Luminescence and defect centres in Tb(3+) doped LaMgAl(11)O(19) phosphors

Terbium (Tb) doped LaMgAl(11)O(19) phosphors have been prepared by the combustion of corresponding metal nitrates (oxidizer) and urea (fuel) at furnace temperature as low as 500 C Combustion synthesized powder phosphor was characterized by X-ray diffraction and field emission scanning electron microscopy techniques LaMgAl(11)O(19) doped with trivalent terbium ions emit weakly in blue and orange light region and strongly in green light region when excited by the ultraviolet light of 261 nm Electron Spin Resonance (ESR) studies were carried out to study the defect centres Induced in the phosphor by gamma irradiation and also to identify the defect centres responsible for the thermally stimulated luminescence (TSL) process Room temperature ESR spectrum of irradiated phosphor appears to be a superposition of at least two defect centres One of the centres (centre I) with principal g-values g(parallel to) = 2 0417 and g(perpendicular to) = 2 0041 is identified as O(2)(-) ion while centre II with an axially symmetric g-tensor with principal values g(parallel to) = 19698 and g(perpendicular to) = 1 9653 is assigned to an F(+) centre (singly ionized oxygen vacancy) An additional defect centre is observed during thermal annealing experiments and this centre (assigned to F(+) centre) seems to originate from an F centre (oxygen vacancy with two electrons) The F centre and also the F+ centre appear to correlate with the observed high temperature TSL peak in LaMgAl(11)O(19) Tb phosphor (C) 2010 Elsevier Masson SAS All rights reserved

Enhanced activity of horseradish peroxidase in Langmuir-Blodgett films of phospholipids

The immobilization of enzymes in nanostructured films has potential applications, e.g. in biosensing, for which the activity may not only be preserved, but also enhanced if optimized conditions are identified. Optimization is not straightforward because several requirements must be fulfilled, including a suitable matrix and film-forming technique. In this study, we show that horseradish peroxidase (HRP) has its activity enhanced when immobilized in Langmuir-Blodgett (LB) films, in conjunction with dipalmitoylphosphaticlylglycerol (DPPG). Incorporation of HRP into a DPPG monolayer at the air-water interface was demonstrated with compression isotherms, and Polarization-Modulation Infrared Reflection Absorption Spectroscopy (PM-IRRAS). From the PM-IRRAS data, we inferred that HRP was not denatured when adsorbed on a pre-formed, low pressure DPPG monolayer. A change in orientation was induced by the phospholipid matrix, with the amide C=O and NH groups from HRP being oriented perpendicular to the surface, parallel to the DPPG acyl chains, i.e. the alpha-helix was inserted into the monolayer. The mixed DPPG-HRP monolayer could be transferred onto solid supports, to which HRP activity was ca. 23% higher than in solution. The control of molecular architecture and choice of a suitable phospholipid matrix allowed HRP-containing LB films to be used in sensing peroxide. (c) 2008 Elsevier B.V. All rights reserved.

Micro Far-Infrared Reflectivity of CaNb(2)O(6) Single Crystal Fibers Grown by the Laser-Heated Pedestal Growth Technique

CaNb(2)O(6) single crystal fibers were grown by the laser-heated pedestal growth technique, directly from the starting reagents. Optically transparent fibers were obtained in the form of rods with elliptical cross-section, free from cracks, impurities, and secondary phases, with an average diameter of 0.4 mm and about 20 mm of length. The fibers grew within the orthorhombic Pbcn columbite structure, with the growth axis nearly parallel to the crystallographic a-direction. The parameters b and c were parallel to the shorter and larger ellipsis axes. A special setup using a microscope was developed to obtain the far-infrared reflectivity spectra of these micrometer-sized fibers, allowing the identification and assignment of 34 of the 38 polar phonons foreseen for the material. From these phonons, the intrinsic dielectric constant ( = 18.2) and quality factor ( of 185 THz) could be estimated, showing the potential of the material for applications in microwave circuitry. These results, along with previous polarized Raman data (Cryst. Growth Des. 2010, 10, 1569), allow us to present a comprehensive set of optical phonon modes and to discuss the potential use of designed CaNb(2)O(6) microcrystals in compact optical devices.

Structural effects and hydrogen bonds on N,N `-di(methoxycarbonylsulfenyl)urea, [CH(3)OC(O)SNH](2)CO, studied by experimental and theoretical methods

Pure N,N`-di(methoxycarbonylsulfenyl)urea, [CH(3)OC(O)SNH](2)CO, is quantitatively prepared by the hydrolysis reaction of CH(3)OC(O)SNCO and characterized by (1)H NMR, GC-MS and FTIR spectroscopy techniques. Structural and conformational properties are analyzed using a combined approach with data obtained from X-ray diffraction, vibrational spectra and theoretical calculation methods. The IR and Raman spectra for normal and deuterated species are reported. The crystal structure of [CH(3)OC(O)SNH](2)CO was determined by X-ray diffraction methods. The substance crystallizes in the orthorhombic P2(1)2(1)2 space group with a = 9.524(2), b = 12.003(1), c = 4.481 (1) angstrom, and Z = 2 moieties in the unit cell. The molecule is sited on a twofold crystallographic axis (C(2)) parallel to c and shows the anti-anti conformation (S-N single bonds antiperiplanar with respect to the opposite C-N single bonds in sulfenyl-urea-sic group). Neighboring molecules are arranged in a chain motif that extends along the C(2)-axis and is held by bifurcated NH center dot center dot center dot O center dot center dot center dot HN intermolecular bonds. A local planar symmetry is observed in the crystal for the central -SN(H)C(O)N(H)S- skeleton. Experimental and calculated data allow to trace this structural feature to the occurrence of N-H center dot center dot center dot O=C hydrogen bonding interactions. Calculated vibrational and structural properties are in good agreement with the experimentally determined features. (C) 2008 Elsevier B.V. All rights reserved.

Emplacement mechanism of the main granite pluton of the Lavras do Sul intrusive complex, South Brazil, determined by magnetic anisotropies

Magnetic fabric and rock magnetism studies were performed on apparently isotropic granite facies from the main intrusion of the Lavras do Sul Intrusive Complex pluton (LSIC, Rio Grande do Sul, South Brazil). This intrusion is roughly circular (similar to 12 x 13.5 km), composed of alkali-calcic and alkaline granitoids, with the latter occupying the margin of the pluton. Magnetic fabrics were determined by applying both anisotropy of low-field magnetic susceptibility (AMS) and anisotropy of anhysteretic remanent magnetization (AARM). The two fabrics are coaxial. The parallelism between AMS and AARM tensors excludes the presence of a single domain (SD) effect on the AMS fabric of the granites. Several rock-magnetism experiments performed in one specimen from each sampled site show that for all sites the magnetic susceptibility is dominantly carried by ferromagnetic minerals, while mainly magnetite carries the magnetic fabrics. Lineations and foliations in the granite facies were successful determined by applying magnetic methods. Magnetic lineations are gently plunging and roughly parallel to the boundaries of the pluton facies, except at the few sites in the central facies which have a radial orientation pattern. In contrast, the magnetic foliations tend to follow the contacts between the different granite facies. They are gently outerward-dipping inside the pluton, and become either steeply southwesterly dipping or vertical towards its margin. The lack of solid-state and subsolidus deformations at outcrop scale and in thin sections precludes deformation after full crystallization of the pluton. This evidence allows us to interpret the observed magnetic fabrics as primary in origin (magmatic) acquired when the rocks were solidified as a result of processes reflecting magma flow. The foliation pattern displays a dome-shaped form for the main LSIC-pluton. However, the alkaline granites which outcrop in the southern part of the studied area have an inward-dipping foliation, and the steeply plunging magnetic lineation suggests that this area could be part of a feeder zone. The magma ascent probably occurred due to ring-diking. (C) 2008 Elsevier B.V. All rights reserved.

Bendadaite, a new iron arsenate mineral of the arthurite group

Bendadaite, ideally Fe(2+)Fe(2)(3+)(AsO(4))(2)(OH)(2 center dot).4H(2)O, is a new member of the arthurite group It was found as a weathering product of arsenopyrite on a single hand specimen from the phosphate pegmatite Bendada. central Portugal (type locality) Co-type locality is the granite pegmatite of La via do Almerindo (Almerindo mine), Linopolis, Divmo das Laranjeiras county, Minas Gerais, Brazil Further localities are the Vein Negra mine, Copiapo province, Chile, mid-East, Bou Azzer district, Morocco, and Para Inferida yard, Fenugu Sibirt mine, Gonnosfanadiga, Medio Campidano Province, Sardinia. Italy Type bendadaite occurs as blackish green to dark brownish tufts (<0 1 mm long) and flattened radiating aggregates. in intimate association with an intermediate member of the scorodite-mansfieldite series It is monoclinic. space group P2(l/c). with a = 10 239(3) angstrom. b = 9 713(2) angstrom, c = 5 552(2) angstrom. beta = 94 11(2)degrees. = 550 7(2) angstrom(3). Z = 2 Electron-microprobe analysis yielded (wt %). CaO 0 04, MnO 0 03. CuO 006, ZnO 004. Fe(2)O(3) (total) 43 92, Al(2)O(3) 115. SnO(2) 0 10, As(2)O(5) 43 27. P(2)O(5) 1 86, SO(3) 0.03 The empirical formula is (Fe(0 52)(2+)Fe(0 32)(3+)rectangle(0 16))(Sigma 1 00)(Fe(1 89)(3+)Al(0 11))(Sigma 2 00)(As(1 87)P(0 13))(Sigma 2 00)O(8)(OH)(2 00) 4H(2)O based. CM 2(As,P) and assuming ideal 80, 2(OH), 4H2O and complete occupancy of the ferric on site by Fe(3+) and Al Optically, bendadaite is biaxial, positive, 2V(est) = 85+/-4 degrees, 2V(eale) = 88 degrees, with alpha 1 734(3). 13 1 759(3), 7 1 787(4) Pleochrosim is medium strong X pale reddish brown. Y yellowish brown, Z dark yellowish brown. absorption Z > V > X, optical dispersion weak, r > v. Optical axis plane Is parallel to (010), with X approximately parallel to a and Z nearly parallel to c Bendadaite has vitreous to sub-adamantine luster, is translucent and non-fluorescent It is brittle, shows irregular fracture and a good cleavage parallel to 1010} 3 15 0 10 g/cm(3), 3 193 g/cm3 (for the empirical formula) The five strongest powder diffraction lines [d in angstrom (I)(hkl] are 10 22 (10)(100), 7 036 (8)(110), 4 250 (5)(11 I), 2 865 (4)(311), 4 833 (3)(020,011) The d spacings are very similar to those of its Zn analogue, ojelaite The crystal structure of bendadaite was solved and refined using a crystal from the co-type locality with the composition (Fe(0 95)(2+)rectangle(0 05))(Sigma 1 00)(Fe(1 80)(3+)Al(0 20))Sigma(2 00)(As(1 48)P(0 52))(Sigma 2 00)O(8)) (OH)(2) 4H(2)O (R = 16%) and confirms an arthurite-type atomic arrangement

The Cariris Velhos tectonic event in Northeast Brazil

The Borborema Province in northeastern South America is a typical Brasiliano-Pan-African branching system of Neoproterozoic orogens that forms part of the Western Gondwana assembly. The province is positioned between the Sao Luis-West Africa craton to the north and the Sao Francisco (Congo-Kasai) craton to the south. For this province the main characteristics are (a) its subdivision into five major tectonic domains, bounded mostly by long shear zones, as follows: Medio Coreau, Ceara Central, Rio Grande do Norte, Transversal, and Southern; (b) the alternation of supracrustal belts with reworked basement inliers (Archean nuclei + Paleoproterozoic belts); and (c) the diversity of granitic plutonism, from Neoproterozoic to Early Cambrian ages, that affect supracrustal rocks as well as basement inliers. Recently, orogenic rock assemblages of early Tonian (1000-920 Ma) orogenic evolution have been recognized, which are restricted to the Transversal and Southern domains of the Province. Within the Transversal Zone, the Alto Pajeu terrane locally includes some remnants of oceanic crust along with island arc and continental arc rock assemblages, but the dominant supracrustal rocks are mature and immature pelitic metasedimentary and metavolcaniclastic rocks. Contiguous and parallel to the Alto Pajeu terrane, the Riacho Gravata subterrane consists mainly of low-grade metamorphic successions of metarhythmites, some of which are clearly turbiditic in origin, metaconglomerates, and sporadic marbles, along with interbedded metarhyolitic and metadacitic volcanic or metavolcaniclastic rocks. Both terrane and subterrane are cut by syn-contractional intrusive sheets of dominantly peraluminous high-K calc-alkaline, granititic to granodioritic metaplutonic rocks. The geochemical patterns of both supracrustal and intrusive rocks show similarities with associations of mature continental arc volcano-sedimentary sequences, but some subordinate intra-plate characteristics are also found. In both the Alto Pajeu and Riacho Gravata terranes, TIMS and SHRIMP U-Pb isotopic data from zircons from both metavolcanic and metaplutonic rocks yield ages between 1.0 and 0.92 Ga, which define the time span for an event of orogenic character, the Cariris Velhos event. Less extensive occurrences of rocks of Cariris Velhos age are recognized mainly in the southernmost domains of the Province, as for example in the Polo Redondo-Maranco terrane, where arc-affinity migmatite-granitic and meta-volcano-sedimentary rocks show U-Pb ages (SHRIMP data) around 0.98-0.97 Ga. For all these domains, Sm-Nd data exhibit Tom model ages between 1.9 and 1.1 Ga with corresponding slightly negative to slightly positive epsilon(Nd)(t) values. These domains, along with the Borborema Province as a whole, were significantly affected by tectonic and magmatic events of the Brasiliano Cycle (0.7-0.5 Ga), so that it is possible that there are some other early Tonian rock assemblages which were completely masked and hidden by these later Brasiliano events. Cariris Velhos processes are younger than the majority of orogenic systems at the end of Mesoproterozoic Era and beginning of Neoproterozoic throughout the world, e.g. Irumide belt, Kibaride belt and Namaqua-Natal belt, and considerably younger than those of the youngest orogenic process (Ottawan) in the Grenvillian System. Therefore, they were probably not associated with the proposed assembly of Rodinia. We suggest, instead, that Cariris Velhos magmatism and tectonism could have been related to a continental margin magmatic arc, with possible back-arc associations, and that this margin may have been a short-lived (<100 m.y.) leading edge of the newly assembled Rodinia supercontinent. (C) 2009 Elsevier Ltd. All rights reserved.

Conflicting structural and geochronological data from the Ibituruna quartz-syenite (SE Brazil): Effect of protracted ""hot"" orogeny and slow cooling rate?

The Ibituruna quartz-syenite was emplaced as a sill in the Ribeira-Aracuai Neoproterozoic belt (Southeastern Brazil) during the last stages of the Gondwana supercontinent amalgamation. We have measured the Anisotropy of Magnetic Susceptibility (AMS) in samples from the Ibituruna sill to unravel its magnetic fabric that is regarded as a proxy for its magmatic fabric. A large magnetic anisotropy, dominantly due to magnetite, and a consistent magnetic fabric have been determined over the entire Ibituruna massif. The magmatic foliation and lineation are strikingly parallel to the solid-state mylonitic foliation and lineation measured in the country-rock. Altogether, these observations suggest that the Ibituruna sill was emplaced during the high temperature (similar to 750 degrees C) regional deformation and was deformed before full solidification coherently with its country-rock. Unexpectedly, geochronological data suggest a rather different conclusion. LA-ICP-MS and SHRIMP ages of zircons from the Ibituruna quartz-syenite are in the range 530-535 Ma and LA-ICP-MS ages of zircons and monazites from synkinematic leucocratic veins in the country-rocks suggest a crystallization at similar to 570-580 Ma, i.e., an HT deformation >35My older than the emplacement of the Ibituruna quartz-syenite. Conclusions from the structural and the geochronological studies are therefore conflicting. A possible explanation arises from (40)Ar-(39)Ar thermochronology. We have dated amphiboles from the quartz-syenite, and amphiboles and biotites from the country-rock. Together with the ages of monazites and zircons in the country-rock, (40)Ar-(39)Ar mineral ages suggest a very low cooling rate: <3 degrees C/My between 570 and similar to 500 Ma and similar to 5 degrees C/My between 500 and 460 Ma. Assuming a protracted regional deformation consistent over tens of My, under such stable thermal conditions the fabric and microstructure of deformed rocks may remain almost unchanged even if they underwent and recorded strain pulses separated by long periods of time. This may be a characteristic of slow cooling ""hot orogens"" that rocks deformed at significantly different periods during the orogeny, but under roughly unchanged temperature conditions, may display almost indiscernible microstructure and fabric. (C) 2009 Elsevier B.V. All rights reserved.

Magnetic fabric and zircon U-Pb geochronology of the Itaoca pluton: Implications for the Brasiliano deformation of the southern Ribeira Belt (SE Brazil)

The Itaoca pluton consists of porphyritic monzogranite that intruded the upper crust into low-grade metasedimentary rocks of the Apiai Dornain (Ribeira Belt). Anisotropy of magnetic susceptibility and zircon U-Pb (Shrimp) geochronology were combined to determine pluton emplacement mechanisms and its chronology relative to the collision structures of the Paranapiacaba (Brasiliano II) orogenic system. Magnetic susceptibility ranges between 4 and 38 x 10(-3) SI, and thermomagnetic measurements indicate multidomain magnetite is the main carrier of anisotropy. The pluton shows an ""onion-skin"" structure roughly elongated to the northeast with its hinge zone including kilometer-wide roof-pendants. Magnetic lineations are variable in orientation in consistency with the dominant oblate symmetry of the magnetic fabric. A distinct NE-trending point-maxima, however, indicates the mean lineation is parallel to the stretching direction of the transpressive deformation that affected the regional host rocks. Prismatic zircon from the monzogranite, both in the core and in the finely-zoned margins, yielded an age of 623 +/- 10 Ma. These results suggest the magmatic fabric recorded the earlier strain increments of the regional shear deformation. It may correspond to the transition from continental arc to collision tectonics of the southern Ribeira Belt. (C) 2008 Elsevier Ltd. All rights reserved.

Paleomagnetic data and K-Ar ages from Mesozoic units of the Santa Marta massif: A preliminary interpretation for block rotation and translations

We report 6 K-Ar ages and paleomagnetic data from 28 sites collected in Jurassic, Lower Cretaceous and Paleocene rocks of the Santa Marta massif, to test previous hypothesis of rotations and translations of this massif, whose rock assemblage differs from other basement-cored ranges adjacent to the Guyana margin. Three magnetic components were identified in this study. A first component has a direction parallel to the present magnetic field and was uncovered in all units (D 352, I = 25.6, k = 57.35, a95 = 5.3, N = 12). A second component was isolated in Cretaceous limestone and Jurassic volcaniclastic rocks (D = 8.8, I = 8.3, k = 24.71, a95 = 13.7, N = 6), and it was interpreted as of Early Cretaceous age. In Jurassic sites with this component, Early Cretaceous K-Ar ages obtained from this and previous studies are interpreted as reset ages. The third component was uncovered in eight sites of Jurassic volcaniclastic rocks, and its direction indicates negative shallow to moderate inclinations and northeastward declinations. K-Ar ages in these sites are of Early (196.5 +/- 4.9 Ma) to early Late Jurassic age (156.6 +/- 8.9 Ma). Due to local structural complexity and too few Cretaceous outcrops to perform a reliable unconformity test, we only used two sites with (1) K-Ar ages, (2) less structural complexity, and (3) reliable structural data for Jurassic and Cretaceous rocks. The mean direction of the Jurassic component is (D = 20.4, I = -18.2, k = 46.9, a95 = 5.1, n = 18 specimens from two sites). These paleomagnetic data support previous models of northward along-margin translations of Grenvillian-cored massifs. Additionally, clockwise vertical-axis rotation of this massif, with respect to the stable craton, is also documented; the sense of rotation is similar to that proposed for the Perija Range and other ranges of the southern Caribbean margin. More data is needed to confirm the magnitudes of rotations and translations. (C) 2009 Elsevier Ltd. All rights reserved.

A criterion for unitary similarity of upper triangular matrices in general position

Each square complex matrix is unitarily similar to an upper triangular matrix with diagonal entries in any prescribed order. Let A = [a(ij)] and B = [b(ij)] be upper triangular n x n matrices that are not similar to direct sums of square matrices of smaller sizes, or are in general position and have the same main diagonal. We prove that A and B are unitarily similar if and only if parallel to h(A(k))parallel to = parallel to h(B(k))parallel to for all h is an element of C vertical bar x vertical bar and k = 1, ..., n, where A(k) := [a(ij)](i.j=1)(k) and B(k) := [b(ij)](i.j=1)(k) are the leading principal k x k submatrices of A and B, and parallel to . parallel to is the Frobenius norm. (C) 2011 Elsevier Inc. All rights reserved.

Occupational airborne contamination in South Brazil: 2. Oxidative stress detected in the blood of workers of incineration of hospital residues

One of the most useful methods for elimination of solid residues of health services (SRHS) is incineration. However, it also provokes the emission of several hazardous air pollutants such as heavy metals, furans and dioxins, which produce reactive oxygen species and oxidative stress. The present study, which is parallel to an accompanied paper (Avila Jr. et al., this issue), investigated several enzymatic and non-enzymatic biomarkers of oxidative stress in the blood (contents of vitamin E, lipoperoxidation = TBARS, reduced glutathione = GSH, oxidized glutathione = GSSG, and activities of glutathione S-transferase = GST, glutathione reductase = GR, glutathione peroxidase = GPx, catalase = CAT and superoxide dismutase = SOD), in three different groups (n = 20 each) exposed to airborne contamination associated with incineration of SRHS: workers directly (ca. 100 m from the incinerator) and indirectly exposed (residents living ca. 5 km the incineration site), and controls (non-exposed subjects). TBARS and GSSG levels were increased whilst GSH, TG and alpha-tocopherol contents were decreased in workers and residents compared to controls. Increased GST and CAT activities and decreased GPx activities were detected in exposed subjects compared to controls, while GR did not show any difference among the groups. In conclusion, subjects directly or indirectly exposed to SRHS are facing an oxidative insult and health risk regarding fly ashes contamination from SRHS incineration.

Redox regulation of the mitochondrial K(ATP) channel in cardioprotection

The mitochondrial ATP-sensitive potassium channel (mK(ATP)) is important in the protective mechanism of ischemic preconditioning (IPC). The channel is reportedly sensitive to reactive oxygen and nitrogen species, and the aim of this study was to compare such species in parallel, to build a more comprehensive picture of mK(ATP) regulation. mK(ATP) activity was measured by both osmotic swelling and Tl(+) flux assays, in isolated rat heart mitochondria. An isolated adult rat cardiomyocyte model of ischemia-reperfusion (IR) injury was also used to determine the role of mK(ATP) in cardioprotection by nitroxyl. Key findings were as follows: (i) mK(ATP) was activated by O(2)(center dot-) and H(2)O(2) but not other peroxides. (ii) mK(ATP) was inhibited by NADPH. (iii) mK(ATP) was activated by S-nitrosothiols, nitroxyl, and nitrolinoleate. The latter two species also inhibited mitochondrial complex II. (iv) Nitroxyl protected cardiomyocytes against IR injury in an mK(ATP)-dependent manner. Overall, these results suggest that the mK(ATP) channel is activated by specific reactive oxygen and nitrogen species, and inhibited by NADPH. The redox modulation of mK(ATP) may be an underlying mechanism for its regulation in the context of IPC. This article is part of a Special Issue entitled: Mitochondria and Cardioprotection. (C) 2010 Elsevier B.V. All rights reserved.

Irreversible inhibition of human cathepsins B, L, S and K by hypervalent tellurium compounds

The inhibition of human cysteine cathepsins B, L, S and K was evaluated by a set of hypervalent tellurium compounds (telluranes) comprising both organic and inorganic derivatives. All telluranes studied showed a time-and concentration-dependent irreversible inhibition of the cathepsins, and their second-order inactivation rate constants were determined. The organic derivatives were potent inhibitors of the cathepsins and clear specificities were detected, which were parallel to their known substrate specificities. In all cases, the activity of the tellurane-inhibited cathepsins was recovered by treatment of the inactivated enzymes with reducing agents. The maximum stoichiometry of the reaction between cysteine residues and telluranes were also determined. The presented data indicate that it is possible to design organic compounds with a tellurium(IV) moiety as a novel warhead that covalently modifies the catalytic cysteine, and which also form strong interactions with subsites of cathepsins B, L, S and K, resulting in more specific inhibition.

Modelling water adsorption on Au(210) surfaces: II. Monte Carlo simulations

Canonical Monte Carlo simulations for the Au(210)/H(2)O interface, using a force field recently proposed by us, are reported. The results exhibit the main features normally observed in simulations of water molecules in contact with different noble metal surfaces. The calculations also assess the influence of the surface topography on the structural aspects of the adsorbed water and on the distribution of the water molecules in the direction normal to the metal surface plane. The adsorption process is preferential at sites in the first layer of the metal. The analysis of the density profiles and dipole moment distributions points to two predominant orientations. Most of the molecules are adsorbed with the molecular plane parallel to surface, while others adsorb with one of the O-H bonds parallel to the surface and the other bond pointing towards the bulk liquid phase. There is also evidence of hydrogen bond formation between the first and second solvent layers at the interface. (c) 2007 Elsevier B.V. All rights reserved.