Lanthanide complexes of 2-hydroxynicotinic acid: synthesis, luminescence properties and the crystal structures of [Ln(HnicO)(2)(mu-HnicO)(H2O)] center dot nH(2)O (Ln = Tb, Eu)

New lanthanide complexes of 2-hydroxynicotinic acid (H(2)nicO) [Ln(HnicO)(2)(mu-HnicO)(H2O)] (.) nH(2)O (Ln = Eu, Gd, Tb, Er, Tm) were prepared. The crystal structures of the [Tb(HnicO)(2)(g-HnicO)(H2O)] (.) 1.75H(2)O(1) and [Eu(HniCO)(2)(mu-HnicO)(H2O)] (.) 1.25H(2)O (2) complexes were determined by X-ray diffraction. The 2-hydroxynicotinate ligand coordinates through O,O-chelation to the lanthanide(III) ions as shown by X-ray diffraction and the infrared, Raman and NMR spectroscopy results. Photoluminescence measurements were performed for the Eu(III) and Tb(III) complexes. Lifetimes of 0.592 +/- 0.007 and 0.113 +/- 0.002 ms were determined for the Eu3+ and Tb3+ emitting states D-5(0) and D-5(4), respectively. A value around 30% was found for the D-5(0) quantum efficiency. The energy transfer mechanisms between the lanthanide ions and the ligands are discussed and compared with those observed in similar complexes involving the 3-hydroxypicolinate ligand based on the luminescence of the respective Gd3+-based complexes. (C) 2003 Published by Elsevier Ltd.

The structure of the mixed OH+H2O overlayer on Pt{111}

The structure of the mixed p(3x3)-(3OH+3H(2)O) phase on Pt{111} has been investigated by low-energy electron diffraction-IV structure analysis. The OH+H2O overlayer consists of hexagonal rings of coplanar oxygen atoms interlinked by hydrogen bonds. Lateral shifts of the O atoms away from atop sites result in different O-O separations and hexagons with only large separations (2.81 and 3.02 angstrom) linked by hexagons with alternating separations of 2.49 and 2.81/3.02 A. This unusual pattern is consistent with a hydrogen-bonded network in which water is adsorbed in cyclic rings separated by OH in a p(3x3) structure. The topmost two layers of the Pt atoms relax inwards with respect to the clean surface and both show vertical buckling of up to 0.06 angstrom. In addition, significant shifts away from the lateral bulk positions have been found for the second layer of Pt atoms. (C) 2005 American Institute of Physics.

Assessment of the consistency of H2O line intensities over the near-infrared using sun-pointing ground-based Fourier transform spectroscopy

We report on the consistency of water vapour line intensities in selected spectral regions between 800���12,000 cm���1 under atmospheric conditions using sun-pointing Fourier transform infrared spectroscopy. Measurements were made across a number of days at both a low and high altitude field site, sampling a relatively moist and relatively dry atmosphere. Our data suggests that across most of the 800���12,000 cm���1 spectral region water vapour line intensities in recent spectral line databases are generally consistent with what was observed. However, we find that HITRAN-2008 water vapour line intensities are systematically lower by up to 20% in the 8000���9200 cm���1 spectral interval relative to other spectral regions. This discrepancy is essentially removed when two new linelists (UCL08, a compilation of linelists and ab-initio calculations, and one based on recent laboratory measurements by Oudot et al. (2010) [10] in the 8000���9200 cm���1 spectral region) are used. This strongly suggests that the H2O line strengths in the HITRAN-2008 database are indeed underestimated in this spectral region and in need of revision. The calculated global-mean clear-sky absorption of solar radiation is increased by about 0.3 W m���2 when using either the UCL08 or Oudot line parameters in the 8000���9200 cm���1 region, instead of HITRAN-2008. We also found that the effect of isotopic fractionation of HDO is evident in the 2500���2900 cm���1 region in the observations.

Synthesis, X-ray crystal structure and catalytic activity of the manganese(II) complex [Mn(bdoa)(H2O)3](bdoaH2 =benzene-1,2-dioxyacetic acid)

Benzene-1,2-dioxyacetic acid (bdoaH2) reacts with Mn(CH3CO2)2��4H2O in an ethanol-water mixture to give the manganese(II) complex [Mn(bdoa)(H2O)3]. The X-ray crystal structure of the complex shows the metal to be pseudo seven-coordinate. The quadridentate bdoa2��� dicar���ylate ligand forms an essentially planar girdle around the metal, being strongly bondedtransoid by a car���ylate oxygen atom from each of the two car���ylate moieties (mean MnO 2.199A��) and also weakly chelated by the two internal ether oxygen atoms (mean MnO 2.413A��). The coordination sphere about the manganese is completed by three water molecules (mean MnO 2.146A��) lying in a meridional plane orthogonal to that of the bdoa2��� ligand. Magnetic, conductivity and voltammetry data for the complex are given, and its use as a catalyst for the disproportionisation of H2O2 is described.

Synthesis, X-ray crystal structure and reactivity of the polymeric copper(II) dicarboxylic acid complex {Cu2(��1��1��2-oda)2(py)4(H2O)2}n(odaH2 = octanedioic acid, PY = pyridine)

An aqueous solution of the ��-��-dicarboxylic acid octanedioic acid (odaH2) reacts with [Cu2(��-O2CCH3)4(H2O)2] in the presence of an excess of pyridine (py) to give the crystalline copper(II) complex {Cu2(��1��1��2-oda)2(py)4(H2O)2}n (1). structure of 1, as determined by X-ray crystallography, consists of polymeric chains in which bridging oda2��� anions link two crystallographically identical copper atoms. The copper atoms are also ligated by two transoidal pyridine nitrogens and an oxygen atom from an apical water molecule, giving the metals an overall N2O3 square-pyramidal geometry. If the blue solid 1 is gently heated, or if it is left to stand in its mother liquor for prolonged periods, it loses one molecule of pyridine and half a molecule of water and the green complex {Cu (oda)(py)(H2O)0.5}n (2) is formed. Spectroscopic and magnetic data for both complexes are given, together with the electrochemical and thermogravimetric measurements for 1.

Synthesis and X-ray crystal structure of the triethylammonium magnesium ��-octamolybdate(VI)salt[Et3NH]2[Mg(H2O)6Mo8O26]��2H2O

[Et3NH]4[Mo8O26] reacted with MgCl2 giving the triethylammonum magnesium ��-octamolybdate(VI) salt [Et3NH]2[Mg(H2O)6Mo8O26]��2H2O (3) and the triethylammonium hydronium ��-octaamolybdate(VI) salt [Et3NH]3[(H3O)Mo8O26��2H2O (4), respectively. A small amount of [Et3NH]2[Mo6O269] was formed as a by-product. The salts 3 and 4 were characterized by X-ray crystallography. The [Mg(H2O)6Mo8O26]2��� moiety in 3 is polymeric, with each octahedral [Mg(H2O)6]2+ ion sandwiched between two ��[Mo8O26]4��� ions, being hydrogen bonded to three terminal MO���O oxygen atoms on one face of each ��[Mo8O26]4��� ion. The X-ray crystal structure of 4 corresponds to the reported previously. IR and conductivity data are given for 3 and 4.

Synthesis and structure of the Mn II,II complex salt [Mn2(��1��1��2-oda)(phen)4(H2O)2][Mn2][Mn2(��1��1��2-oda)(phen)4(��1-oda)2].4H2O (odah2 = octanedioic acid): a catalyst for H2O2 disproportionation

The synthesis and X-ray crystal structure of the MnII,11 complex double salt [Mn2(��1��1��2-oda)(phen)4(H2O)2][Mn2(��1��1��2-oda(phen)4(��1-oda)2]��4H2O is reported, together with its catalytic activity towards the disproportionation of H2O2.

Formation of isopolyoxometallate(VI) anions in the reaction between M(CO)6 (M = W, Mo) and acetic acid: X-ray crystal structure of [W3(��3-O)2(��2��2-O2CCH3)6(H2O)3]2[W10O32��solvent

W(CO)6 reacts with a mixture of acetic acid/acetic anhydride to give [W3 (��3-O)2(��2��2-O2CCH3)6(H2O)3](CH3CO2)2 (1), which was converted by HClO4 to [W3 (��3-O)2(��2��2-O2CCH3)6(H2O)3](ClO4)2 (2). Addition of CH3CO2Na to the above reaction mixture, and prolonged exposure of the solution to air, results in the formation of the WIV/WVI complex salt [W3(��3-O)2(��2��2-O2CCH3)6(H2O)3]2[W10O32]��solvent (3). Complex 3 was also prepared by reacting 1 with Na2WO4��2H2O in acetic acid, and it has been characterized by X-ray crystallography. Addition of [CH3(CH2)3]4N(ClO4) to the reaction filtrate remaining after the preparation of [Mo2(��-O2CCH3)4][from Mo(CO)6, CH3CO2H and (CH3CO)2O], followed by exposure to air, gives ([CH3(CH2)3]4N)2[Mo6O19] (4).

Facile oxidation of phenylphosphinic acid to phenylphosphonic acid using [Cu2(��-O2CCH3)4(H2O)2]: X-ray crystal structures of monomeric [Cu(PhPO3H)2(C5H5N)4]��2CH3OH and [Cu(PhPO3H)2(C5H5N)4]

Phenylphosphinic acid (HPhPO2H) is oxidized to phenylphosphonic acid (PhPO3H2) at room temperature using a solution of [Cu2(��-O2CCH3)4(H2O)2] in pyridine. The phenylphosphonic acid was recovered as the monomeric copper(II) complex [Cu(PhPO3H)2(C5H5N)4]��H2O (1a), and the reaction thought to proceed via a copper(I) intermediate. Recrystallization of 1a from methanol gave [Cu(PhPO3H)2(C5H5N)4]��2CH3OH (1b). The unsolvated complex [Cu(PhPO3H)2(C5H5N)4] (1c) was prepared by refluxing polymeric [Cu(PhPO3)(H2O)] (2) in pyridine. The X-ray crystal structures of 1b and 1c show that in each of these monomeric complexes the copper(II) ion is ligated by four equatorial pyridine molecules and two axial monoanionic phenylphosphonate groups. A cyclic voltammetric study of 1a revealed a quasi-reversible Cu2+/Cu+ couple with E1/2 = +228 mV (vs Ag/AgCl).

Reaction of (��)-1,1���-binaphthyl-2,2���-diyl hydrogen phosphate {(��)-phosH} with copper(II), cobalt(II) and iron(II) compounds; Identification by x-ray diffraction of [Co(CH3OH)4(H2O)2][(+)-phos][(���)-phos]. 2CH3OH��H2O

[Cu2(��O2CCH3)4(H2O)2], [CuCO3��Cu(OH)2], [CoSO4��7H2O], [Co((+)-tartrate)], and [FeSO4��7H2O] react with excess racemic (��)- 1,1���-binaphthyl-2,2���-diyl hydrogen phosphate {(��)-PhosH} to give mononuclear CuII, CoII and FeII products. The cobalt product, [Co(CH3OH)4(H2O)2]((+)-Phos)((���)-Phos) ��2CH3OH��H2O (7), has been identified by X-ray diffraction. The high-spin, octahedral CoII atom is ligated by four equatorial methanol molecules and two axial water molecules. A (+)- and a (���)-Phos��� ion are associated with each molecule of the complex but are not coordinated to the metal centre. For the other CoII, CuII and FeII samples of similar formulation to (7) it is also thought that the Phos��� ions are not bonded directly to the metal. When some of the CuII and CoII samples are heated under high vacuum there is evidence that the Phos��� ions are coordinated directly to the metals in the products.

Binuclear and polymeric manganese(II) salicylate complexes: synthesis, crystal structure and catalytic activity of [Mn2(Hsal)4(H2O)4] and [{Mn2(sal)2(Hsal)(H2O)-(H3O)(py)4���2py}n](H2sal = salicylic acid, py = pyridine)

The two air-stable manganese(II) salicylate complexes [Mn2(Hsal)4(H2O)4]1 and polymeric [{Mn2(sal)2(Hsal)(H2O)(H3O)(py)4��2py}n]2(H2sal = salicylic acid and py = pyridine) have been synthesised easily, and their crystal structures determined. Both contain unsymmetrically bridging salicylate ligands. In the presence of added pyridine 1 and 2 vigorously catalyse the disproportionation of H2O2.

Contested H2O: science, policy and politics in water resources management in Chile

This paper critically explores the politics that mediate the use of environmental science assessments as the basis of resource management policy. Drawing on recent literature in the political ecology tradition that has emphasised the politicised nature of the production and use of scientific knowledge in environmental management, the paper analyses a hydrological assessment in a small river basin in Chile, undertaken in response to concerns over the possible overexploitation of groundwater resources. The case study illustrates the limitations of an approach based predominantly on hydrogeological modelling to ascertain the effects of increased groundwater abstraction. In particular, it identifies the subjective ways in which the assessment was interpreted and used by the state water resources agency to underpin water allocation decisions in accordance with its own interests, and the role that a desocialised assessment played in reproducing unequal patterns of resource use and configuring uneven waterscapes. Nevertheless, as Chile���s ���neoliberal��� political-economic framework privileges the role of science and technocracy, producing other forms of environmental knowledge to complement environmental science is likely to be contentious. In conclusion, the paper considers the potential of mobilising the concept of the hydrosocial cycle to further critically engage with environmental science.

A global view of the extratropical tropopause transition layer from Atmospheric Chemistry Experiment Fourier Transform Spectrometer O3, H2O, and CO

The global behavior of the extratropical tropopause transition layer (ExTL) is investigated using O3, H2O, and CO measurements from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) on Canada���s SCISAT-1 satellite obtained between February 2004 and May 2007. The ExTL depth is derived using H2O-O3 and CO-O3 correlations. The ExTL top derived from H2O-O3 shows an increase from roughly 1���1.5 km above the thermal tropopause in the subtropics to 3���4 km (2.5���3.5 km) in the north (south) polar region, implying somewhat weaker tropospherestratosphere- transport in the Southern Hemisphere. The ExTL bottom extends ~1 km below the thermal tropopause, indicating a persistent stratospheric influence on the troposphere at all latitudes. The ExTL top derived from the CO-O3 correlation is lower, at 2 km or ~345 K (1.5 km or ~335 K) in the Northern (Southern) Hemisphere. Its annual mean coincides with the relative temperature maximum just above the thermal tropopause. The vertical CO gradient maximizes at the thermal tropopause, indicating a local minimum in mixing within the tropopause region. The seasonal changes in and the scales of the vertical H2O gradients show a similar pattern as the static stability structure of the tropopause inversion layer (TIL), which provides observational support for the hypothesis that H2O plays a radiative role in forcing and maintaining the structure of the TIL.

Seasonal cycles and variability of O3 and H2O in the UT/LMS during SPURT

Airborne high resolution in situ measurements of a large set of trace gases including ozone (O3) and total water (H2O) in the upper troposphere and the lowermost stratosphere (UT/LMS) have been performed above Europe within the SPURT project. SPURT provides an extensive data coverage of the UT/LMS in each season within the time period between November 2001 and July 2003. In the LMS a distinct spring maximum and autumn minimum is observed in O3, whereas its annual cycle in the UT is shifted by 2���3 months later towards the end of the year. The more variable H2O measurements reveal a maximum during summer and a minimum during autumn/winter with no phase shift between the two atmospheric compartments. For a comprehensive insight into trace gas composition and variability in the UT/LMS several statistical methods are applied using chemical, thermal and dynamical vertical coordinates. In particular, 2-dimensional probability distribution functions serve as a tool to transform localised aircraft data to a more comprehensive view of the probed atmospheric region. It appears that both trace gases, O3 and H2O, reveal the most compact arrangement and are best correlated in the view of potential vorticity (PV) and distance to the local tropopause, indicating an advanced mixing state on these surfaces. Thus, strong gradients of PV seem to act as a transport barrier both in the vertical and the horizontal direction. The alignment of trace gas isopleths reflects the existence of a year-round extra-tropical tropopause transition layer. The SPURT measurements reveal that this layer is mainly affected by stratospheric air during winter/spring and by tropospheric air during autumn/summer. Normalised mixing entropy values for O3 and H2O in the LMS appear to be maximal during spring and summer, respectively, indicating highest variability of these trace gases during the respective seasons.

New Ni(II)-sulfonamide complexes: Synthesis, structural characterization and antibacterial properties. X-ray diffraction of [Ni(sulfisoxazole)(2)(H2O)(4)] center dot 2H(2)O and [Ni(sulfapyridine)(2)]

The synthesis, structural characterization, voltammetric experiments and antibacterial activity of [Ni(sulfisoxazole)(2)(H2O)(4)] center dot 2H(2)O and [Ni(sulfapyridine)(2)] were studied and compared with similar previously reported copper complexes. [Ni(sulfisoxazole)(2)(H2O)(4)] center dot 2H(2)O crystallized in a monoclinic system, space group C2/c where the nickel ion was in a slightly distorted octahedral environment, coordinated with two sulfisoxazole molecules through the heterocyclic nitrogen and four water molecules. [Ni(sulfapyridine)(2)] crystallized in a orthorhombic crystal system, space group Pnab. The nickel ion was in a distorted octahedral environment, coordinated by two aryl amine N from two sulfonamides acting as monodentate ligands and four N atoms (two sulfonamidic N and two heterocyclic N) from two different sulfonamide molecules acting as bidentate ligands. Differential pulse voltammograms were recorded showing irreversible peaks at 1040 and 1070 mV, respectively, attributed to Ni(II)/Ni(III) process. [Ni(sulfisoxazole)(2)(H2O)(4)] center dot 2H(2)O and [Ni(sulfapyridine)(2)] presented different antibacterial behavior against Staphylococcus aureus and Escherichia coli from the similar copper complexes and they were inactive against Mycobacterium tuberculosis. (c) 2007 Elsevier Inc. All rights reserved.