increases largely with increasing solution pH and temperature of the system. Specific surface area and pore volume have been investigated by Brunauer-Emmett-Teller (BET) method. The N(2) adsorption isotherm presents a type IV isotherm with narrow hysteresis loop which indicates the presence of mesopores related to inter-particle voids. Thermodynamic results indicate that the sorption follows an endothermic physisorption process. It has been found that these exchangers have good sorption capacity and out of which MOR4 has highest sorption capacity. Thus, nanocrystalline MOR4 is proved to be good sorbent for both Th(IV) and Eu(III).     

Ion exchange studies of U(VI), Th(IV), Pu(IV) and Eu(III) on a macroreticular resin in TBP-Shell Sol-T solutions

Ion exchange studies of uranium(VI), thorium(IV), plutonium(IV) and europium(III) ions on a macroreticular cation exchange resin, Amberlyst A-15, from solutions of 30% and 5% TBP—Shell Sol-T have been carried out. The metal ions were extracted into TBP Shell Sol-T phase from 8M NH₄NO₃ at different nitric acid concentrations. Ion exchange distribution ratios as a function of organic phase acidity of 30% and 5% TBP have been computed. Separation factors computed from the observed Kd values are plotted as a function of organic phase acidity.     

Reactivity of trihexyl(tetradecyl)phosphonium chloride, a room-temperature phosphonium ionic liquid

Trihexyl(tetradecyl)phosphonium chloride 1, a room-temperature ionic liquid, readily undergoes deuterium isotope exchange reaction in deuterated solvents. Under basic conditions, ionic liquid 1 was reactive and 50% deuterium exchanged on all four P–CH₂ methylene groups in 9 h at ambient temperature, 30 min at 50 °C, or 12 min at 65 °C. In addition, ionic liquid 1 reacted with sodium salts of substituted benzoates apparently through the direct S_N2 carboxylate alkylation to form esters 2 and the resulting esters further converted, via Wittig reaction, to finally afford aryl ketones 4.     

A comparative study of the complexation of Am(III) and Eu(III) with TODGA in room temperature ionic liquid

On the growing awareness of the environmental impact associated with the use of volatile organic diluents, room temperature ionic liquid gained world-wild acceptance as environmentally benign diluents for actinide partitioning. The observed unusual behavior of less extraction efficiency of Eu with TODGA in RTIL in comparison with that of Am-TODGA was addressed in this paper. The stoichiometry of Am-TODGA complex was found to be 1:2 while that of Eu-TODGA was 1:1. More the ligand molecules associated in the metal ligand complex, the organophilicity of the complex will be more and the solubility of the metal–ligand complex in RTIL will be more which reflects in the higher distribution ratio for Am. In RTIL both Am and Eu showed slower kinetics of extraction with TODGA which can be attributed to the high viscosity coefficient of RTIL compared to the molecular diluents. The observed slower kinetics of extraction was quantified and found to follow first order kinetics with the rate constant of 5.5 × 10^?4 s^?1. The formation constant of Am-TODGA complex was found to be more (4.18 × 10⁸ M^?1) than Eu-TODGA complex (3.31 × 10⁸ M^?1) in RTIL. The parameters viz. diffusion coefficient, activation energy for Eu(III)/Eu(II) were determined and found to be 3.08 × 10^?8/cm² s^?1 (at 303 K) and 39.34 kJ mol^?1 respectively. The thermodynamic parameters ΔG, ΔH and ΔS for the reaction were evaluated using the linear regression of the plot of E ^0* versus T. The redox reaction was found to be exothermic with decrease in entropy value.     

Dibutyl N,N-dibutylcarbamoylmethylphosphonate extraction of Eu(III) from perchlorate and nitrate solutions

Dibutyl N,N,-dibutylcarbamoylmethylphosphonate (DBDBCMP) has been used in the extraction study of Eu(III) from low acidic solutions. The different parameters affecting the distribution ratio have been studied. The reaction is considered as a chelate interaction and the extracted species are Eu(OH)₂ DBDBCMP·2HDBDBCMP and Eu(NO₃)₂ DBDBCMP. HDBDBCMP from perchlorate and nitrate, respectively. The equilibrium constants corresponding to the different species formed are calculated and discussed. The effect of changing diluent on extraction capacity of the phosphonate is also studied and discussed.     

Molecular dynamics simulation of the energetic room-temperature ionic liquid, 1-hydroxyethyl-4-amino-1,2,4-triazolium nitrate (HEATN)

Molecular dynamics (MD) simulations have been performed to investigate the structure and dynamics of an energetic ionic liquid, 1-hydroxyethyl-4-amino-1,2,4-triazolium nitrate (HEATN). The generalized amber force field (GAFF) was used, and an electronically polarizable model was further developed in the spirit of our previous work (Yan, T.; Burnham, C. J.; Del Popolo, M. G.; Voth, G. A. J. Phys. Chem. B 2004, 108, 11877). In the process of simulated annealing from a liquid state at 475 K down to a glassy state at 175 K, the MD simulations identify a glass-transition temperature region at around 250-275 K, in agreement with experiment. The self-intermediate scattering functions show vanishing boson peaks in the supercooled region, indicating that HEATN may be a fragile glass former. The coupling/decoupling of translational and reorientational ion motion is also discussed, and various other physical properties of the liquid state are intensively studied at 400 K. A complex hydrogen bond network was revealed with the calculation of partial radial distribution functions. When compared to the similarly sized 1-ethyl-4-methyl-1,4-imidazolium nitrate ionic liquid, EMIM+/NO3-, a hydrogen bond network directly resulting in the poorer packing efficiency of ions is observed, which is responsible for the lower melting/glass-transition point. The structural properties of the liquid/vacuum interface shows that there is vanishing layering at the interface, in accordance with the poor ion packing. The effects of electronic polarization on the self-diffusion, viscosity, and surface tension of HEATN are found to be significant, in agreement with an earlier study on EMIM+/NO3- (Yan, T.; Burnham, C. J.; Del Popolo, M. G.; Voth, G. A. J. Phys. Chem. B 2004, 108, 11877).     

Efficient white-light-emission from a heterometallo-supramolecular polymer with Eu(III) and Zn(II) ions introduced alternately

By utilizing energy transfer from ligands to metal ions, efficient white-light-emission (Φ_PL: 0.54, x?=?0.31, y?=?0.33) was realized in a heterometallo-supramolecular polymer with Eu(III) and Zn(II) ions introduced alternately. The polymer showed strong white-light-emission even in the film state as well as in solution.