Metal ion and anion coordination in the thiamine-[Pt-II(NO2)(4)](2-) system. Structures of a metal complex, Pt(thiamine)(NO2)(3), and two salts, (H-thiamine)[Pt(NO2)(4)]center dot 2H(2)O and (thiamine monophosphate)(2)[Pt(NO2)(4)]center dot 2H(2)O

Reaction of thiamine or thiamine monophosphate (TMP) with K2Pt(NO2)(4) afforded a metal complex, Pt(thiamine)(NO2)(3) (1), and two salt-type compounds, (H-thiamine)[Pt(NO2)(4)]. 2H(2)O (2) and (TMP)(2)[Pt(NO2)(4)]. 2H(2)O (3), which were structurally characterized by X-ray diffraction. In 1, the square-planar Pt2+ ion is coordinated to the pyrimidine N(1'), a usual metal-binding site, and three NO2- groups. The thiamine molecule exists as a monovalent cation in 1 and a divalent cation in 2 while the TMP molecule is a monovalent cation in 3. In each compound, thiamine or TMP adopts the usual F conformation and forms two types of host-guest-like interactions with anions, which are of the bridging forms, C(2)-H . . . anion . . . pyrimidine-ring and N(4'1)-H(...)anion(...)thiazolium-ring. In 3, there is an additional anion-bridging interaction between the pyrimidine and thiazolium rings of TMP, being of the form C(6')-H . . . anion . . . thiazolium-ring. The salts 2 and 3 show similar hydrogen-bonded cyclic dimers of thiamine or TMP between which the anions are held. Results are compared with those of the other thiamine-platinum complexes. (C) 2001 Elsevier Science B.V. All rights reserved.

Vibronic transitions and site substitution of Eu2+ and codoped ions in KMgF3 : Eu-X (X=Ce, Cr, Gd, Cu) system

The high-resolution emission spectra of KMgF3 : Eu and KMgF3 : Eu-X(X = Ce, Cr, Gd, Cu) single crystals were measured at 300 and 77 K. The vibronic side bands of Eu2+ were characterized and an assignment of the normal mode frequencies to particular vibrations has been made. The correlation between the vibronic frequencies of Eu2+ and the site substitution of other co-dopcd ions was first found. The relationship between vibronic intensity of Eu2+ and other doped ions concentration showed that Cr3+, Gd3+ ions competed K+ sites with Eu2+ ions. Ce3+ and Eu3+ occurred the electron transference. The introduction of Cu+ made for Eu2+ substuting for K+ sites.

Synthesis, crystal structure and luminescence studies of a lanthanide coordination polymer with a new double betaine ligand

A novel europium(III) coordination polymer with a new double betaine derivative, {[Eu(L')(NO3)(H2O)(3)](NO3)(2). 3.5H(2)O}(n) (L-1 = 1,3-bis(pyridinio-4-carboxylato)-propane) has been synthesized and its structure determined. Its luminescence properties have also been studied. The title metal carboxylate coordination polymer contains centrosymmetric dimeric units in which each pair of metal ions is linked by a pair of syn-anti carboxylato-O,O' groups, and each pair of such dimeric units is bridged by the backbones of L-1 ligands to form infinite double chains in the b direction. These metal carboxylate chains are further cross-linked by hydrogen bonds among both coordinated and discrete nitrate anions, aqua ligands and lattice water molecules to form a three-dimensional network. Luminescent data show that the L-1 ligand is a good energy donor and the complex has a relatively long luminescent lifetime.

Synthesis, characterisation and catalytic activity of propionamide complexes of rare earth chlorides

Propionamide complexes of rare earth chlorides were synthesized, Formula of the complexes is LnCl(3). 3BA. The ligand is shown to behave as a normal amide donor With the oxygen of the carbonyl group coordinated to the metal ions. Binary system composed Elf propionamide and aluminum alkyl shows higher activity and stereospecificity for butadiene polymerization. The cis-1,4 content of polybutadiene is more than 98%.

Rapid automated in-situ monitoring of total dissolved iron and total dissolved manganese in underground water by reverse-flow injection with chemiluminescence detection during the process of water treatment

Measurement of iron and manganese is very important in evaluating the quality of natural waters. We have constructed an automated Fe(II), total dissolved iron(TDI), Mn(II), and total dissolved manganese(TDM) analysis system for the quality control of underground drinking water by reverse flow injection analysis and chemiluminescence detection(rFIA-CL), The method is based on the measurement of the metal-catalyzed light emission from luminol oxidation by potassium periodate. The typical signal is a narrow peak, in which the height is proportional to light emitted and hence to the concentration of metal ions. The detection limits were 3 x 10(-6) mu g ml(-1) for Fe(II) and the linear range extents up to 1.0 x 10(-4) and 5 x 10(-6) mu g ml(-1) for Mn(II) cover a linear range to 1.0 x 10(-4) mu g ml(-1). This method was used for automated in-situ monitoring of total dissolved iron and total dissolved in underground water during water treatment. (C) 1997 Elsevier Science B.V.

Hydrolysis of adenosine monophosphate and guanosine monophosphate by lanthanides

The hydrolysis of adenosine-5'-monophosphate(5'-AMP) and guanosine-5'-monophosphate(5'-GMP) by lanthanides was investigated. 5'-AMP and 5'-GMP was efficiently hydrolyzed by cerium(III) chloride under air at pH 9 and 37 degrees C, and other lanthanides (III) showed less efficiency at the same condition. The hydrolysis rate of 5'-AMP by cerium was greater than that of 5'-GMP. UV spectra showed that Ce(III) was oxidized to Ce(IV) in the reaction mixture. The active species for the hydrolysis of 5'-AMP and 5'-GMP was ascribed to the Ce(IV) hydroxide cluster in the reaction mixture.

Preparation and crystal structures of LaCl3(15-crown-5) and [LaCl2(phen)(H2O)(2)(mu-Cl)](2)center dot(15-crown-5)center dot MeCN

LaCl3(15-crown-5), I was prepared by the reaction of LaCl(3)nH(2)O with 15-crown-5 and bipy (2,2'-bipyridyl). [LaCl2(phen)(H2O)(2)(mu-Cl)](2) .(15-crown-5). MeCN, II, was crystallized from a mixture of LaC1(3) . nH(2)O, phen (1,10-phenanthroline) and 15-crown-5 in MeOH/MeCN, Crystal structures of these two complexes have been determined by X-ray methods. The La(III) ion in I is coordinated by three Cl anions and five oxygen atoms of a crown ether. The two metal ions in II are bridged by two Cl anions and the crown ligand is hydrogen-bonded to the coordinated water molecules to form polymeric... crown/cation/cation/crown... chains.

SPECTRAL CHARACTERISTICS OF ER3+-ACTIVATED AND CE3+-SENSITIZED YTTRIUM-ALUMINUM-GARNET LASER CRYSTALS

We report in this paper the spectral characteristics of Er3+ (2 at.%)-activated and Ce3+ (0.3 at.%)-sensitized yttrium aluminium garnet (YAG:Er,Ce) laser crystals grown by the Czochralski technique. The absorption and emission spectra were measured at room temperature. By using absorption spectra and Judd-Ofelt theory the experimental oscillator strengths of the Er3+ transitions in the YAG:Er,Ce crystals were calculated. The energy transfer between the Er3+ and Ce3+ ions is also discussed.

EFFECT OF LANTHANIDE IONS ON THE PHASE-BEHAVIOR OF DIPALMITOYLPHOSPHATIDYLCHOLINE MULTILAMELLAR LIPOSOMES

The effect of lanthanide ions (Ln(3+)) and their coordination compounds of diethylenetriamine pentaacetic acid (DTPA) on the phase behavior of dipalmitoylphosphatidycholine (DPPC) multilamellar liposomes has been studied by differential scanning calorimet

LUMINESCENCE AND ENERGY-TRANSFER IN GDP5O14-EU3+,SM3+ SINGLE-CRYSTALS

In this paper we report on the luminescence and energy transfer in GdP4O14:Eu3+,Sm3+ (GdPP:Eu,Sm) in single crystals grown by the hydrothermal method. The room temperature excitation, emission, absorption and IR spectra of the crystals have been measured and analysed. The energy transfer from Gd3+ and Sm3+ to Eu3+ ions in GPP:Eu,Sm crystals is also discussed.

ELECTROCHEMICAL DETECTION OF COBALT IN HAIR FOLLOWING ON-COLUMN DERIVATIZATION WITH 1-(2-PYRIDYLAZO)-2-NAPHTHOL-6-SULFONIC ACID AND REVERSED-PHASE LIQUID-CHROMATOGRAPHY

A method for the specific determination of cobalt based on reversed-phase liquid chromatography with amperometric detection via on-column complex formation has been developed. A water-soluble chelating agent, 1-(2-pyridylazo)-2-naphthol-6-sulphonic acid (PAN-6S), is added to the mobile phase and aqueous cobalt solutions are injected directly into the column to form in situ the cobalt-PAN-6S chelate, which is then separated from other metal PAN-6S chelates and subjected to reductive amperometric detection at a moderate potential of -0.3 V. Because the procedure eliminates the interference of oxygen and depresses the electrochemical reduction of the mobile phase-containing ligand PAN-6S, by virtue of the quasi:reversible electrode process of the cobalt-PAN-6S complex, a low detection limit of 0.06 ng can be readily obtained. Interference effects were examined for sixteen common metal species, and at a 5- to 8000-fold excess by mass no obvious interference was observed. The feasibility of the method as an approach to the specific analysis of cobalt in a hair sample has been demonstrated.

SYNTHESES AND CRYSTAL STRUCTURES OF THE COMPLEXES OF RARE EARTH WITH FUMARIC ACID

Six compounds of M2F3 center dot 1.2H(2)O (M=EU, Ga, Tb, Y, Er, LU: H2F=Fumaric acid) have been synthesized. The structures of Eu(III), T b(III), Y(III), Er(III) and Lu(III) compounds have been determined by singal crystal X-ray diffraction method. The complex of Eu(III) crystallizes in tri-clinic space group P (1) over bar, and the coordination number of Eu3+ is ten. The other four complexes crystallize in monclinic space P2(1)/c, and the coordination numbers of the metal ions are eight. Each of the complexes shows a three-dimensional net structures.

SOLID DEFECT STRUCTURE AND CATALYTIC ACTIVITY OF PEROVSKITE-TYPE CATALYSTS LA1-XSRXNIO3-LAMBDA AND LA1-1.333XTHXNIO3-LAMBDA

Two series of La1-xSrxNiO3-lambda and La1-1.333xThxNiO3-lambda catalysts have been prepared, and the relationships between the solid defect structure and catalytic activity for NH3 oxidation were measured. The results showed that in the range of x < 0.3, the samples possessed single perovskite-type structure, and as the content of Sr2+ decreased and that of Th4+ increased the catalytic activity increased which was paralleled with the Ni3+ concentration within the catalysts. The active oxygen species (O- or O2(2-)) were present not only on the surface but also in the bulk of the samples. The synergistic effect of transition metal ions with higher oxidation states and randomly distributed oxygen vacancies was the key factor determining catalytic activity of perovskite-type oxides. A redox mechanism for NH3 oxidation over ABO3 is proposed.

Sorption and desorption of Cu and Cd by macroalgae and microalgae

The sorption and desorption of Cu and Cd by two species of brown macroalgae and five species of microalgae were studied. The two brown macroalgae, Laminaria japonica and Sargassum kjellmanianum, were found to have high capacities at pHs between 4.0 and 5.0 while for microalgae, optimum pH lay at 6.7. The presence of other cations in solution was found to reduce the sorption of the target cation, suggesting a competition for sorption sites on organisms. Sorption isotherms obeyed the Freundlich equation, suggesting involvement of a multiplicity of mechanisms and sorption sites. For the microalgae tested, Spirulina platensis had the highest capacity for Cd, followed by Nannochloropsis oculata, Phaeodactylum tricornutum, Platymonas cordifolia and Chaetoceros minutissimus. The reversibility of metal sorption by macroalgae was examined and the results show that both HCl and EDTA solutions were very effective in desorbing sorbed metal ions from macroalgae, with up to 99.5% of metals being recovered. The regenerated biomass showed undiminished sorption performance for the two metals studied, suggesting the potential of such material for use in water and wastewater treatment. (C) 1998 Elsevier Science Ltd. All rights reserved.

Sorption and desorption of lead (II) from wastewater by green algae Cladophora fascicularis

Biosorption is an effective method to remove heavy metals from wastewater. In this work, adsorption features of Cladophora fascicularis were investigated as a function of time, initial pH, initial Pb(II) concentrations, temperature and co-existing ions. Kinetics and equilibria were obtained from batch experiments. The biosorption kinetics followed the pseudo-second order model. Adsorption equilibria were well described by the Langmuir and Freundlich isotherm models. The maximum adsorption capacity was 198.5 mg/g at 298 K and pH 5.0. The adsorption processes were endothermic and the biosorption heat was 29.6 kJ/mol. Desorption experiments indicated that 0.01 mol/L Na(2)EDTA was an efficient desorbent for the recovery of Pb(II) from biomass. IR spectrum analysis suggested amido or hydroxy, C=O and C-O could combine intensively with Pb(II). (C) 2006 Elsevier B.V. All rights reserved.