Extraction spectrophotometry using a lithium-ion selective metallacrown: temperature effect on extraction reaction and application to determination of lithium in serum and seawater.

A metallacrown-type ionophore, 2,3-pyridinediolate-bridged (3,5-dimethylanisole)ruthenium trinuclear complex, has a high extraction selectivity for Li, but the extraction reaction is very slow. To solve this problem, the effect of temperature on the rapidity and equilibrium of the extraction of Li and Na as picrates from water to toluene with the metallacrown was investigated in this study. While the extraction of Li requires 6 h of shaking for equilibration at 25 °C, the distribution ratio becomes nearly constant after 4 h and 2 h of shaking at 37 °C and 50 °C, respectively.

Use of ionic liquids for extraction separation and concentration of iodide ions in brine samples.

Iodine in natural salt waters such as iodine-rich underground brine generally exists as iodide ions, and to extract iodide ions, it is necessary to oxidize them to nonpolar iodine molecules. In this study, we report that iodide ions in natural brine containing high concentrations of chloride ions can be quantitatively extracted without oxidation by extraction using ionic liquids. Extraction with the ionic liquids trihexyltetradecylphosphonium chloride and trioctyl ammonium chloride was found to be able to enrich trace amounts of iodide in brine samples up to 40- and 100-fold, respectively.

Planning study: prone versus supine position for stereotactic body radiotherapy in prostate by CyberKnife.

This study aimed to clarify the differences in radiotherapy dose characteristics and delivery efficiency between the supine and prone positions in patients with prostate cancer using the CyberKnife. The planning computed tomography (CT) and delineations of the prone position were obtained by rotating the supine CT images with delineations of 180° using image processing software. The optimization parameters for planning target volume (PTV) and organs at risk (OARs) were based on the prone position.

Separation of Light and Middle Lanthanides Using Multistage Extraction with Diglycolamide Extractant.

We investigated the chemical behavior of lanthanides (Ln) by multistage extraction. Using 10 aqueous phases with Ln and 3 organic phases, we drew the breakthrough curves for light and middle Ln. Our study reveals that the limit of metal extraction depends on their D values and the metal concentration employed in experiments.

Performance of a newly designed end-to-end phantom compatible with magnetic resonance-guided radiotherapy systems.

Purpose: In this study, we report on our proposed phantom based on the new end-to-end (E2E) methodology and its results. In addition, we verify whether the proposed phantom can replace conventional phantoms.

Methods: The hexagonal-shaped newly designed phantom has pockets on each side for a film dosimeter of size 80 × 90 mm , which is easily removable, considering the Co penumbra.

An Ionic Liquid-based Microextraction Method for Ultra-High Preconcentration of Paraquat Traces in Water Samples Prior to HPLC Determination.

An ionic liquid (IL)-based microextraction method was developed for the preconcentration of paraquat traces in water samples prior to HPLC determination. On the basis of the relationship between the aqueous solubility and the extractability of known ILs, 1-ethyl-3-methylimidazolium bis(nonafluorobutanesulfonyl)amide ([EMIm][NNf]) was selected as the extractant for paraquat. The distribution ratio of paraquat dication in the [EMIm][NNf]/water biphasic system was theoretically estimated to be nearly 10 at its maximum level, indicating that [EMIm][NNf] was suitable for the ultra-high preconcentration (a maximum of 10-fold concentration) of paraquat with a quantitative recovery (more than 99%).

Application of a Lithium-ion Selective Metallacrown to Extraction-Spectrophotometric Determination of Lithium in Saline Water.

The solvent-extraction behavior of Li and Na with a Li selective metallacrown, [{Ru(η-3,5-dimethylanisole)(2,3-pyridinediolate)}], was investigated in the presence of organic dye anions, 3',3″,5',5″-tetrabromophenolphthalein ethyl ester ([TBPE]), 2,6-dichloroindophenolate, and picrate ([pic]). Each alkali metal ion was extracted as a 1:1:1 ternary complex of the metal ion, metallacrown, and anion. The Li/Na extraction selectivity is anion dependent and highest with [pic].

The laws governing ionic liquid extraction of cations: partition of 1-ethylpyridinium monocation and paraquat dication in ionic liquid/water biphasic systems.

To find the laws governing the extraction of cations from aqueous solutions into hydrophobic ionic liquids (ILs), we investigated the partition of 1-ethylpyridinium monocation and paraquat (1,1'-dimethyl-4,4'-bipyridinium) dication in various IL/water biphasic systems. Ten different ILs of 1-butyl-3-methylimidazolium-based or bis(trifluoromethanesulfonyl)amide-based salts were used. The distribution ratio of the target cations (T(n+)) was dependent on the initial concentration in the aqueous phase and also very sensitive to the kind of IL.

Adsorption behavior of beryllium(II) on copper-oxide nanoparticles dispersed in water: A model for (7)Be colloid formation in the cooling water for electromagnets at high-energy accelerator facilities.

The adsorption behavior of Be(II) on CuO nanoparticles dispersed in water was studied as a model for colloid formation of radioactive (7)Be nuclides in the cooling water used for electromagnets at high-energy proton accelerator facilities. An aqueous Be(II) solution and commercially available CuO nanoparticles were mixed, and the adsorption of Be(II) on CuO was quantitatively examined. From a detailed analysis of the adsorption data measured as a function of the pH, it was confirmed that Be(II) is adsorbed on the CuO nanoparticles by complex formation with the hydroxyl groups on the CuO surface (>S-OH) according to the following equation: n > S-OH + Be(2+) ⇔ (>S-O)n Be((2-n)+) + nH(+) (n = 2, 3) S : solid surface.

Extraction of gallium(III) from hydrochloric acid solutions by trioctylammonium-based mixed ionic liquids.

The extractabilities of aluminium(III), gallium(III), and indium(III) from hydrochloric acid solutions were investigated using a mixture of two protic ionic liquids, trioctylammonium bis(trifluoromethanesulfonyl)amide ([TOAH][NTf(2)]) and trioctylammonium nitrate ([TOAH][NO(3)]). At a HCl concentration of 4 mol L(-1) or more, gallium(III) was nearly quantitatively extracted and the extractability order was Ga > Al >> In. The extractability of gallium(III) increased with increasing [TOAH][NO(3)] content in the mixed ionic liquid.

Mechanisms and rules of anion partition into ionic liquids: phenolate ions in ionic liquid/water biphasic systems.

It is important to understand the mechanisms and general rules of ion partitioning in hydrophobic ionic liquid (IL)/water biphasic systems in order to predict the extractability of an ionic species with various ILs. In this study, we have investigated the partition of picrate ion (target anion, T(-)) from aqueous sodium picrate solutions into several ILs and the accompanying changes in aqueous concentrations of the IL component cation (C(+)) and anion (A(-)) at 298.2 K.

Ion-pair formation between Cd(II), Na(I), and Ag(I) complex ions with 18-crown-6 ether derivatives and various pairing anions in water: an understanding of the ion-pair formation based on the HSAB principle.

The ion-pair formation constants (K(MLX)(0)/mol(-1) dm(3)) of CdL(2+) with Br(-) or NaL(+) with N,N-diethyldithiocarbamate ion (DDTC(-)) in water were determined potentiometrically at 25°C; ionic strength (I)→0: L denotes 18-crown-6 ether (18C6) and its mono-benzo derivative for the CdBr(2)-L system and 15-crown-5 ether and 18C6 for the NaDDTC-L one. The formation constant corresponding to the simple salt, NaDDTC, in water was also determined at I→0. Using the log K(CdLX)(0) values of CdLCl(+), CdLBr(+), CdLPic(+), and CdLSO(4), then CdL(2+) and picrate ion (Pic(-)) in water have been classified with the hard and soft acids and bases principle, where the values were available in the literature, except for CdLBr(+).

Extraction of some univalent salts into 1,2-dichloroethane and nitrobenzene: analysis of overall extraction equilibrium based on elucidating ion-pair formation and evaluation of standard potentials for ion transfers at the interfaces between their diluents and water.

Sodium permanganate, sodium picrate (NaPic), Bu(4)NPic, Me(4)NPic, and Et(4)NPic were extracted at an ionic strength of 2 × 10(-5) to 0.08 mol dm(-3) and 25°C from water (w)-phases into the organic (o)-ones, 1,2-dichloroethane (DCE) and nitrobenzene (NB). Thereby, apparent distribution constants (K(D,±)) of the anions (A(-)) or the cations (M(+)) and ion-pair formation ones (K(MA)(org)) of the univalent salts (MA) in the o-phases were determined at 25 °C, where K(D,±) = ([A(-)](o)[M(+)](o)/[A(-)][M(+)])(1/2) = (K(D,A)K(D,M))(1/2) and K(MA)(org) = [MA](o)/[M(+)](o)[A(-)](o).

New method for obtaining position and time structure of source in HDR remote afterloading brachytherapy unit utilizing light emission from scintillator.

When using a HDR remote afterloading brachytherapy unit, results of treatment can be greatly influenced by both source position and treatment time. The purpose of this study is to obtain information on the source of the HDR remote afterloading unit, such as its position and time structure, with the use of a simple system consisting of a plastic scintillator block and a charge-coupled device (CCD) camera. The CCD camera was used for recording images of scintillation luminescence at a fixed rate of 30 frames per second in real time.

Evaluation of the hydrophilic properties of crown ether-ion-pair complexes with alkali metal picrates by their distribution into less-polar diluents.

Cohesive energy densities (C(w,MLA)/J cm(-3)) for ion-pair complexes (MLA: M(+) = Li(+) to Cs+; w: water) with six crown ethers (L), such as 18-crown-6 ether (18C6), benzo-18C6, and dibenzo-24-crown-8 one, and A(-) = picrate were calculated at 298 K by a procedure that uses either (i) an equation rearranged from that underlying log K(D,MLA)-vs.-log K(D,L) plots or (ii) intercepts of their plots and from both procedures. Here, K(D,MLA) and K(D,L) denote the distribution constants of MLA and L from w into a diluent, respectively.

Solvent extraction of silver picrate by 3m-crown-m ethers (m = 5, 6) and its mono-benzo-derivative from water into benzene or chloroform: elucidation of an extraction equilibrium using component equilibrium constants.

Ion-pair formation constant (K(AgPic) in mol(-1)dm(3)) of silver picrate (AgPic), those (K(AgLPic)) of its ion-pair complexes (AgLPic) with crown ethers (L) and complex formation constants (K(AgL)) of Ag(+) with L (15-crown-5 ether (15C5) and benzo-15C5) in water (w) were determined potentiometrically at 25 degrees C. Compounds used as L were 18-crown-6 ether (18C6), its benzo-derivative (B18C6) and the two 15C5 derivatives. Extraction constants (K(ex) in mol(-1)dm(3)) of AgPic with L (15C5, 18C6, B18C6) from acidic w-phases into either C(6)H(6) or CHCl(3) were recalculated from K(AgPic), K(AgL), K(AgLPic) and data opened in previous papers.

Solvent extraction of permanganates (Na, K) by 18-crown-6 ether from water into 1,2-dichloroethane: elucidation of an extraction equilibrium based on component equilibria.

Ion-pair formation constants (K(MLA) mol(-1) dm(3)) of Na(+)- and K(+)-18-crown-6 ether (18C6) complexes with MnO(4)(-) in water (w) were determined potentiometrically at 25 degrees C. Simultaneously, extraction constants (K(ex) mol(-2) dm(6)) of the permanganates with 18C6 from w into 1,2-dichloroethane at 25 degrees C were obtained from the spectrophotometric determination of distribution ratios of the permanganates. These K(ex) values were divided into K(MLA) and other three component equilibrium constants and thereby extraction-selectivity and -ability were discussed in comparison with corresponding metal picrate-18C6 extraction systems reported before.

Extraction of sodium and potassium perchlorates with benzo-18-crown-6 into various organic solvents. Quantitative elucidation of anion effects on the extraction-ability and -selectivity for Na(+) and K(+).

To investigate quantitatively the anion effect on the extraction-ability and -selectivity of benzo-18-crown-6 (B18C6) for alkali metal ions, the constants for overall extraction into various diluents having low dielectric constants (K(ex)) and aqueous ion-pair formation (K(MLA)) of B18C6-sodium and potassium perchlorate 1:1:1 complexes (MLA) were determined at 25 degrees C. The K(ex) value was analyzed by the four fundamental equilibrium constants. The K(MLA) values were determined by applying our established method to this perchlorate extraction system.

Distribution of 1-alkyl-3-methylimidazolium ions and their ion pairs between dichloromethane and water.

The distribution behavior of the salts of a series of 1-alkyl-3-methylimidazolium cations (RMeIm(+); R = butyl, hexyl, and octyl) with tetrafluoroborate (BF(4)(-)), hexafluorophosphate (PF(6)(-)), bis(trifluoromethanesulfonyl)amide (NTf(2)(-)), and 2,4,6-trinitrophenolate (Pic(-)) anions has been investigated in a dichloromethane-water system at 25 degrees C. The distribution constants (K(D)) of the ion pairs and the transfer activity coefficients ((o)gamma(w)) of the single ions were determined. For the ion pairs with a given anion, the log K(D) value increases linearly with the number of methylene groups (N(CH2)) in the cation, which can be explained by using the regular solution theory.

Selective extraction of lithium with a macrocyclic trinuclear complex of (1,3,5-trimethylbenzene)ruthenium(II) bridged by 2,3-dioxopyridine.

A macrocyclic trinuclear complex of (1,3,5-trimethylbenzene)ruthenium(II) bridged by 2,3-dioxopyridine was synthesized, and the extraction properties for lithium and sodium picrates were investigated in a dichloromethane/water system at 25 degrees C. The complex was found to have extremely high extractability and selectivity for lithium picrate; the logarithmic values of the extraction constants are 5.86 and 2.

Evaluation of the hydrophilic property of sodium ion-pair complexes with 3m-crown-m ethers (m = 5, 6) and their benzo-derivatives by solvent extraction.

The ion-pair formation constants {K(j)(0): j = MA (metal salt), MLA} of NaO(2)CCF(3) (Na(+)tfa(-)) and its ion-pair complexes (MLA) in water (w) were determined potentiometrically at 25 degrees C and an ionic strength (I) of zero. 15-Crown-5 (15C5), 18-crown-6 ethers (18C6), and their mono-benzo derivatives were used as crown ethers (L). The extraction of Natfa by these four L from w into 1,2-dichloroethane was done at 25 degrees C, and then the extraction constants (K(ex)) for NaLtfa were calculated by using the K(j) values, which were estimated from the corresponding K(j)(0) ones at I of the w-phases, and other equilibrium constants.

Hydration effect on the ion-pair extraction of lithium picrate by hydrophobic benzo-15-crown-5 ether into various less-polar diluents.

The ion-pair formation constant (K(MLA)(0) in mol(-1) dm(3)) for Li(B15C5)(+) with a picrate ion (Pic(-)) in water was determined by potentiometry with a K(+)-selective electrode at 25 degrees C and an ionic strength of 0, where B15C5 denotes benzo-15-crown-5 ether. Using the concentration equilibrium constants, K(MLA), estimated from this value, the extraction constants (mol(-2) dm(6) unit) of about ten diluents were re-calculated from previously reported extraction data. Also, the distribution constants of an ion-pair complex, Li(B15C5)Pic, between water and the diluents were re-estimated.

Proton-beam therapy for olfactory neuroblastoma.

Purpose: To analyze the feasibility and efficacy of proton-beam therapy (PBT) for olfactory neuroblastoma (ONB) as a definitive treatment, by reviewing our preliminary experience. Olfactory neuroblastoma is a rare disease, and a standard treatment strategy has not been established. Radiation therapy for ONB is challenging because of the proximity of ONBs to critical organs.

Solvent extraction of sodium perrhenate by 3m-crown-m ethers (m=5, 6) and their mono-benzo-derivatives into 1,2-dichloroethane: Elucidation of an overall extraction equilibrium based on component equilibria containing an ion-pair formation in water.

Equilibrium constants (K(MLA)(0)/mol(-1)dm(3)) for the ion-pair formation of a complex ion NaL(+) with ReO(4)(-) in water were determined potentiometrically at 25 degrees C and the ionic strength (I) of 0mol dm(-3) using a Na(+)-selective electrode. Here, crown ethers, L, were 15-crown-5 ether (15C5), benzo-15C5, 18-crown-6 ether (18C6) and benzo-18C6. Also, NaReO(4) was extracted by the L into 1,2-dichloroethane and then extraction constants (K(ex)/mol(-2)dm(6)) for the species, NaLReO(4), were determined at 25 degrees C by AAS.

Determination of ion-pair formation constants of univalent metal-crown ether complex ions with anions in water using ion-selective electrodes: application of modified determination methods to several salts.

Ion-pair formation constants (mol(-1) dm3 unit), K(MX) for a univalent metal salt (MX) and K(MLX) for its ion-pair complex (ML+X-) with a crown ether (L) in water, were determined at various ionic strengths (I) and 25 degrees C by potentiometry with ion-selective electrodes for MX=NaPic, NaMnO4, NaBPh4, KPic, and KMnO4; and MLX = Na(18C6)Pic, K(18C6)Pic, and Na(18C6)BPh4, where Pic- and 18C6 denote a picrate ion and 18-crown-6 ether, respectively. Equations for analyzing I-dependence of logK(MLX) and logK(MX) were derived and fitted well to the I-dependence using a non-linear regression analysis. The equilibrium constants at I = 0 mol dm(-3), K(MLX) degrees and K(MX) degrees, were simultaneously obtained from the analysis.