Selective Crystallization of Phosphoester Coordination Polymer for the Separation of Neodymium and Dysprosium: A Thermodynamic Approach.

Thermodynamics of the formation of coordination polymers (CPs) or metal-organic frameworks (MOFs) has not been focused on, whereas many CPs or MOFs have been synthesized in a solution. With a view of separating Nd3+ and Dy3+ in an aqueous solution, we demonstrate that crystallization of the CPs of Nd3+ and Dy3+ based on dibutyl phosphoric acid (Hdbp) can be thermodynamically described; crystallization yields of [Ln(dbp)3] (Ln = Nd or Dy) complex are predicted well using a simple calculation, which takes the apparent solubility products (Kspa) for [Ln(dbp)3] and the acid dissociation constant of Hdbp into account. The Kspa values of [Nd(dbp)3] and [Dy(dbp)3] are experimentally determined to be (1.3 ± 0.1) × 10-14 and (2.9 ± 0.4) × 10-18 M4, respectively, at 20 °C. The ratio of these Kspa values, that is, ca. 4500, is significantly larger than the ratio of the solubility products for inorganic salts of Nd3+ and Dy3+. Therefore, Nd3+ and Dy3+ are selectively crystallized in an aqueous solution via the formation of CPs. Under optimized conditions, Dy3+ crystallization is preferable, whereas Nd3+ remains in the solution phase, where the ratio of the Dy molar content to the total metal content (i.e., Nd + Dy) in the crystal is higher than 0.9. The use of acids, such as HCl or HNO3, has no practical impact on the separation in an aqueous solution.

Magnitude and Directionality of Halogen Bond of Benzene with C6F5X, C6H5X, and CF3X (X = I, Br, Cl, and F).

Geometries of benzene complexes with C6F5X, C6H5X, and CF3X (X is I, Br, Cl, and F) were optimized, and their interaction energies were evaluated. The CCSD(T) interaction energies at the basis set limit (Eint) of C6F5X (X is I, Br, Cl, and F) with benzene were -3.24, -2.88, -2.31, and -0.92 kcal mol(-1). Eint of C6H5X (X is I, Br, and Cl) with benzene were -2.31, -1.97, and -1.48 kcal mol(-1). The fluorination of halobenzenes slightly enhances the attraction. Eint of CF3X (X is I, Br, Cl, and F) with benzene (-3.11, -2.74, -2.22, and -0.71 kcal mol(-1)) were very close to Eint of corresponding C6F5X with benzene. In contrast to the halogen bond of iodine and bromine with pyridine (n-type halogen bond acceptor) where the main cause of the attraction is the electrostatic interactions, that of halogen bond with benzene (p-type acceptor) is dispersion interaction. In the halogen bonds with p-type acceptors (halogen-π interactions), the electrostatic interactions and induction interactions are small. The overall orbital-orbital interactions are repulsive. The directionality of halogen bonds with p-type acceptors is very weak, owing to the weak electrostatic interactions, in contrast to the strong directionality of the halogen bonds with n-type acceptors and hydrogen bonds.

Central metal ion exchange in a coordination polymer based on lanthanide ions and di(2-ethylhexyl)phosphoric acid: exchange rate and tunable affinity.

In this paper the exchange of lanthanide(III) ions (Ln(3+)) between a solution and a coordination polymer (CP) of di(2-ethylhexyl)phosphoric acid (Hdehp), [Ln(dehp)3], is studied. Kinetic and selectivity studies suggest that a polymeric network of [Ln(dehp)3] has different characteristics than the corresponding monomeric complex. The reaction rate is remarkably slow and requires over 600 h to reach in nearly equilibrium, and this can be explained by the polymeric crystalline structure and high valency of Ln(3+). The affinity of the exchange reaction reaches a maximum with the Ln(3+) possessing an ionic radius 7% smaller than that of the central Ln(3+), therefore, the affinity of the [Ln(dehp)3] is tunable based on the choice of the central metal ion. Such unique affinity, which differs from the monomeric complex, can be explained by two factors: the coordination preference and steric strain caused by the polymeric structure. The latter likely becomes predominant for Ln(3+) exchange when the ionic radius of the ion in solution is smaller than the original Ln(3+) by more than 7%. Structural studies suggest that the incoming Ln(3+) forms a new phase though an exchange reaction, and this could plausibly cause the structural strain.

Steric effect involved in Ln3+/Ce3+ exchange in a coordination polymer based on di(2-ethylhexyl)phosphoric acid.

Coordination polymers can be attractive ion exchange materials because of their crystallinity and semi-flexibility, which are rather opposing properties, and play integral and synergistic roles in introducing unique ion-exchange behavior. In this paper, Ln(3+)/Ce(3+) exchange (Ln(3+) = Nd(3+), Gd(3+), Dy(3+), or Lu(3+)) in a coordination polymer, [Ce(dehp)3], based on di(2-ethylhexyl)phosphoric acid (Hdehp) is studied by distribution coefficient measurements, ion-exchange isotherms, Kielland plot analysis, and morphology observation. The ion-exchange selectivity is in the order Nd(3+) < Gd(3+) < Dy(3+) < Lu(3+) when a small amount of Ln(3+) is loaded, but Lu(3+) ≈ Nd(3+) < Gd(3+) ≈ Dy(3+) for a high loading ratio. The Kielland plot suggests that a steric effect is involved in the reactions, which becomes stronger in the order of Nd(3+)/Ce(3+) < Gd(3+)/Ce(3+) < Dy(3+)/Ce(3+) < Lu(3+)/Ce(3+) for exchange systems. This trend is attributable to the differences in the ionic sizes between an incoming Ln(3+) and original Ce(3+). Scanning electron microscopy observations reveal the generation of a new phase via the Ln(3+)/Ce(3+) exchange. Such a phenomena results from solid-solid transformation, rather than dissolution-recrystallization. The small steric strain in the Nd(3+)/Ce(3+) system leads to the formation of a Nd(3+)-and-Ce(3+) solid-solution, whereas the morphological change is possibly restrained by the strong strain caused by loaded Ln(3+) with an ionic size significantly smaller than the original Ce(3+).

Tunable selectivity of lanthanide ion exchange within a coordination polymer.

The exchange of lanthanide(III) ions (Ln(3+)) between a solution and a coordination polymer (CP) formed by cerium(III) or samarium(III) ion and an organophosphorous ligand has been studied. The CPs exhibit distinctive Ln(3+) affinity that varies with a small change in its framework, depending on the central Ln(3+).

CCSD(T) level interaction energy for halogen bond between pyridine and substituted iodobenzenes: origin and additivity of substituent effects.

The CCSD(T) level interaction energies at the basis set limit (E(int)) were calculated for 33 halogen bonded pyridine complexes with substituted iodobenzenes. The CCSD(T) level electron correlation correction substantially decreases the magnitude of attraction in comparison with the MP2. The E(int) for the pyridine complexes with mono substituted iodobenzenes varies from -3.14 to -4.42 kcal mol(-1), depending on the substituent. The electron-withdrawing substituents such as NO2 enhance the attraction, while the effects of electron-donating substituents reduce. The additivity of the substituent effects is observed for the E(int) of the pyridine complexes with multiple substituted iodobenzenes. The electrostatic interactions are mainly responsible for the substituent effects on the magnitude of the attraction in the halogen-bonded complexes. The electrostatic energy depends significantly on the substituent. They have a strong correlation with the E(int). On the other hand the effects of the substituent on the dispersion energy are small, however the dispersion does contribute greatly to the attraction.

Data mining of supersecondary structure homology between light chains of immunogloblins and MHC molecules: absence of the common conformational fragment in the human IgM rheumatoid factor.

It is shown that fuzzy search and data mining techniques of supersecondary structure homology for subunits of proteins using conformational code patterns of α-helix-type (3ß5α4ß) and ß-sheet-type (6α4ß4ß) fragments can be used to extract correlations between fragments of MHC class I molecules and the light chain of immunoglobulins. The new method of conformational pattern analysis with fuzzy search of structural code homology reflects well the shape of main chain rather than secondary structure in comparison with the DSSP method. Further, the data mining technique using the combination of h- and s-fragment patterns can quantify the supersecondary structure homology between any subunits of proteins with different amino acid sequences. Characteristic fragment patterns (string "shhshss"), which were sandwiched between two identical amino acid sequences His and Pro, were found in light chains of various types of immunogloblins, α-chain and ß-2 microglobulin of MHC class I and α-chain and ß-chain of MHC class II, but not in heavy chains of Fab immunoglobulin fragments and T cell receptors (TCR). Leukocyte immunoglobulin-like receptors (LILR) are related by the conformational fragment (string "shhshss") to ß-2 microglobulins as a type of pair forms (string "sohsss"). Further, human IgM rheumatoid factor, one of the immunogloblins, did not strongly exhibit the conformational fragment pattern. Nonclassic MHC class I molecules CD1D, MIC-A, and MIC-B, which have functions to activate NKT, NK, and T cells, did not also clearly show the patterns. These code-driven mining techniques can be utilized as a metadata-generating tool for systems biology to elucidate the biological function of such conformational fragments of MHC I and II molecules, which come in contact with various signal ligands on the surface of T cells and natural killer cells.

Magnitude and origin of the attraction and directionality of the halogen bonds of the complexes of C6F5X and C6H5X (X = I, Br, Cl and F) with pyridine.

The geometries and interaction energies of complexes of pyridine with C(6)F(5)X, C(6)H(5)X (X = I, Br, Cl, F and H) and R(F)I (R(F) = CF(3), C(2)F(5) and C(3)F(7)) have been studied by ab initio molecular orbital calculations. The CCSD(T) interaction energies (E(int)) for the C(6)F(5)X-pyridine (X = I, Br, Cl, F and H) complexes at the basis set limit were estimated to be -5.59, -4.06, -2.78, -0.19 and -4.37 kcal mol(-1) , respectively, whereas the E(int) values for the C(6)H(5)X-pyridine (X = I, Br, Cl and H) complexes were estimated to be -3.27, -2.17, -1.23 and -1.78 kcal mol(-1), respectively. Electrostatic interactions are the cause of the halogen dependence of the interaction energies and the enhancement of the attraction by the fluorine atoms in C(6)F(5)X. The values of E(int) estimated for the R(F)I-pyridine (R(F) = CF(3), C(2)F(5) and C(3)F(7)) complexes (-5.14, -5.38 and -5.44 kcal mol(-1), respectively) are close to that for the C(6)F(5)I-pyridine complex. Electrostatic interactions are the major source of the attraction in the strong halogen bond although induction and dispersion interactions also contribute to the attraction. Short-range (charge-transfer) interactions do not contribute significantly to the attraction. The magnitude of the directionality of the halogen bond correlates with the magnitude of the attraction. Electrostatic interactions are mainly responsible for the directionality of the halogen bond. The directionality of halogen bonds involving iodine and bromine is high, whereas that of chlorine is low and that of fluorine is negligible. The directionality of the halogen bonds in the C(6)F(5)I- and C(2)F(5)I-pyridine complexes is higher than that in the hydrogen bonds in the water dimer and water-formaldehyde complex. The calculations suggest that the C-I and C-Br halogen bonds play an important role in controlling the structures of molecular assemblies, that the C-Cl bonds play a less important role and that C-F bonds have a negligible impact.

Cluster structure of imidazolium salts in methanol controlled by the balance of interactions: cation-anion, cation-solvent, and anion-solvent.

We have studied the cluster structure of 1-butyl-3-methylimidazolium halide, bmimX (X = Cl, Br, I), in methanol solution by means of an electrospray mass spectrometer, which is specially designed for analysis of clusters isolated from solution. In positive ion mode experiments, the ratio of solvated bmim(+), bmim(+)(MeOH)(n) and ion-pair clusters, bmim(bmim(+)X(-))(m) was dependent on the counter anion. As for bmimCl solutions, few solvated bmim(+) clusters were observed, and the ion-pair clusters were clearly observed. On the other hand, bmimBr and bmimI with large anions, the solvated bmim(+) clusters increased obviously, and the ion-pair clusters were in turn remarkably decreased. In negative ion-mode experiments, the solvation for Br(-) by the methanol is found to be the most prominent among those for Cl(-), Br(-), and I(-). These results were reasonably explained in consideration of the balance between ion-solvent and ion-counterion interactions.

Nucleation in alkali metal chloride solution observed at the cluster level.

Nucleation processes of alkali metal chlorides (MCl) in methanol were studied by specially designed electrospray ionization mass spectrometry at the cluster level. From solutions of LiCl, NaCl, KCl and RbCl, the M+ (MCl)n clusters with n = 4, 13 and 22 were observed prominently as magic number clusters. These clusters correspond to a square-planar 3 x 3 x 1, cubic 3 x 3 x 3, and cuboid 3 x 3 x 5 structure, respectively. On the other hand, from the solution of CsCl, the Cs+ (CsCl)n clusters were almost monotonically decreased with an increase in the cluster size n, without showing any magic number species. This has a good correlation with the difference in the crystalline structures. When nucleation occurs in the condensed phase, the difference in the crystalline structure will be realised at the cluster level. Moreover, it was demonstrated that the mass distributions of K+ (KCl)n and Cl-(KCl)n' clusters look very similar. When these inter-cluster interactions take place efficiently, the crystal growth will be accelerated rapidly.

Small-angle x-ray scattering measurement of a mist of ethanol nanodroplets: an approach to understanding ultrasonic separation of ethanol-water mixtures.

Small-angle x-ray scattering measurements using a brilliant x-ray source revealed nanometer sized liquid droplets in a mist formed by ultrasonic atomization. Ultrasonic atomization of ethanol-water mixtures produced a combination of water-rich droplets of micrometer order and ethanol-rich droplets as small as 1 nm, which is 10(-3) times smaller than the predicted size. These sizes were also obtained for mists generated from the pure liquids. These results will help to clarify the mechanism of "ultrasonic ethanol separation," which has the potential to become an alternative to distillation.

WITHDRAWN: Solvent effect on PCR from a viewpoint of a change of microscopic environment of Mg(2+) in a solution.

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Camphor ionic liquid: correlation between stereoselectivity and cation-anion interaction.

[structure: see text] As a halogen-free anion for an imidazolium room temperature ionic liquid, the use of a camphorsulfonate causes an increase in the number of free (naked) imidazolium cations, which produces an effective endo/exo stereoselective Diels-Alder reaction.

Solvation of tetraalkylammonium chlorides in acetonitrile-water mixtures: mass spectrometry and molecular dynamics simulations.

The solvation of tetramethylammonium chloride (Me4NCl) and tetra-n-butylammonium chloride (Bu4NCl) in water-acetonitrile mixtures was investigated by mass spectrometry of clusters isolated from the solution. As far as the positive ions are concerned, clusters composed of alkylammonium ions and acetonitrile molecules only were observed, even for mixtures with high water content. In contrast, for the negative ions, clusters composed of chloride with both water and/or acetonitrile molecules were observed. For the smaller system (Me4NCl) we performed quantum chemical calculations and molecular dynamics simulations. It was found that even though water is present in the solvation shell of Me4N+, only acetonitrile has a strong electrostatic interaction with the cation. Water molecules around Me4N+ form hydrogen bonds with other water molecules, and they interact with Me4N+ mainly via dispersive interactions. These results indicate that Me4N+ behaves like a hydrophobic solute. On the other hand, the interaction of Cl- with water and acetonitrile is of comparable strength and, in both cases, the electrostatic interaction dominates. Herein we demonstrate experimentally and theoretically that positive and negative ions give rise to characteristic solvation structures in mixed solvents: even a relatively small organic cation, such as Me4N+, exhibits a hydrophobic-like solvation shell.

Phase separation of water-alcohol binary mixtures induced by the microheterogeneity.

The relationship between liquid-liquid phase separation and microheterogeneity in water-primary alcohol mixtures was examined by analysing the mass spectra of clusters generated through the fragmentation of liquid droplets. By comparing the cluster structures of water-ethanol, -1-propanol, and -1-butanol binary mixtures at various alcohol concentrations, we discovered differences in the molecular clusters that control phase separation. We also studied the role of water in alcohol self-association. Alcohol self-association is promoted in the presence of a small amount of water (ca. 10 approximately 20 wt%), in which the water-water hydrogen-bonding network is weak and does not contribute to alcohol self-association. We have demonstrated that alcohol self-association is also promoted by non-ideal mixing with other alcohols. The self-association of alcohol molecules complements the loss of stabilization energy caused by the relatively weak coexisting interactions. This complementary relationship among intermolecular interactions is an inherent property of solutions, and plays a key role in the phase separation process.

Clustering structure of aqueous solution of kinetic inhibitor of gas hydrates.

Poly-[N-vinylcaprolactam] (PVCAP) and its related compounds are specific polymeric compounds for inhibiting hydrate formation. To clarify the inhibition mechanism of these compounds on hydrate nucleation at the molecular level, we measured the mass spectra of clusters generated from the fragmentation of liquid droplets including N-methylcaprolactam (NMCAP; functional group of PVCAP). By comparing the mass spectra of clusters of the solutions--pure D2O, tetrahydrofuran (THF)-D2O, NMCAP-D2O, and THF-NMCAP-D2O--it was found that the interaction of NMCAP with D2O was much stronger than that of THF with D2O. The relative intensity ratio of D+(NMCAP)m(D2O)n clusters to all the clusters observed for the NMCAP-D2O (1:250) mixed solution was 0.45. On the other hand, the relative intensity ratio of D+(THF)1(D2O)n clusters to all the clusters observed for the THF-D2O (1:17) mixed solution was 0.15. In the case of the THF-NMCAP-D2O three-component mixed solution, the NMCAP-D2O interaction was more predominant than the THF-D2O interaction, even at a lower NMCAP concentration. NMCAP reduces free mobile water molecules around NMCAP, but THF does not. This correlates with the facts that THF forms its hydrate below the freezing point and that PVCAP works as an inhibitor of gas hydrates.

Nature of the chemical bond formed with the structural metal ion at the A9/G10.1 motif derived from hammerhead ribozymes.

We have studied the interaction between metal ions and the metal ion-binding motif in hammerhead ribozymes, as well as the functions of the metal ion at the motif, with heteronuclear NMR spectroscopy. In this study, we employed model RNA systems which mimic the metal ion-binding motif and the altered motif. In Co(NH3)6(III) titrations, we observed large 1H and 31P chemical shift perturbations for the motif and found that outer-sphere complexation of Co(NH3)6(III) is possible for this motif. From the reinvestigation of our previous 15N chemical shift data for Cd(II) binding, in comparison with those of organometallic compounds, we conclude that Cd(II) can form an inner-sphere complex with the nucleobase in the motif. Therefore, the A9/G10.1 site was found to accept both inner-sphere and outer-sphere complexations. The Mg(II) titration for a slightly different motif from the A9/G10.1 site (G10.1-C11.1 to A10.1-U11.1) revealed that its affinity to Mg(II) was drastically reduced, although the ribozyme with this altered motif is known to retain enzymatic activities. This observation suggests that the metal ion at these motifs is not a catalytic center of hammerhead ribozymes.

Microscopic environment of metal ion controlled by the balance between preferential solvation and coordination.

The preferential solvation and the coordination characterizing metal ions (Mg2+ and Zn2+) in solution, which control the microscopic environments around the metal ions, were directly observed through the mass spectrometric analysis of clusters isolated from liquid droplets.