Spectroscopic study of the photophysical properties of rare earth ions encapsulated: Water soluble functional calixresorcin[4]arene

A novel macrocyclic compound-water soluble functional calixresorcin[4]arenes-tetra para sulfo-phenylmethyl-calixresorcin[4]are was synthesized for the first time. The photophysical properties of terbium and europium ions encapsulated in the macrocyclic ligand were studied in detail. The triplet state energy of the calixresorcin[4]arene was determined to be 24400 cm(-1) by the low temperature phosphorescence spectrum and it was found that it can sensitize both terbium ion and europium ion. The possible energy transfer process between the functional calixresorcin[4]arene and the encapsulated Tb3+ and Eu3+ was discussed. The luminescence quantum efficiency of Tb3+- calixresorcin[4]arene was calculated.

Fragmentation reactions of adduct ions [M+CH3CO](+) of isomeric phenylenediamines

The dissociation routes of the adduct ions [M+CH3CO](+) formed by ion-molecule reaction of isomeric phenylenediamines with acetyl ion from acetone under chemical ionization condition were investigated by using collision-induced dissociation (CID) technique performed at ion kinetic energies of 40eV. The adduct ions are intermediate ion-neutral complexes.

Effect of metal ions on Ru(bpy)(3)(2+) electrochemiluminescence

Ethylenediaminetetraacetate (EDTA) was chosen for the investigation of the effect of metal ions on Ru(bpy)(3)(2+) electrochemiluminescence (ECL). Metal ions that are preferentially bound to the oxygen atoms (MIO) have no effect on the intensity of ECL except for Al3+ and Y3+, whereas metal ions that are preferentially bound to the nitrogen atoms (MIN) preclude the oxidation of EDTA and decrease the ECL intensity.

The change of Eu3+-surroundings in the system Al2O3-B2O3 containing Eu3+ ions

The change of Eu3+-surroundings with the Al/B ratio varying from 4.5 to 2 and Eu/(Al + B) = 0.02, was investigated through X-ray diffraction, infrared spectra, excitation and emission spectra, and phonon sideband. The results show coexistence of the crystal phase Al18B4O33 and the amorphous phase and Eu3+ ions of the samples with the Al/B ratio from 3 to 2 are incorporated into the amorphous phase. It was also found that electron-phonon coupling strength decreases with the Al/B ratio from 3 to 2, non-radiative decay rate decreases, resulting in an increase of the Eu3+-emission intensity. (C) 1999 Elsevier Science Ltd. All rights reserved.

Studies on the interaction of rare earth ions with BSA

Studies on the bounding character of rare earth ions with borine serum albumin(BSA) are significant for understanding the state of rare earth ions in body and their effects on the structure and function of protein. The fluorescence spectrum and pH potentiometry showed consistent results of apparent complexion constant of Tb-2 . BSA. The equilibrium dialysis showed that there are two specific binding sites and more than six non-specific binding sites of RE ions onto BSA molecule with the conditional stable constants lg K-1 = 5. 157 and lgK(2) = 3. 435. Na-23 NMR studies revealed that the BSA peptide chain bound to RE ions was expanded and the mobility of its molecular backbone was increased.

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometric analysis of phospholipase A(2) and fibrinolytic enzyme, two enzymes obtained from Chinese Agkistrodon blomhoffii Ussurensis venom

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) was used to analyze two enzymes, phospholipase AZ and fibrinolytic enzyme isolated from Chinese Agkistrodon blomhoffii Ussurensis venom. Using sinapinic acid as the matrix, positive ion mass spectra of the enzymes were obtained, In addition to the dominant protein [M+H](+) ions, multimeric and multiply charged ions were also observed in the mass spectra, The higher the concentration of the enzymes, the more multiply charged polymer and multimeric ions were detected, Our results indicate that MALDI-TOFMS can provide a rapid and accurate method for molecular weight determination of snake venom enzymes, Mass accuracies of 0.1 and 0.3 % were achieved by analysis of highly dialyzed phospholipase A2 and fibrinolytic enzyme, and these results are much better than those obtained using sodium dodecyl sulfate-palyacrylamide gel electrophoresis. MALDI-TOFMS thus provides a reliable method to determine the purity and molecular weight of these enzymes, which are of potential use as therapeutants, Copyright (C) 1999 John Wiley & Sons, Ltd.

Classification of valence changes of trivalent rare earth ions in alkaline earth borates using artificial neural networks

The investigations of classification on the valence changes from RE3+ to RE2+ (RE = Eu, Sm, Yb, Tm) in host compounds of alkaline earth berate were performed using artificial neural networks (ANNs). For comparison, the common methods of pattern recognition, such as SIMCA, KNN, Fisher discriminant analysis and stepwise discriminant analysis were adopted. A learning set consisting of 24 host compounds and a test set consisting of 12 host compounds were characterized by eight crystal structure parameters. These parameters were reduced from 8 to 4 by leaps and bounds algorithm. The recognition rates from 87.5 to 95.8% and prediction capabilities from 75.0 to 91.7% were obtained. The results provided by ANN method were better than that achieved by the other four methods. (C) 1999 Elsevier Science B.V. All rights reserved.

Investigation of the structures of the product ions produced via self-CI of acetone

The ion-molecule reactions in acetone were investigated which were induced under the chemical ionization. The structural information of the reaction products were obtained by using collision-induced dissociation (CID) technique performed at ion kinetic energies of 30eV.

A new high efficiency green luminescent material - the system Al2O3-B2O3 containing Ce3+ and Tb3+ ions

To obtain high efficiency luminescent materials, the system Al2O3-B2O3 containing Ce3+ and Tb3+ ions with variation of B2O3-content, has been prepared by Al2O3, H3BO3, CeO2 and Tb4O7 under reducing atmosphere at 1250(j)ae. It is notable that the brightness of the sample with appropriate composition is similar to that of commercial phosphorous containing Ce3+ and Tb3+, indicating that a new high efficency green luminescent material was obtained with appropriate B2O3-content.

Electrospray ionization mass spectrometry of cyclodextrin complexes with amino acids in incubated solutions and in eluates of gel permeation chromatography

1:1 complexes of beta-cyclodextrin (CD) with three amino acids (Gly, Phe and Trp) have been detected as ions in the gas phase using infusion positive and negative ion electrospray ionization mass spectrometry (ESI-MS). In contrast with the positive ion ESI mass spectra of simple aqueous solutions, the aggregates and adducts usually formed in the ESI process did not appear in the positive ion ESI spectra of solutions buffered with ammonium acetate (NH4Ac), even at higher analyte concentrations, These studies suggest that addition of buffer and/or use of a low analyte concentration should be used to overcome formation of aggregates and metal ion adducts in such mass spectrometry studies. Also, the deprotonated complexes are dissociated by collision induced dissociation (CID) to form an abundant product ion, the deprotonated CD, requiring transfer of a proton to the amino acid carboxyl group, To understand formation of complexes in the gas phase, gel permeation chromatography (GPC) was used to separate free amino acids (AAs) from complexes in an incubated solution. The ESI mass spectra of the GPC fractions show the presence of 1:1 complexes of both CD-aromatic amino acids and CD-aliphatic amino acids. Compared with CD-aliphatic amino acid complexes, CD-aromatic amino acid complexes appear to be destabilized in the gas phase, possibly because the hydrophobic interaction which binds the aromatic group of amino acids in the CD cavity in solution may become repulsive when solvent evaporates from the droplets during the electrospray process, whereas those complex ions formed as proton bound dimers are stabilized by electrostatic forces, the major binding force for such complexes in the gas phase. In addition, the GPC technique coupled with off-line ESI-MS can rapidly separate CD complexes by size, and provides some information on the character of the complexes in solution. (C) 1998 John Wiley & Sons, Ltd.

Probing lanthanide ions binding on tRNA(Phe) by H-1 NMR

The structure of phenylalanine transfer ribonucleic acid (tRNA(Phe)) in solution was explored by H-1 NMR spectroscopy to evaluate the effect of lanthanide ion on the structural and conformational change. It was found that La3+ ions possess specific effects on the imino proton region of the H-1 NMR spectra for yeast tRNA(Phe). The dependence of the imino proton spectra of yeast tRNA(Phe) as a function of La3+ concentration was examined, and the results suggest that the tertiary base pair G(15). C-48, which is located in the terminal in the augmented dihydrouridine helix (D-helix), was markedly affected by La3+ (shifted to downfield by as much as 0.35). Base pair U-8. A(14) in yeast tRNA(Phe), which are stacked on G(15). C-48, was also affected by added La3+ when 1 similar to 2 Mg2+ were also present. Another imino proton that may be affected by La3+ in yeast tRNA(Phe) is that of the tertiary base pair G(19). C-56. The assignment of this resonance in yeast tRNA(Phe) is tentative since it is located in the region of highly overlapping resonances beween 12.6 and 12.2. This base pair helps to anchor the D-loop to the T Psi C loop. The binding of La3+ caused conformational change of tRNA, which is responsible for shifts to upfield or downfield in H-1 NMR spectra.

Chemical bond properties of rare earth ions in crystals

By using the dielectric description theory of ionicity of solids, chemical bond properties of rare earth ions with various ligands are studied. Calculated results show that chemical bond properties of the same rare earth ion and the same ligand in different crystals depend on the crystal structures. In a series of compounds, chemical bond properties of crystals containing different rare earth ions are similar. The magnitude of covalency of chemical bonds of trivalent rare earth ions and various ligands has an order like F

The phenomenon of mutual media in polypyrrole with electroactive ions

The dependence of the differential capacitance of polypyrrole doped with several typical dopants on potential is presented, which shows that the differential capacitance varies with the potential, the doped polypyrroles with electroactive ions give the largest capacitance near their formal potentials, which is attributed to the mutual media for electron transfer between polypyrrole and electroactive dopants. The existence of two conducting phases was observed in the complex capacitance plots. The electroactive anions act as an intra-conducting-phase medium for electron transfer, the electroactive cations act as an inter-conducting-phase medium for electron transfer. The mutual media between polypyrrole and redox dopants lead to the increase of the discharging time.

Studies on beta-cyclodextrin amino acids inclusion complexes by electrospray ionization mass spectrometry

The positive- and negative-ion electrospray ionization mass spectra of beta-cyclodextrin-amino acids complexes in NH4Ac buffer have been reported in this paper. Compared with positive-ion ESI mass spectra of beta-cyclodextrin-amino acids complexes under the same condition, negative-ion mass spectra obtained for inclusion complexes of beta-cyclodextrin (CD) with tyrosine, phenylalanine and tryptophan, respectively, were completely dominated by deprotonated complex ions and [CD-H](-) ion which is the only daughter ion in collision-induced dissociation (CID) experiment of deprotonated complexes, The results indicated that the charged position for protonated and deprotonated complexes is different from each other. In addition, two complex ions for the same complex have similarly relative dissociation energies, which are higher than that of [CD+NH4](+), indicating that complexes observed in gasphase are not electrostatic adducts at all but complexes formed by hydrogen bonds.

Effect of lanthanum ions on tRNA(Phe) structure: Imino proton NMR spectroscopy

The effect of lanthanum ions on the structural and conformational change of yeast tRNA(Phe) was studied by H-1 NMR. The results suggest that the tertiary base pair (G-15)(C-48), which was located in the terminal in the augmented dihydrouridine helix (D-helix), was markedly affected by adding La3+ and shifted 0.33 downfield. Based pair (U-8)(A-14), which is associated with a tertiary interaction, links the base of the acceptor stem to the D-stem and anchors the elbow of the L structure, shifted 0.20 upfield. Another imino proton that may be affected by La3+ in tRNA(Phe) is the tertiary base pair (G-19)(C-56). The assignment of this resonance is tentative since it is located in the region of highly overlapping resonances between 12.6 and 12.2. This base pair helps to anchor the D-loop to the T psi C loop.