Calculation of electrostatic energy H-e(fd) on 4f(N-1)5d configurations for heavy lanthanide ions

For the 4f(N-1)5d configuration the Coulomb interaction between f and d electrons was parameterized by F-k(fd) with K = 2, 4, and G(K)(fd) with K = 1, 3, 5. The spin-orbit interaction for 4f and 5d electrons can be parameterized by xi (f) and xi (d) respectively, which can be compounded into one lambda : lambda = axi (f) + bxi (d), where a and b are the corresponding coefficients. The energy expressions of H-e(fd) of the chief low-energy levels of 4f(N-) (1)5d configuration for heavy lanthanide ions were calculated and the corresponding spin-orbit parameters lambda were also given in LS coupling, which are profitable in analyzing the spectra of the heavy lanthanide ions.

The optical spectroscopic properties of rare earth-activated barium orthophosphate in VUV-Vis range

The optical properties of rare earth ions-activated barium orthophosphate phosphors, Ba-3(PO4)(2):RE (RE = Ce3+, Sm3+, Eu3+, Eu2+, and Tb3+), were investigated in vacuum ultraviolet (VLTV)-Vis range. A band-band transition Of PO43- in Ba-3(PO4)(2) is observed in the region of 150-170 nm. The partial reduction of Eu3+ to Eu2+ was observed and confirmed by luminescent spectra under the VUV-UV excitation. It is proposed that the electronegative defects that formed by aliovalent substitution of Eu3+ on the Ba2+ site in the host are responsible for the reduction process.

Solvent extraction of scandium(III), yttrium(III), lanthanides(III), and divalent metal ions with sec-nonylphenoxy acetic acid

Such physicochemical properties of sec-nonylphenoxy acetic acid (CA-100) as the solubility in water, acid dissociation constant in water, dimerization constant in heptane, and distribution constant in organic solvent-water were measured by two-phase titration. The extraction behaviors of scandium (III), yttrium (III), lanthanides (III), and divalent metal ions from hydrochloric acid solutions with CA-100 in heptane have been investigated, and the possibilities of separating scandium (yttrium) from lanthanides and divalent metal ions have been carefully discussed. The stoichiometries of the extracted metal complexes were investigated by the slope-analysis technique. The effect of the nature of diluent on the extraction of yttrium (III) with CA100 has been studied and correlated with the dielectric constant.

Solvent effects of a fluorescent polyquinoline chemosensor for metal ions

Red shift and quenching effects of the fluorecence spectra of polyquinoline (PQH) solutions in different solvents are observed upon the addition of metal ions, which demonstrates the extraordinary solvent effects on metal-ion recognition and sensing ability (including sensitivity and selectivity) of PQH.

Alkali metal ions transfer across a water/1,2-dichloroethane interface facilitated by a novel monoaza-B15C5 derivative

In this paper, a novel monoaza-B15C5 derivative, N-(2-tosylamino)-isopentyl-monoaza-15-crown-5 (L), is used as an ionophore to facilitate alkali metal cations transfer across a water/1,2-dichloroethane (W/DCE) interface. Well-defined voltammetric behaviors are observed at the polarized W/DCE interfaces supported at micro- and nano-pipets except Cs+. The diffusion coefficient of this ionophore in the DCE phase is calculated to be equal to (3.3+/-0.2) x 10(-6) cm(2) s(-1). The experimental results indicate that a 1:1 (metal: ionophore) complex is formed at the interface with a TIC/TID mechanism. The selectivity of this ionophore towards alkali ions follows the sequence Na+ > Li+ > K+ > Rb+ > Cs+. The logarithm of the association constants (log beta(1)(0)) of the LiL+, NaL+, KL+ and RbL+ complexes in the DCE phase are calculated to be 10.6, 11.6, 9.0 and 7.1, respectively. The kinetic parameters are determined by steady-state voltammograms using nanopipets. The standard rate constants (k(0)) for Li+, Na+, K+ and Rb+ transfers facilitated by L are 0.54+/-0.05, 0.63+/-0.09, 0.51+/-0.04 and 0.46+/-0.06 cm s(-1), respectively. The pH values of aqueous solution have little effect on the electrochemical behaviors of these facilitated processes. The results predicate that this new type of ionophore might be useful to fabricate electrochemical sensor of sodium ion.

Sol-gel derived silicate oxyapatite phosphor films doped with rare earth ions

Rare-earth (Eu3+, Tb3+)-doped Ca2Y8(SiO4)(6)O-2 luminescent thin films were dip-coated on silicon and quartz glass substrates through a sol-gel route. X-ray diffraction (XRD), scanning electron microscopy (SEM) and luminescence excitation and emission spectra as well as luminescence decays were used to characterize the resultant films. The results of XRD reveal that these films remain amorphous below 700 degreesC, begin to crystallize at 800 degreesC, and crystallize completely around 1000 degreesC with an oxyapatite structure. The grain structure of the film can be seen clearly from SEM micrographs, where particles with various shape and average size of 250 nm can be resolved. The Eu3+ and Tb3+ ions show their characteristic red (D-5(0)-F-7(2)) and green (D-5(4)-F-7(5)) emission in the films with a quenching concentration of 10 and 6 mol% (of Y3+), respectively. The lifetime of Eu-3divided by increases with the heat treatment temperature front 700 to 1100 degreesC.

Phenanthroline-functionalized MCM-41 doped with europium ions

Organo-functionalized MCM-41 containing non-covalently linked 1,10-phenanthroline (denoted as Phen-MCM-41) was synthesized by template-directed co-condensation of tetraethoxysilane and the modified phenanthroline (denoted as Phen-Si). XRD, FTIR, UV/VIS spectroscopy as well as luminescence spectroscopy were employed to characterize Phen-MCM-41. No disintegration or loss of the Phen-Si during the solvent extraction procedure could be observed. When monitored by the ligand absorption wavelength (272 nm), the undoped MCM-41 produces a broad band emission centered at 450 run, whereas europium (III) doped Phen-MCM-41 displays the emission of the Eu3+, i.e., D-5(0) --> F-7(J) (J = 0, 1, 2, 3, 4) transition lines due to the energy transfer from the ligands to Eu3+ as well as a broad band emission centered at 442 nm.

Mechanisms of sodium and potassium ions transfer facilitated by dibenzo-15-crown-5 across the water /1,2-dichloroethane interface using micropipettes

The transfer of sodium and potassium ions facilitated by dibenzo-15-crown-5 (DB15C5) has been studied at the micro-water/1,2-dichloroethane (water/DCE) interface supported at the tip of a micropipette. Cyclic volt-ammetric measurements were performed in two limiting conditions: the bulk concentration of Na+ or K+ in the aqueous phase is much higher than that of DB15C5 in the organic phase (DB15C5 diffusion controlled process) and the reverse condition (metal ion diffusion controlled process). The mechanisms of the facilitated Na+ transfer by DB15C5 are both transfer by interfacial complexation (TIC) with 1 : 1 stoichiometry under these two conditions, and the corresponding association constants were determined at log beta(1) = 8.97 +/- 0.05 or log beta(1) = 8.63 +/- 0.03. However, the transfers of K+ facilitated by DB15C5 show different behavior. In the former case it is a TIC process and its stoichiometry is 1 : 2, whereas in the latter case two peaks during the forward scan were observed, the first of which was confirmed as the formation of K (DB15C5)(2) at the interface by a TIC mechanism, while the second one may be another TIC process with 1 : 1 stoichiometry in the more positive potential. The relevant association constants calculated for the complexed ion, K+(DB15C5)(2), in the organic phase in two cases, logbeta(2), are 13.64 +/- 0.03 and 11.34 +/- 0.24, respectively.

The interaction of aldolase with the cytoplasmic domain of human erythrocyte band 3 inhibited by lanthanum ions

The effect of lanthanum ions on the activity of the cytoplasmic domain of human erythrocyte band 3 (CDB3), which was measured according to the inhibition to aldolase, was studied. In the presence of low concentration of lanthanum ions, the function of CDB3 to inhibit aldolase activity decreased significantly. It indicated that lanthanum ions in the erythrocyte would change the conformation of CDB3 and influence the control on aldolase activity.

Study of the interaction between lanthanide ions and a supported bilayer lipid membrane by cyclic voltammetry and ac impedance

The interaction of lanthanide ions with a supported bilayer lipid (1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine) membrane (sBLM) was investigated by cyclic voltammetry and ac impedance spectroscopy in this paper, Lanthanide can affect the conformation of the supported bilayer lipid membrane and cause pore formation. Through the pores, Fe(CN)(6)(3) (4) can reach the electrode surface and show its redox behaviour. Furthermore the redox currents or Fe(CN)(6)(3) (4) increased with increasing concentration of lanthanides and leveled off at 1.2 muM for Eu3+. The interaction ability of three lanthanides with sBLM follows the sequence: Eu3+ > Tb3+ > La3+.

Promoter effects of rare earth ions on electrocatalytic oxidation of methanol

The promoter effects of rare earth ions on the electrocatalytic oxidation of methanol at the Pt electrode were studied using the cyclic voltammetry and stable polarization techniques. It was found for the first time that Eu, Ho, Dy ions could accelerate the electrocatalytic oxidation of methanol at the Pt electrode, while Lu, Pr, Yb, Sm ions showed inhibitor effects.

VUV excited luminescence of europium activated calcium borophosphate prepared in air

XAFS (EXAFS and XANES) at Eu-L-3 edge were used to determine the local structure and the valences of europium in CaBPO5:Eu prepared in air. The results of EXAFS showed that the doped europium atoms were nine-coordinated by oxygen atoms and the distances of bond Eu-O were 2.39 Angstrom in the host lattice. XANES at Eu-L-3 edge exhibited that Eu2+ and Eu3+ coexisted in the matrix. The luminescent spectrum of the material excited by VUV at 147 nm presented a similar spectrum with that excited by f-f transition of Eu2+ at 396 nm and f-d transition of Eu2+ at 312 nm. The broad emission band due to both 4f(6)5d - 4f(7) transition of EU2+ and f - f transition of Eu3+ could be observed in emission spectra, which indicated that the trivalent europium ions were reduced in air in the matrix at high temperature by the defects [V-Cn]" formed by aliovalent substitution between Ca2+ and Eu3+ ions. The UV excitation spectrum showed the typical f-f transition of Eu3+ and f-d transition of Eu2+. The bands with the maxima at about 113 and 158 nm in VUV excitation spectrum were assigned to originate from the absorption of the host lattice.

Sol-gel deposition and luminescent properties of oxyapatite Ca-2(Y,Gd)(8)(SiO4)(6)O-2 phosphor films doped with rare earth and lead ions

Rare-earth and lead ions (Eu3+, Tb3+, Dy3+, Pb2+) doped Ca2Y8 (SiO4)(6)O-2 and Ca2Gd8(SiO4)(6)O-2 thin films have been dip- coated on silicon and quartz glass substrates through the sol- gel route. X- Ray diffraction (XRD), TG- DTA, scanning electron microscopy (SEM), atomic force microscopy (AFM), FT- IR and luminescence excitation and emission spectra as well as luminescence decays were used to characterize the resulting films. The results of XRD reveal that these films remain amorphous below 700 degreesC, begin to crystallize at 800 degreesC and crystallize completely around 1000 degreesC with an oxyapatite structure. The grain structure of the film can be seen clearly from SEM and AFM micrographs, where particles with various shapes and average size of 250 nm can be resolved. Eu3+ and Tb3+ show their characteristic red (D-5(0)-F-7(2)) and green (D-5(4) - F-7(5)) emission in the films with a quenching concentration of 10 and 6 mol% (of Y3+), respectively. The lifetime and emission intensity of Eu3+ increase with the temperature treatment from 700 to 1100 degreesC, while those of Tb3+ show a maximum at 800 degreesC. Energy transfer phenomena have been observed by activating the oxyapatite film host- lattice Ca2Gd8(SiO4)(6)O-2 with Tb3+ (Dy3+). In addition, Pb2+ can sensitize the Gd3+ sublattice in Ca2Gd8(SiO4)(6)O-2.