Determination of trace phosphate ion in water by visual method after preconcentration on a membrane filter for field work

A sensitive visual method based on comparing the color intensity of precipitate as phosphomolybdenum blue on a membrane filter, has been developed for the determination of trace phosphate ion in water for field work. A sample solution containing 0.05-5.0 mug of phosphate was treated in a 25-ml polypropylene syringe, and the resulting precipitate was filtered through a membrane filter attached to the syringe. The color intensity of the precipitate on the membrane filter was measured visually following the standard series method. The coefficient of variation for five measurements at 0.5 mug of phosphate is 11%. The detection limit is 0.02 mug of phosphate ion in 22.5 ml (0.9 mug PO(3-)(4)/l) of water sample when the effective filtration area is 0.78 cm(2). The interference of various ions was studied and optimum conditions were developed for the determination of phosphate ion in natural water.     

Anion binding with a tripodal amine

Binding studies of the tren-based amine, L (N,N',N' '-tris(2-benzylaminoethyl)amine), with inorganic anions and two crystal structures, [H(3)L][H(2)PO(4)](3).H(3)PO(4) and [H(3)L][Br](3), are reported. NMR titration results indicate that the ligand binds H(2)PO(4)(-) and HSO(4)(-) more strongly than NO(3)(-) and halides. In the crystal structure of the phosphate complex, the ligand is triprotonated with the three arms pointing outward in a trigonal-planar-like arrangement. Four phosphate species are associated with the receptor, and have been assigned as three H(2)PO(4)(-) counterions located between each of the tren arms, and an additional H(3)PO(4) molecule above the quasi-planar tren. The structure of the bromide complex is slightly different, although again the tren receptor is triprotonated and quasi-planar, but in this case C(2v)-like symmetry is seen with two of the arms pointed in the same direction with a bromide ion in between. The other two bromides lie outside of the tren arms.     

Lattice energies of apatites and the estimation of DeltaH f degrees (PO 4 3-, g)

Experimentally based lattice energies are calculated for the apatite family of double salts M(5)(PO(4))(3)X, where M is a divalent metal cation (Ca, Sr, Ba) and X is hydroxide or a halide. These values are also shown to be estimable, generally to within 4%, using the recently derived Glasser-Jenkins equation, U(POT) = AI(2I/V(m))(1/3), where A = 121.39 kJ mol(-)(1). The apatites exhibiting greater covalent character (e.g., M = Pb, Cd, etc.) are less well reproduced but are within 8% of the experimentally based value. The lattice energy for ionic apatites (having identical lattice ionic strengths, I) takes the particularly simple form U(POT)/kJ mol(-)(1) = 26680/(V(m)/nm(3))(1/3), reproducing cycle values of U(POT) well when V(m) is estimated by ion volume summation and employing a volume for the PO(4)(3)(-) ion (not previously quantified with an associated error) of 0.063 +/- 0.003 nm(3). A value for the enthalpy of formation of the gaseous phosphate ion, DeltaH(f)( ) degrees (PO(4)(3)(-), g), is absent from current thermochemical tabulations. Examination of solution and solid state thermochemical cycles for apatites, however, leads us to a remarkably consistent value of 321.8 +/- 1.2 kJ mol(-)(1). Experimental and estimated lattice energies were used along with other thermodynamic data to determine enthalpies, entropies, and free energies of dissolution for apatites of uncertain stabilities. These dissolution values are compared with the corresponding values for stable apatites and are used to rationalize the relative instability of certain derivatives.     

Single, binary and multi-component adsorption of some anions and heavy metals on environmentally friendly Carpobrotus edulis plant

A low-cost adsorbent and environmentally friendly adsorbent from Carpobrotus edulis plant was used for the removal of NO(3)(-), H(2)PO(4)(-), Pb(2+) and Cd(2+) ions from single, binary and multi-component systems. The efficiency of the adsorbent was studied using batch adsorption technique under different experimental conditions by varying parameters such as pH, initial concentration and contact time. In single component systems, the dried C. edulis has the highest affinity for Pb(2+), followed by NO(3)(-), Cd(2+) and H(2)PO(4)(-), with adsorption capacities of 175mg/g, 125mg/g, 28mg/g and 26mg/g, respectively. These results showed that the adsorption of NO(3)(-) and H(2)PO(4)(-) ions from single and binary component systems can be successfully described by Langmuir and Freundlich isotherms. Freundlich adsorption model, showed the best fit to the single and binary experimental adsorption data. These results also indicated that the adsorption yield of Pb(2+) ion was reduced by the presence of Cd(2+) ion in binary metal mixture. The competitive adsorption of NO(3)(-), H(2)PO(4)(-), Pb(2+) and Cd(2+) ions on dried C. edulis plant shows that NO(3)(-) and H(2)PO(4)(-) anions are able to adsorb on different free binding sites and Pb(2+) and Cd(2+) cations are able to adsorb on the same active sites of C. edulis particles. The dried C. edulis was found to be efficient in removing nitrate, phosphate, cadmium and lead from aqueous solution as compared to other adsorbents already used for the removal of these ions.     

Syntheses, structures, and ion-exchange properties of the three-dimensional framework uranyl gallium phosphates, Cs4[(UO2)2(GaOH)2(PO4)4].H2O and Cs[UO2Ga(PO4)2

The reaction of UO(2)(NO(3))(2).6H(2)O with Cs(2)CO(3) or CsCl, H(3)PO(4), and Ga(2)O(3) under mild hydrothermal conditions results in the formation of Cs(4)[(UO(2))(2)(GaOH)(2)(PO(4))(4)].H(2)O (UGaP-1) or Cs[UO(2)Ga(PO(4))(2)] (UGaP-2). The structure of UGaP-1 was solved from a twinned crystal revealing a three-dimensional framework structure consisting of one-dimensional (1)(infinity)[Ga(OH)(PO(4))(2)](4-) chains composed of corner-sharing GaO(6) octahedra and bridging PO(4) tetrahedra that extend along the c axis. The phosphate anions bind the UO(2)(2+) cations to form UO(7) pentagonal bipyramids. The UO(7) moieties edge-share to create dimers that link the gallium phosphate substructure into a three-dimensional (3)(infinity)[(UO(2))(2)(GaOH)(2)(PO(4))(4)](4-) anionic lattice that has intersecting channels running down the b and c axes. Cs(+) cations and water molecules occupy these channels. The structure of UGaP-2 is also three-dimensional and contains one-dimensional (1)(infinity)[Ga(PO(4))(2)](3-) gallium phosphate chains that extend down the a axis. These chains are formed from fused eight-membered rings of corner-sharing GaO(4) and PO(4) tetrahedra. The chains are in turn linked together into a three-dimensional (3)(infinity)[UO(2)Ga(PO(4))(2)](1-) framework by edge-sharing UO(7) dimers as occurs in UGaP-1. There are channels that run down the a and b axes through the framework. These channels contain the Cs(+) cations. Ion-exchange studies indicate that the Cs(+) cations in UGaP-1 and UGaP-2 can be exchanged for Ca(2+) and Ba(2+). Crystallographic data: UGaP-1, monoclinic, space group P2(1)/c, a = 18.872(1), b = 9.5105(7), c = 14.007(1) A, beta = 109.65(3)(o) , Z = 4 (T = 295 K); UGaP-2, triclinic, space group P, a = 7.7765(6), b = 8.5043(7), c = 8.9115(7) A, alpha = 66.642(1)(o), beta = 70.563(1)(o), gamma = 84.003(2)(o), Z = 2 (T = 193 K).     

Selective recognition of monohydrogen phosphate by fluorescence enhancement of a new cerium complex

Bis(8-hydroxy quinoline-5-solphonate) cerium(III) chloride (Ce(QS)(2)Cl) (L) was synthesized and then used as a novel fluorescent sensor for anion recognition. Preliminarily study showed that fluorescence of L enhanced selectively in the presence of HPO(4)(2-) ion. This enhancement is attributed to a 1:1 complex formation between L and HPO(4)(2-) anion. The association constant of 1:1 complex of L-HPO(4)(2-) was calculated as 3.0×10(6). Thus, L was utilized as a basis for a selective detection of HPO(4)(2-) anion in solution. The linear response range of the proposed fluorescent chemo-sensor covers a concentration range of HPO(4)(2-) from 3.3×10(-7) to 5.0×10(-6) mol L(-1) with a detection limit of 2.5×10(-8) mol L(-1). L showed selective and sensitive fluorescence enhancement response toward HPO(4)(2-) ion in comparison with I(3)(-), NO(3)(-), CN(-), CO(3)(2-), Br(-), Cl(-), F(-), H(2)PO(4)(-) and SO(4)(2-) ions. It was probably attributed to the higher stability of the inorganic complex between HPO(4)(2-) ion and L. The method was successfully applied for analysis of phosphate ions in some fertilizers samples.     

Nutrient removal and energy production in a urine treatment process using magnesium ammonium phosphate precipitation and a microbial fuel cell technique

Urine pretreatment has attracted increasing interest as it is able to relieve the nitrogen and phosphorus overloading problems in municipal wastewater treatment plants. In this study, an integrated process, which combines magnesium ammonium phosphate (MAP) precipitation with a microbial fuel cell (MFC), is proposed for the recovery of a slow-release fertilizer and electricity from urine. In such a two-step process, both nitrogen and phosphorus are recovered through the MAP process, and organic matters in the urine are converted into electricity in the MFCs. With this integrated process, when the phosphorus recovery is maximized without a dose of PO(4)(3-)-P in the MAP precipitation process, removal efficiencies for PO(4)(3)-P and NH(4)(+)-N of 94.6% and 28.6%, respectively, were achieved with a chemical oxygen demand (COD) of 64.9% accompanied by a power output of 2.6 W m(-3). Whereas removal efficiencies for PO(4)(3)-P and NH(4)(+)-N of 42.6% and 40%, respectively, and a COD of 62.4% and power density of 0.9 W m(-3) were obtained if simultaneous recovery of phosphorus and nitrogen was required through dosing with 620 mg L(-1) of PO(4)(3-)-P in the MAP process. This work provides a new sustainable approach for the efficient and cost-effective treatment of urine with the recovery of energy and resources.     

A simple mixed-solvothermal route for LaPO4 nanorods: synthesis, characterization, affecting factors and PL properties of LaPO4:Ce3+

In this paper, LaPO(4) nanorods have been successfully synthesized via a simple water-ethyleneglycol (H(2)O-EG) mixed-solvothermal route, employing lanthanum nitrate (La(NO(3))(3)·xH(2)O) as a La(3+) ion source and monobasic sodium phosphate (NaH(2)PO(4)·2H(2)O) as a PO(4)(3-) ion source. The as-obtained products were characterized by means of X-ray powder diffraction (XRD), energy dispersive spectrometry (EDS), (high resolution) transmission electron microscopy (HR/TEM), selected area electron diffraction (SAED) and field emission scanning electron microscopy (FESEM). Some factors influencing the formation of LaPO(4) nanorods, including the reaction temperature, the volume ratio of water/EG and the original amount of H(2)PO(4)(-) ions, were investigated. Experiments showed that the volume ratio of water/EG and the original amount of H(2)PO(4)(-) ions could markedly affect the morphology of the final product.     

Phosphate recovery by high flux low pressure multilayer membranes

This work illustrates the potential use of PEI/PSS bilayers assembled via layer by layer (lbl) method on a nylon microfiltration membrane for the recovery of phosphate from water in the presence of chloride under ultrafiltration conditions. A total of nine bilayers were used for the selective recovery of phosphate. Bilayers were constructed from polyelectrolyte solutions of varying ionic strength (0-1 M of NaCl). The selected pH for deposition of PEI (5.9) and the presence of supporting salt in the polyelectrolyte solution is expected to provide membranes with high permeability and high charge density. This particular combination of bilayers yielded high flux membranes that allowed selective removal of H(2)PO(4)(-) in the presence of Cl(-) at low pressure (0.28 bar). The magnitude of negative solute rejection of chloride showed increasing trend with the number of bilayer for a particular salt concentration. Whereas the increase in magnitude with ionic strength is so high (-6.18 to -269.17 at 0.5 M NaCl for 9 bl) that gave the best observed Cl(-)/H(2)PO(4)(-) selectivity (310.23, flux 13.53 m(3)/m(2)-day). To the best of our knowledge, this is the first time a multilayer polyelectrolyte system with such a high selectivity and rejection for H(2)PO(4)(-) is reported. The solution flux decreased with the number of bilayers and ionic strength. The rejection of phosphate was dependent on feed pH, concentration of deposited polyelectrolyte solution, and composition of membrane support.     

Multi-competitive interaction of As(III) and As(V) oxyanions with Ca(2+), Mg(2+), PO(3-)(4), and CO(2-)(3) ions on goethite

Complex systems, simulating natural conditions like in groundwater, have rarely been studied, since measuring and in particular, modeling of such systems is very challenging. In this paper, the adsorption of the oxyanions of As(III) and As(V) on goethite has been studied in presence of various inorganic macro-elements (Mg(2+), Ca(2+), PO(3-)(4), CO(2-)(3)). We have used 'single-,' 'dual-,' and 'triple-ion' systems. The presence of Ca(2+) and Mg(2+) has no significant effect on As(III) oxyanion (arsenite) adsorption in the pH range relevant for natural groundwater (pH 5-9). In contrast, both Ca(2+) and Mg(2+) promote the adsorption of PO(3-)(4). A similar (electrostatic) effect is expected for the Ca(2+) and Mg(2+) interaction with As(V) oxyanions (arsenate). Phosphate is a major competitor for arsenate as well as arsenite. Although carbonate may act as competitor for both types of As oxyanions, the presence of significant concentrations of phosphate makes the interaction of (bi)carbonate insignificant. The data have been modeled with the charge distribution (CD) model in combination with the extended Stern model option. In the modeling, independently calculated CD values were used for the oxyanions. The CD values for these complexes have been obtained from a bond valence interpretation of MO/DFT (molecular orbital/density functional theory) optimized geometries. The affinity constants (logK) have been found by calibrating the model on data from 'single-ion' systems. The parameters are used to predict the ion adsorption behavior in the multi-component systems. The thus calibrated model is able to predict successfully the ion concentrations in the mixed 2- and 3-component systems as a function of pH and loading. From a practical perspective, data as well as calculations show the dominance of phosphate in regulating the As concentrations. Arsenite (As(OH)(3)) is often less strongly bound than arsenate (AsO(3-)(4)) but arsenite responses less strongly to changes in the phosphate concentration compared to arsenate, i.e., deltalogc(As(III))/deltalogc(PO(4)) approximately 0.4 and deltalogc(As(V))/deltalogc(PO(4)) approximately 0.9 at pH 7. Therefore, the response of As in a sediment on a change in redox conditions will be variable and will depend on the phosphate concentration level.     

Binding of phosphate with a simple hexaaza polyammonium macrocycle

A mixture of dihydrogen phosphate and phosphoric acid has been crystallized with a hexaprotonated 26-membered polyammonium macrocycle, 1,4,7,14,17,20-hexaazacyclohexacosane, as the counterion. The complex crystallizes in the monoclinic space group P2(1)/c with unit cell parameters of a = 10.006(2) A, b = 12.525(1) A, c = 19.210(2) A, beta = 102.91(1) degrees, and V = 2346.6(5) A3. The hexaprotonated macrocycle is located on a crystallographic center of inversion and is surrounded by eight phosphate anions. Six of the phosphates are dihydrogen phosphates (H2PO4-), and the other two are neutral phosphoric acid molecules. Intricate hydrogen-bonding networks, involving the anionic and neutral phosphates and the protonated macrocycle, dominate the crystal lattice. Potentiometric studies using NaCl as the supporting electrolyte indicate high formation constants for the triprotonated macrocycle, H3L3+, with PO4(3-) at pH approximately 9.5 (log K = 4.55(4)), for the tetraprotonated macrocycle, H4L4+, with monohydrogen phosphate, HPO4(2-), at pH approximately 8.0 (log K = 6.01(3)), and for ditopic complexes with H5L5+ and H6L6+ and dihydrogen phosphate, H2PO4-, at pH approximately 4.0 (log K = 6.16(6)) and pH approximately 2.5 (log K = 6.44(5)), respectively. The ditopic behavior in the simple polyazamacrocycle receptor is a somewhat unusual occurrence, as is the finding of phosphoric acid species in the crystal structure.     

Discrimination in metal-ion binding to RNA dinucleotides with a non-bridging oxygen or sulfur in the phosphate diester link

Replacement of a non-bridging oxygen in the phosphate diester bond by a sulfur has become quite popular in nucleic acid research and is often used as a probe, for example, in ribozymes, where the normally essential Mg(2+) is partly replaced by a thiophilic metal ion to reactivate the system. Despite these widely applied rescue experiments no detailed studies exist quantifying the affinity of metal ions to such terminal sulfur atoms. Therefore, we performed potentiometric pH titrations to determine the binding properties of pUp((S))U(3-) towards Mg(2+), Mn(2+), Zn(2+), Cd(2+), and Pb(2+), and compared these data with those previously obtained for the corresponding pUpU(3-) complexes. The primary binding site in both dinucleotides is the terminal phosphate group. Theoretically, also the formation of 10-membered chelates involving the terminal oxygen or sulfur atoms of the (thio)phosphate bridge is possible with both ligands. The results show that Mg(2+) and Mn(2+) exist as open (op) isomers binding to both dinucleotides only at the terminal phosphate group. Whereas Cd(pUpU)(-) only exists as Cd(pUpU)(-)(op), Cd(pUp((S))U)(-) is present to about 64 % as the S-coordinated macrochelate, Cd(pUp((S))U)(-)(cl/PS). Zn(2+) forms with pUp((S))U(3-) three isomeric species, that is, Zn(pUp((S))U)(-)(op), Zn(pUp((S))U)(-)(cl/PO), and Zn(pUp((S))U)(-)(cl/PS), which occur to about 33, 12 (O-bound), and 55 %, respectively. Pb(2+) forms the 10-membered chelate with both nucleotides involving only the terminal oxygen atoms of the (thio)phosphate bridge, that is, no indication of S binding was discovered in this case. Hence, Zn(2+) and Cd(2+) show pronounced thiophilic properties, whereas Mg(2+), Mn(2+), and Pb(2+) coordinate to the oxygen, macrochelate formation being of relevance with Pb(2+) only.     

Indirect spectrophotometric determination of sulphide with the ternary complex system Ag(I)-phen-BPR

Trace amounts of sulphide can be determined from its effect on the ternary complex system of Ag(+), Bromopyrogallol Red (BPR), and 1,10-phenanthroline (phen). Sulphide in the range 5-120 ng/ml causes a decrease in absorption, that is a linear function of the concentration. Common metal ions such as Na(+), K(+), Ca(2+), Mg(2+), Al(3+), Mn(2+) and anions such as F(-), Cl(-), NO(-)(3), SO(2-)(4), CO(2-)(3), and PO(3-)(4) at the 4 mug/ml level or more do not interfere, but I(-) or CN(-) must be absent.     

Copper(II) complexes of a series of polypyridine ligands possessing a 1,2-bis(2-pyridyl)ethane common moiety: incorporation and hydrolysis of phosphate esters

Two tetradentate ligands 1,2-bis[2-((dimethylamino)methyl)-6-pyridyl]ethane (L1) and 1,2-bis[2-(N-piperidinomethyl)-6-pyridyl]ethane (L2) and a hexadentate ligand 1,2-bis(2-((methyl(pyridylmethyl)amino)methyl)-6-pyridyl)ethane (L3) were prepared as part of a series of new polypyridine ligands possessing a 1,2-bis(2-pyridyl)ethane common moiety. L1 and L2 form mononuclear Cu(II) complexes [Cu(L)(Cl)](ClO4) [L = L1 (1) and L2 (2)], respectively. L3 forms a dinuclear Cu(II) complex [Cu2(L3)((PhO)2PO2)2](ClO4)2 (3) or a hexanuclear Cu(II) complex [Cu6(L3)3((PhO)PO3)4](ClO4)4 (4) in the presence of (PhO)2PO2- monoanion or (PhO)PO3(2-) dianion, respectively. The structures of 1-4 were determined by X-ray analysis. The structures in solution were investigated by means of FAB and CSI MS spectrometers. The structural flexibility of the common 1,2-bis(2-pyridyl)ethane moiety and of the pendant groups allows complexes 1-4 to adapt to the various structures. Each Cu ion in 1 and 2 adopts a square pyramidal geometry with one Cl ion and two pendant groups (L1 and L2) binding in a bis-bidentate chelate mode. There is no steric repulsion between the pendant groups, so that the ligands specifically stabilize the mononuclear structures. L3 binds two Cu(II) ions with two pendant groups in tridentate chelate modes and, with the incorporation of phosphate esters, various dinuclear units are formed in 3 and 4. In 4, a dinuclear unit of [Cu2(L3)]4+ links two dinuclear units of [Cu2(L3)(PhOPO3)2] with four (mu3)-1,3-PhOPO3(2-) bridges. The hydrolytic activity of 2 and a dicopper(II) complex of L3 was examined with tris(p-nitrophenyl) phosphate (TNP) as a substrate.     

Flow-injection determination of phosphate with a cadmium ion-selective electrode

A flow-injection method is described, in which phosphate standards are introduced into a reagent stream containing Cd(2+) ,resulting in the formation of Cd(3)(PO(4))(2). The associated reduction in free metal concentration is sensed by a cadmium-selective electrode. With the exception of major interference from iodide and moderate interference from bromide and thiocyanate, the system exhibits excellent response to phosphate and selectivity over several common anions in solutions buffered at pH 8.4. A maximum sampling rate of 160/hr is possible for phosphate standards in the concentration range 10(-1)-10(-1)M with a 10(-4)M Cd(2+) reagent stream at a total flow-rate (carrier and reagent stream combined) of 8.4 ml/min.     

A near-infrared spectroscopic study of the phosphate mineral pyromorphite Pb5(PO4)3Cl

Spectral properties as a function composition are analysed for a series of selected pyromorphite minerals of Australian origin. The minerals are characterised by d-d transitions in NIR from 12,000 to 8000 cm(-1) (0.83-1.25 microm). A broad signal observed at approximately 10,000cm(-1) (1.00 microm) is the result of ferrous ion impurity in pyromorphites and follows a relationship between band intensity in the near-infrared spectra and ferrous ion concentration. The iron impurity causes a change in colour from green-yellow to brown in the pyromorphite samples. The observation of overtones of the OH(-) fundamentals, confirms the presence OH(-) in the mineral structure. The contribution of water-OH overtones in the NIR at 5100 cm(-1) (1.96 microm) is an indication of bonded water in the minerals of pyromorphite. Spectra in the mid-IR show that pyromorphite is a known mixed phosphate and arsenate complex, Pb5(PO4,AsO4)3Cl. A series of bands are resolved in the infrared spectrum of pyromorphite at 1017, 961 and 894 cm(-1). The first two bands are assigned to nu(3), the antisymmetric stretching mode and the third band at 894 cm(-1) is the symmetric mode of the phosphate ion. Similar patterns are shown by other pyromorphite samples with variation in intensity. The cause of multiple bands near 800 cm(-1) is the result of isomorphic substitution of (PO4)(3-) by (AsO4)(3-) and the spectral pattern relates to the chemical variability in pyromorphite. The presence of (AsO4)(3-) is significant in certain pyromorphite samples.     

From the tetra(amino) phosphonium cation, [P(NHPh)4]+, to the tetra(imino) phosphate trianion, [P(NPh)4]3-, two-faced ligands that bind anions and cations

The tetraanilino phosphonium cation, [P(N(H)Ph)4]+, 1+, is sequentially deprotonated by Bu(n)Li in thf. The deprotonation reaction of the chloride derivative, Cl, was monitored by (31)P NMR, which revealed the successive formation of the neutral [P(N(H)Ph)3(NPh)], 2, the monoanionic [P(N(H)Ph)2(NPh)2]-, 3-, the dianionic [P(N(H)Ph)(NPh)3]2-, 4(2-), and finally the trianionic species [P(NPh)(4)](3-), (3-). Considering the isoelectronic relationship of oxo, =O, and imino groups, =NR, as well as hydroxy, -OH, and amino groups, -N(H)R, the neutral complex corresponds to phosphoric acid, H3PO4, whereas the anions 3-, 4(2-) and 5(3-) are analogues of dihydrogen phosphate, H2PO4-, monohydrogenphosphate, HPO4(2-), and orthophosphate ions, PO4(3-), respectively. Solid state structures were obtained of 1Cl, 2LiCl(thf)(2), 3Li(thf)(3.5), 3Li(2)Cl(thf)(4.25), 3Li(2)Cl(thf)(6) and 5Li(4)Cl(thf)(4). All systems provide two separate N-P-N chelation sites at opposite ligand faces, either consisting of the di(amino) arrangement P(NH)(2), acting as a double H-bond donor, the di(imino) arrangement PN(2), donating two electron pairs, or the mixed amino imino arrangement P(N)(NH), which supplies both electron pair and H-donor site. Interesting in this aspect is the mixed amino imino derivative 3- which has the ability to chelate a Lewis acid, such as a metal ion, at one face and a Lewis base, such as an anionic or neutral donor at the opposite ligand face. The formation of 1-D aggregates and the entrapment of lithium chloride are key characteristics of the supramolecular structures of the discussed complexes.     

Formation of tungstate-containing cluster ions by polyoxotungstate anions under matrix-assisted laser desorption/ionization conditions in the gas phase

The gas-phase studies of transition-metal oxides continue to attract interest as such oxides are being used as catalysts in various oxidation processes. In this paper, singly negatively charged heteropolyoxotungstate and isopolyoxotungstate ion clusters were produced from Keggin-type polyoxotungstates by matrix-assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry (MALDI-FTICR MS). It was found that the ion series [(PO(3))(WO(3))(n)](-), [(WO(3))(n)](-) and [(OH)(WO(3))(n)](-) were the main fragment ions in the mass spectra and the matrix greatly influenced the resulting cluster ion abundances. [(PO(3))(WO(3))(3)](-), [(WO(3))(3)](-) and [(OH)(WO(3))(4)](-) were the most intense ions in each series when 2-(4-hydroxyphenylazo)benzoic acid was the matrix, whereas [(PO(3))(WO(3))(4)](-), [(WO(3))(6)](-) and [(OH)(WO(3))(4)](-) were the most intense when dithranol (DIT) was the matrix. In addition, a new kind of hybrid ion [W(2)C(14)H(7)O(8)](-) was produced through the reaction of DIT and [(OH)(WO(3))](-) in the plume of the gas phase. These results highlight the utility of the MALDI-FT method for obtaining novel ion clusters and also show the stability of these clusters.     

Encapsulation of trivalent phosphate anion within a rigidified π-stacked dimeric capsular assembly of tripodal receptor

The tris(thiourea) receptor, L, in the presence of excess H(2)PO(4)(-) has been found to encapsulate a trivalent phosphate ion within a π-stacked dimeric capsular assembly of the receptor with twelve strong H-bonds via deprotonation, as evident from the origin of a new set of signals in the (1)H NMR titration experiments.     

FTIR spectroscopic, thermal and XRD characterization of hydroxyapatite from new natural sources

The inorganic constituents of 5 different plants (leaves and stalks) were investigated by using Fourier transformer infrared spectroscopy (FTIR), X-ray diffraction (XRD) and thermal analysis including thermal gravimetric analysis (TGA), derivative thermogravimetry (DTG) and differential scanning calorimetry (DSC). These plants are Catha edulis (Khat), basil, mint, green tea and trifolium. The absorption bands of carbonate ions CO(3)(2-) was exhibited at 1446 cm(-1), and the phosphate ions PO(4)(3-) was assigned at 1105 and 1035 cm(-1). At high temperatures (600, 700 and 600°C) further absorption bands of the phosphate ions PO(4)(3-) was assigned at the frequencies 572, 617, 962, 1043 and 1110 cm(-1) and the vibrational absorption band of the carbonate ions CO(3)(2-) was assigned at 871, 1416 and 1461 cm(-1). X-ray diffraction and thermal analysis confirm the obtained results of FITR. Results showed that the main inorganic constituents of C. edulis and basil leaves are hydroxyapatite whereas the hydroxyapatite content in the other plant samples is less than that in case of C. edulis and basil plant leaves.