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The electronic structure of monolayers of iron(II) phthalocyanine (FePc), iron(II) octaethylporphyrin (FeOEP), and iron(II) tetraphenylporphyrin (FeTPP), adsorbed on Au(111), was examined with X-ray and UV photoelectron spectroscopy (XPS/UPS). Comparison of the Fe 2p3/2 signals of FePc multilayers and monolayers revealed an additional component in the monolayer signal with a binding energy characteristic of Fe(0). This component accounts for ∼20% of the integral Fe 2p3/2 intensity, in agreement with previous observations on cobalt porphyrins on Au(111). The partial modification of the Fe 2p3/2 states suggests a laterally inhomogeneous interaction of the adsorbed molecules with the metal surface and is possibly related to the complex, reconstructed Au(111) surface morphology. Similar results obtained for FeTPP and FeOEP monolayers indicate that this effect is independent from the structure of the peripheral substituents on the core porphin moiety. The UP spectra of FePc and FeTPP monolayers show further in...

The adsorption and reaction of terephthaloyl chloride (TPC) on a Ag(111) surface was investigated with X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations. Below 120 K, TPC forms multilayers without reacting with the Ag(111) substrate. Multilayer desorption starts above 120 K and is accompanied by a chemical reaction between the TPC molecules and the Ag surface. This reaction involves scission of the carbon–chlorine bond, resulting in the formation of adsorbed chlorine atoms and a p-phenylene dicarbonyl (pPDC) species. This molecular fragment is stable at room temperature and does not undergo further decomposition, presumably due to stabilization by adsorbate–substrate interactions and/or oligomerization. The DFT calculations confirm that pPDC is a possible intermediate or final reaction product and show that the two carbonyl C atoms form covalent bonds to the Ag substrate.

Interfaces between organic semiconductors and metallic layers are ubiquitous in organic (opto-) electronic devices and can significantly influence their functionality. Here, we studied in situ prepared metal-organic interfaces, which were obtained by vapor deposition of metals (Co, Fe) onto organic semiconductor films (2H-tetraphenylporphyrin), with hard x-ray photoelectron spectroscopy. In these systems, the interphase zones, which are formed by diffusion and reaction of the metal in the organic material, can be clearly distinguished spectroscopically from the unreacted organic bulk, since they comprise the corresponding metalloporphyrins, CoTPP and FeTPP. In order to gain control over the thickness of the interphase layers, we varied process parameters such as sample temperature and metal-atom flux during interface preparation. We found that the temperature of the organic film during metal deposition was the only parameter that significantly influenced the formation of the interphase layers: their thicknesses were typically ~0.5 nm for deposition at 90 K, compared to ~1 nm at 300 K, irrespective of metal atom flux and chemical nature of the metal atom (Fe versus Co). Notably, these values are significantly smaller than the thicknesses of other metal/organics interphase regions reported in the literature.

Well dispersed and homogeneously distributed Pd nanoparticles within a silica matrix were synthesized by a two stage process: (1) intercalation of palladium tetrammine ions into the layered aluminium-free silicate Na ilerite followed by (2) a self-reduction of the complex through decomposition of the tetrammine ligands by calcination at 550 °C for 5 h under N2 or air. Samples calcined in N2 predominantly contained nanoparticles of metallic Pd, while calcination in air led largely to the formation of PdO, as confirmed by XPS and supported by XRD and TGA. Thus, the Pd/PdO loading in the silica can be selectively tuned through this method. The intercalates were characterized by standard methods such as XRD, TGA, ICP and TEM. TGA of the intercalates indicated that the stabilization of the palladium tetrammine complex was enhanced by intercalation into Na ilerite. Based on ICP analysis, the Pd loadings in the intercalates were estimated to be about 18 mass-%, which was also in agreement with the results from TGA. TEM revealed that the Pd/PdO nanoparticles were well dispersed in the silica matrix with an average particle size of approximately 8–10 nm after calcination in air.

We investigated the compound 1T-Cu x Ta1-x S2 with respect to its synthesis, homogeneity range, structure and electronic properties. The average structure of 1T-Cu x Ta1-x S2 resembles that of the high-temperature phase of the layered transition metal dichalcogenide 1T-TaS2 in which tantalum is partially substituted by copper. 1T-Cu x Ta1-x S2 readily decomposes at elevated temperatures and can only be prepared and stabilized by a sufficiently high amount of sulfur excess. XPS and NEXAFS measurements reveal that copper has the oxidation state +I in 1T-Cu x Ta1-x S2, which is supported by quantum chemical calculations. The disorder introduced by copper doping causes an Anderson-type localization of the conduction electrons as manifested by a strong increase of the electrical resistivity and a Curie-type paramagnetism at low temperatures as in other doped systems 1T-M x Ta1-x S2 with higher valent metals. Quantum chemical calculations support this interpretation.

Alpine ecosystems (alpine tundra) occur at a range of air density, water availability and seasonality worldwide on the treeless high terrain of mountains. They vary along geographic scales: boreal dwarf-shrub heaths, temperate sedge heaths, subtropical dwarf shrubs and tussock grasslands, and tropical giant forblands. Along local topographic gradients plant cover changes from windswept dwarf-shrub heath, to dense grass-sedge heath, to snowbank vegetation. These cold and relatively little exploited alpine ecosystems, nonetheless, are among those where climate warming impacts are forecast to be pronounced and detectable early on. We first review alpine life conditions and organism traits as a background to understanding climate impact related processes. Next, we provide an account of how alpine flora and vegetation have been impacted by recently observed climate change. Finally, a global network for long-term monitoring of climate-induced changes of vegetation and biodiversity in alpine environments is described. Alpine Environments – Definition, Distribution, Elevation, Zonation

Tetraphenylporphyrin (2HTPP) molecules were vapor-deposited onto a gold(111) surface to serve as reactive ligands for the direct synthesis of nickel(II) tetraphenylporphyrin (NiTPP) under ultrahigh vacuum (UHV) conditions. The surface-confined coordination reaction between a 2HTPP monolayer and coadsorbed Ni as well as the structure of 2HTPP multilayer films on Au(111) was characterized in detail using synchrotron radiation photoelectron spectroscopy (SRPES), X-ray photoelectron spectroscopy (XPS), and near-edge X-ray absorption fine structure spectroscopy (NEXAFS). It is shown that the vapor-deposited 2HTPP multilayer on Au(111) has a high degree of ordering with a preferential orientation of the molecular plane relative to the substrate. Monolayers of 2HTPP on Au(111) were obtained by annealing the 2HTPP multilayers to 520 K and were found to be thermally stable up to at least 580 K. NiTPP can be synthesized directly on the Au(111) surface through reaction of the 2HTPP monolayer with postadsorbed Ni ato...

Oligopyrroles and their metal complexes are versatile materials for surface and interface functionalization [1]. While monolayers of these molecules can sometimes be prepared by physical vapor deposition under vacuum conditions, this approach is limited to chemically and thermally stable species. An interesting alternative is the on-surface synthesis, which provides access to monolayers of species that are too fragile for vapor deposition or that cannot be made by solution-based synthesis at all. In this contribution, I introduce several strategies for the on-surface synthesis of oligopyrroles: (1) On-surface metalation of pre-deposited free-base porphyrin, phthalocyanine, or corrole ligands. With this approach, surface-stabilized complexes with metal centers in unusual oxidation states can be prepared. The attachment of additional ligands on the metal center can lead to bonding competition such as the surface trans effect. (2) Phthalocyanines, naphthalocyanines and their expanded homologs can be prepared by template-directed on-surface synthesis from suitable dinitrile-based precursors. (3) On-surface synthesis also gives access to linear open-chain counterparts of phthalocyanines, which represent a novel class of non-cyclic oligopyrroles. Structure, electronic properties and reactivities of the oligopyrrole monolayers will be discussed on the basis of extensive experimental and theoretical results. [1] J.M. Gottfried, Surface Chemistry of Porphyrins and Phthalocyanines, Surf. Sci. Rep. 70 (2015) 259-379.

The adsorption of Ca on electron-irradiated poly(3-hexylthiophene) (P3HT) surfaces at 300 K (E(kin) = 100 eV) has been studied by adsorption microcalorimetry, atomic beam/surface scattering, X-ray photoelectron spectroscopy (XPS), and low-energy He(+) ion scattering spectroscopy (LEIS). The results are compared to previous studies of Ca adsorption on pristine P3HT. The major structural effect of electron irradiation is a substantial increase in the fraction of unsaturated carbon atoms, probably a result of electron-induced hydrogen abstraction from the hexyl chains and formation of new C=C double bonds. No loss of sulfur was observed. The combined XPS, LEIS, and calorimetry data indicate that the reaction and growth behavior of Ca on P3HT surfaces is not significantly affected by this electron damage, apart from an increased sticking probability at low coverages. The sticking probability of Ca on the irradiated P3HT is initially 0.63, compared to 0.36 on the pristine surface. It increases with coverage, approaching unity between 4 and 5 ML. The heat of adsorption stays nearly constant at 405 kJ/mol up to a coverage of 0.6 ML, which is ascribed to Ca diffusing below the surface and forming CaS clusters by abstraction of sulfur from the thiophene rings, based on XPS and LEIS data. The heat of adsorption then decreases gradually until it reaches the heat of sublimation of bulk Ca, 178 kJ/mol, by 4 ML; this is attributed to the formation of 3D Ca islands on top of the polymer, which eventually coalesce into a continuous Ca film by 11 ML. The heat of reaction versus coverage and the ultimate depth up to which the Ca atoms react with the polymer thiophene groups (approximately 3 nm) are nearly independent of electron damage, except for a difference in the heat of adsorption below 0.1 ML associated with defects or impurities. The increase in initial sticking probability caused by electron damage is attributed to stronger bonding of Ca adatoms to unsaturated versus saturated hydrocarbons. These very weakly held Ca adatoms are transient precursors to the two reactions which dominate the measured heat of adsorption (reaction with thiophene units and Ca cluster formation), but they can also desorb in this three-path kinetic competition. Mass spectrometer data show that these precursors have longer surface residence times on the electron-damaged surface.

The adsorption of Ca on poly(3-hexylthiophene) (P3HT) has been studied by adsorption microcalorimetry, atomic beam/surface scattering, X-ray photoelectron spectroscopy (XPS), low-energy He(+) ion scattering spectroscopy (LEIS), and first-principles calculations. The sticking probability of Ca on P3HT is initially 0.35 and increases to almost unity by 5 ML. A very high initial heat of adsorption in the first 0.02 ML (625-500 kJ/mol) is attributed to the reaction of Ca with defect sites or residual contamination. Between 0.1 and 0.5 ML, there is a high and nearly constant heat of adsorption of 405 kJ/mol, which we ascribe to Ca reacting with subsurface sulfur atoms from the thiophene rings of the polymer. This is supported by the absence of LEIS signal for Ca and the shift of the S 2p XPS binding energy by -2.8 eV for reacted S atoms. The heat of adsorption decreases above 0.6 ML coverage, reaching the sublimation enthalpy of Ca, 178 kJ/mol, by 4 ML. This is attributed to the formation of Ca nanoparticles and eventually a continuous solid Ca film, on top of the polymer. LEIS and XPS measurements, which show only a slow increase of the signals related to solid Ca, support this model. Incoming Ca atoms are subject to a kinetic competition between diffusing into the polymer to react with subsurface thiophene units versus forming or adding to three-dimensional Ca clusters on the surface. At approximately 1.6 ML Ca coverage, Ca atoms have similar probabilities for either process, with the former dominating at lower coverage. Ultimately about 1.6 ML of Ca (1.2 x 10(15) atoms/cm(2)) reacts with S atoms, corresponding to a reacted depth of approximately 3 nm, or nearly five monomer-unit layers. Density-functional theory calculations confirm that the heat of reaction and the shift of the S 2p signal are consistent with Ca abstracting S from the thiophene rings to form small CaS clusters.

An aromatic triphenylene molecule (2,3-diethyl-1,4-dimethoxytriphenylene; TPH) and its regioselectively Cr(CO)3-labeled complex (η6-(1,2,3,4,4a,12b)-tricarbonyl(2,3-diethyl-1,4-dimethoxytriphenylene)chromium(0); α-TPHC) were deposited on a Ag(111) surface by vapor deposition. The monolayers were investigated by X-ray photoelectron spectroscopy and scanning tunneling microscopy. Both substances adsorb with the extended π-system parallel to the surface and form long-range ordered monolayers. The Cr(CO)3 group of the α-TPHC complex is oriented toward the vacuum. Although the footprints of both substances are similar, the additional Cr(CO)3 group on the α-TPHC leads to a lateral order (unit cell) that is significantly different from that of TPH.

The unique properties of gold especially in low temperature CO oxidation have been ascribed to a combination of various effects. In particular, particle sizes below a few nanometers and specific particle-support interactions have been shown to play important roles. In contrast, recent reports revealed that monolithic nanoporous gold (npAu) prepared by leaching a less noble metal, such as Ag, out of the corresponding alloy can also exhibit a remarkably high catalytic activity for CO oxidation, even though no support is present. Therefore, it was claimed to be a pure and unsupported gold catalyst. We investigated npAu with respect to its morphology, surface composition, and catalytic properties. In particular, we studied the reaction kinetics for low temperature CO oxidation in detail, taking the mass transport limitation due to the porous structure of the material into account. Our results reveal that Ag, even if removed almost completely from the bulk, segregates to the surface, resulting in surface concentrations of up to 10 atom %. Our data suggest that this Ag plays a significant role in activating of molecular oxygen. Therefore, npAu should be considered a bimetallic catalyst rather than a pure Au catalyst.

Different metallophthalocyanines and 2,4,6-triphenylpyrylium (TP +) ions were entrapped in different inorganic supports such as Y zeolite, mesoporous MCM-41, TiO2-SiO2 and SiO2 following a specific protocol. The resulting supramolecular structures were characterized by chemical analysis and diffuse reflectance UV-Vis measurements. The determination of the band gap on the basis of UV-Vis measurements showed that the host is not a spectator in this process and an electronic interaction occurs that lowers the band gap of the support. The XPS measurements were performed with an in situ X-ray photoelectron spectrometer, which can be operated at pressures of up to 1 mbar at the sample. They indicated that the formation of the supramolecular structure generates a stable environment, in which the oxidation state of the metal can still be influenced by reaction of the metal center with gas molecules. The photocatalytic tests carried out in photodecomposition of dipropyl sulfide showed a good correlation between the band gap values and the photocatalytic activity for metallophthalocyanine complexes. It is remarkable that the triphenylpyrylium ion follows the same trend observed for metallophthalocyanines, although it is a different type of photosensitizer.

Recent years have seen rapid progress in the field of surface-confined coordination chemistry. Adsorbed metal complexes of tetrapyrroles (porphyrins, phthalocyanines, corroles) are especially interesting in this context, since they combine a planar structure-determining element with an active site. While earlier studies of adsorbed metallo-tetrapyrroles mainly addressed aspects of molecular self-assembly, the focus of interest has shifted gradually to electronic structure and chemical reactivity. This article gives an overview of recent advances in the field of surface chemistry with tetrapyrroles. In particular, the following aspects will be discussed: intramolecular conformation and supramolecular ordering, electronic interaction with the substrate, surface-confined synthesis, and ligand-related effects such as the surface trans effect.

The in situ metalation of monolayers and multilayers of 2H-tetraphenylporphyrin (2HTPP) with Fe atoms on Ag(111) was studied with scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). This surface-confined coordination reaction results in the formation of adsorbed iron(II)-tetraphenylporphyrin (FeTPP). It is demonstrated that metalation of 2HTPP is achieved either by depositing iron atoms onto a monolayer of 2HTPP at room temperature or, alternatively, by depositing 2HTPP onto a Ag(111) surface with predeposited iron. The latter route requires elevated temperatures, indicating that this reaction includes at least one step with an activation barrier. In addition, it is demonstrated that vapor deposited Fe atoms also react with multilayers of the porphyrin at room temperature under the formation of FeTPP.

The heat of adsorption and sticking probability of cyclohexene on Pt(111) were measured as a function of coverage using single-crystal adsorption calorimetry in the temperature range from 100 to 300 K. At 100 K, cyclohexene adsorbs as intact di-sigma bonded cyclohexene on Pt(111), and the heat of adsorption is well described by a second-order polynomial (130 - 47 theta - 1250 theta(2)) kJ/mol, yielding a standard enthalpy of formation of di-sigma bonded cyclohexene on Pt(111) at low coverages of -135 kJ/mol and a C-Pt sigma bond strength of 205 kJ/mol. At 281 K, cyclohexene dehydrogenates upon adsorption, forming adsorbed 2-cyclohexenyl (c-C6H(9,a)) and adsorbed hydrogen, and the heat of adsorption is well described by another second-order polynomial (174 - 700 theta + 761 theta(2)) kJ/mol. This yields a standard enthalpy of formation of adsorbed 2-cyclohexenyl on Pt(111) at a low coverage of -143 kJ/mol. At coverages below 0.10 ML, the sticking probability of cyclohexene on Pt(111) is close to unity (>0.95), independent of temperature.

We have studied the reaction of NO2 with BaO nanoparticles supported on an ordered Al2O3 thin film on NiAl(110). Combining chemical analysis by X-ray photoelectron spectroscopy (XPS) and vibrational spectroscopy by infrared reflection absorption spectroscopy (IRAS), performed in combination with molecular beam (MB) techniques, the sequence of appearance of various nitrogen−oxo surface intermediates and their spectral properties are identified. The initial intermediates at 300 K are surface nitrites (NO2-), which are preferentially oriented parallel to the surface. Whereas formation of nitrites is rapid even at 300 K, conversion of nitrites into surface nitrates (NO3-) occurs at a very low rate. After surface nitrate formation, no further reaction is observed. At higher temperature (500 K), conversion into surface nitrates is more facile and is followed by formation of ionic nitrates. All three nitrogen−oxo species can be clearly identified via their characteristic vibrational spectra. No spectroscopic evi...

International audience; Aim In the alpine life zone, plant diversity is strongly determined by local topography and microclimate. We assessed the extent to which aspect and its relatedness to temperature affect plant species diversity, and the colonization and disappearance of species on alpine summits on a pan-European scale. Location Mountain summits in Europe's alpine life zone. Methods Vascular plant species and their percentage cover were recorded in permanent plots in each cardinal direction on 123 summits in 32 regions across Europe. For a subset from 17 regions, resurvey data and 6-year soil temperature series were available. Differences in temperature sum and Shannon index as well as species richness, colonization and disappearance of species among cardinal directions were analysed using linear mixed-effects and generalised mixed-effects models, respectively. Results Temperature sums were higher in east- and south-facing aspects than in the north-facing ones, while the west-facing ones were intermediate; differences were smallest in northern Europe. The patterns of temperature sums among aspects were consistent among years. In temperate regions, thermal differences were reflected by plant diversity, whereas this relationship was weaker or absent on Mediterranean and boreal mountains. Colonization of species was positively related to temperature on Mediterranean and temperate mountains, whereas disappearance of species was not related to temperature. Main conclusions Thermal differences caused by solar radiation determine plant species diversity on temperate mountains. Advantages for plants on eastern slopes may result from the combined effects of a longer diurnal period of radiation due to convection cloud effects in the afternoon and the sheltered position against the prevailing westerly winds. In northern Europe, long summer days and low sun angles can even out differences among aspects. On Mediterranean summits, summer drought may limit species numbers on the warmer slopes. Warmer aspects support a higher number of colonization events. Hence, aspect can be a principal determinant of the pace of climate-induced migration processes.

12 páginas, 3 figuras, 3 tablas.-- et al., [1]: The stress gradient hypothesis suggests a shift from predominant competition to facilitation along gradients of increasing environmental severity. This shift is proposed to cause parallel changes from prevailing spatial segregation to aggregation among the species within a community. [2]: We used 904 1-m2 plots, each subdivided into 100 10 × 10 cm, or 25 20 × 20 cm cells, respectively, from 67 European mountain summits grouped into 18 regional altitudinal transects, to test this hypothesized correlation between fine-scale spatial patterns and environmental severity. [3]: The data were analysed by first calculating standardized differences between observed and simulated random co-occurrence patterns for each plot. These standardized effect sizes were correlated to indicators of environmental severity by means of linear mixed models. In a factorial design, separate analyses were made for four different indicators of environmental severity (the mean temperature of the coldest month, the temperature sum of the growing season, the altitude above tree line, and the percentage cover of vascular plants in the whole plot), four different species groups (all species, graminoids, herbs, and all growth forms considered as pseudospecies) and at the 10 × 10 cm and 20 × 20 cm grain sizes. [4]: The hypothesized trends were generally weak and could only be detected by using the mean temperature of the coldest month or the percentage cover of vascular plants as the indicator of environmental severity. The spatial arrangement of the full species set proved more responsive to changes in severity than that of herbs or graminoids. The expected trends were more pronounced at a grain size of 10 × 10 cm than at 20 × 20 cm. [5. Synthesis]: In European alpine plant communities the relationships between small-scale co-occurrence patterns of vascular plants and environmental severity are weak and variable. This variation indicates that shifts in net interactions with environmental severity may differ among indicators of severity, growth forms and scales. Recognition of such variation may help to resolve some of the current debate surrounding the stress gradient hypothesis., The data used in this study were collected within the project GLORIA-Europe in the 5th RTD Framework Programme of the European Union (2001–03; No. EVK2-CT-2000–00056) with the support of Switzerland (OFES 00.0184–1). The analysis was supported by the Austrian Federal Ministry of Agriculture, Forestry, Environment and Water Management and through the project ALARM (‘Assessing large-scale risks for biodiversity with tested methods’; No. GOCE-CT- 2003–506675) of the 6th RTD Framework Programme of the EU.

We report the first example of a surface-confined two-step synthesis of axially coordinated metalloporphyrin complexes in an ultrahigh vacuum environment. Specifically, a monolayer of tetraphenylporphyrin on an Ag(111) surface was metalated with coadsorbed Zn atoms, and thereafter, NH3 ligands were attached to the metal centers. The surface reactions were monitored with X-ray photoelectron spectroscopy. The approach outlined in this work can be employed to produce and study adsorbates of various axially coordinated porphyrin complexes, including biologically relevant systems.

The interaction of cobalt(II) tetraphenylporphyrin (CoTPP) and cobalt(II) tetrakis-(3,5-di-tert-butylphenyl)porphyrin (CoTTBPP) with a Ag(111) surface has been investigated with photoelectron spectroscopy (XPS/UPS). It is demonstrated that these adsorbed metal complexes are excellent model systems for studying the electronic interaction between a coordinated metal ion and a metal surface. The photoelectron spectra and work function data provide evidence that the electronic interaction between the cobalt ion and the silver surface results in a transfer of electron density from the surface to the ion. The presence of an additional electronic state located ∼1 eV above the singly occupied molecular orbital (SOMO) of the metalloporphyrins is consistent with a molecular orbital (MO) model of the Co−Ag interaction as is the fact that the energetic position of this state depends on the distance between the Co ion and the Ag surface. The adsorbate-induced work function changes for the saturated monolayers amount t...

High mountain ecosystems are defined by low temperatures and are therefore considered to react sensitively to climate warming. Responding to observed changes in plant species richness on high peaks of the European Alps, an extensive setup of 1 m � 1 m permanent plots was established at the alpine-nival ecotone (between 2900 and 3450 m) on Mount Schrankogel, a GLORIA master site in the central Tyrolean Alps, Austria, in 1994. Recording was repeated in a representative selection of 362 quadrats in 2004. Ten years after the first recording, we observed an average change in vascular plant species richness from 11.4 to 12.7 species per plot, an increase of 11.8% (or of at least 10.6% at a 95% confidence level). The increase in species richness involved 23 species (about 43% of all taxa found at the ecotone), comprising both alpine and nival species and was pronouncedly higher in plots with subnival/nival vegetation than in plots with alpine grassland vegetation. Only three species showed a decrease in plot occupancy: one was an annual species, one was rare, and one a common nival plant that decreased in one part of the area but increased in the uppermost part. Species cover changed in relation to altitudinal preferences of species, showing significant declines of all subnival to nival plants, whereas alpine pioneer species increased in cover. Recent climate warming in the Alps, which has been twice as high as the global average, is considered to be the primary driver of the observed differential changes in species cover. Our results indicate an ongoing range contraction of subnival to nival species at their rear (i.e. lower) edge and a concurrent expansion of alpine pioneer species at their leading edge. Although this was expected from predictive distribution models and different temperature-related habitat preferences of alpine and nival species, we provide first evidence on – most likely – warming-induced species declines in the high European Alps. The projected acceleration of climate warming raises concerns that this phenomenon could become the major threat to biodiversity in high mountains.

A Li4Ti5O12 (LTO) film was coated as buffer layer onto a LiNi0.5Mn1.5O4 (LNMO) high-voltage cathode, and after cycling of the cathode in a battery electrolyte, the LTO film was investigated by means of synchrotron radiation based hard X-ray photoelectron spectroscopy (HAXPES). By tuning the photon energy between 2 keV and 6 keV, we obtained non-destructive depth profiles of the coating material with probing depths ranging from 6 nm to 20 nm. The coating was found to be covered by a few nanometers thin surface layer resulting from electrolyte decomposition. This layer consisted predominantly of organic polymers as well as metal fluorides and fluorophosphates. A positive influence of the Li4Ti5O12 coating with regard to the size and stability of the surface layer was found. The coating itself consisted of a uniform mixture of Li(I), Ti(IV), Ni(II) and Mn(IV) oxides that most likely adopted a spinel structure by forming a solid solution of the two spinels LiNi0.5Mn1.5O4 and Li4Ti5O12 with Li, Mn, Ni and Ti cations mixing on the spinel octahedral sites. The diffusion of Ni and Mn ions into the Li4Ti5O12 lattice occurred during the heat treatment when preparing the cathode. The doping of Li4Ti5O12 with the open d-shell ions Ni(2+) (d(8)) and Mn(4+) (d(3)) should increase the electronic conductivity of the coating significantly, as was found in previous studies. The complex signal structure of the Ti 2p, Ni 2p and Mn 2p core levels provides insight into the chemical nature of the transition metal ions.

ConspectusCarbon-based nanostructures have attracted tremendous interest because of their versatile and tunable properties, which depend on the bonding type of the constituting carbon atoms. Graphene, as the most prominent representative of the π-conjugated carbon-based materials, consists entirely of sp2-hybridized carbon atoms and exhibits a zero band gap. Recently, countless efforts were made to open and tune the band gap of graphene for its applications in semiconductor devices. One promising method is periodic perforation, resulting in a graphene nanomesh (GNM), which opens the band gap while maintaining the exceptional transport properties. However, the typically employed lithographic approach for graphene perforation is difficult to control at the atomic level. The complementary bottom-up method using surface-assisted carbon–carbon (C–C) covalent coupling between organic molecules has opened up new possibilities for atomically precise fabrication of conjugated nanostructures like GNM and graphene n...

The temperature-controlled surface-assisted synthesis of halogen bonded, organometallic, and covalent nanostructures based on 1,3,5-tribromo-benzene (TriBB) was studied with scanning tunneling microscopy and X-ray photoemission spectroscopy in ultrahigh vacuum. Vapor deposition of TriBB onto a Cu(111) surface held at 90 K leads to the formation of large domains of a honeycomb-like organic monolayer structure stabilized by triangular nodes with Br⋯Br intermolecular bonds. Upon annealing the organic monolayer to ∼140 K, a new hexagonal close-packed structure with intact TriBB molecules connected by Cu adatoms is formed. Further warming up the sample to 300 K gives rise to the scission of C–Br bonds and formation of C–Cu–C bonds between phenyl fragments such that stable dendritic organometallic networks are formed. Larger islands of organometallic networks are obtained by maintaining the temperature of Cu(111) at 420 K during deposition of TriBB. Simultaneously, large islands of Br atoms are formed around the organometallic networks. Annealing the more extended organometallic network (prepared at 420 K) to 520 K leads to the formation of a branched covalent organic framework (COF) which comprises structural elements of porous graphene and is surrounded by Br islands. These organometallic networks and COFs appear as small dendritic and branched domains, most likely due to the steric influence exerted by the Br islands.

Low temperatures and the short growing season in high altitude snow patches in temperate mountains constrain life cycles and reproduction of snowbed species. This leads to a highly adapted timing of sexual reproduction. Winter precipitation and temperature, the main factors determining growing season length, are predicted to change with global warming. To understand their impacts on plant phenology, we studied the responses of seven alpine vascular plant species during 2001. Temperature had a clear impact on phenological patterns. The start of the reproductive development was not directly linked with the date of snowmelt, but rather with the cumulative energy input. In addition, photoperiodism may also contribute to the control of plant development through an increasing temporal adjustment of phenology until flowering.

Background: Most pragmatic abilities are relatively preserved in aphasia, while ability to express spatial relationships is compromised. Do aphasic speakers observe the pragmatic constraint that unexpected information should be expressed while inferrable information may be omitted?Aims: Asking aphasic speakers to describe unexpected spatial arrangements on objects should produce attempts at expressing spatial information that are likely to contain errors.Methods & Procedures: A total of 16 participants with various types of aphasia and 10 controls described pictures showing expected and unexpected arrangements of furniture.Outcomes & Results: As predicted, this pragmatic manipulation of stimulus materials produced large amounts of data for analysis: Participants tried to produce elaborated descriptions of unexpected arrangements, and these efforts contained many errors. Qualitative analysis showed that these errors were not perceptual or conceptual, yet involved encoding problems much broader than “diffic...

Tip-enhanced Raman spectroscopy combines scanning probe techniques with Raman spectroscopy. Latest developments permit the chemical mapping of individual adsorbed molecules by monitoring molecular vibrations with sub-nanometer resolution. Increased efficiency and reduced photodegradation make this method suitable for studies of adsorbed organic and biomolecules in surface science, catalysis, biochemistry, and related fields.

The objective of the present study was to map dominant plant communities of an alpine area in the northeast- ern Alps (Austria), based on computer modelling. We em- ployed gradient analysis by means of Canonical Correspond- ence Analysis (CCA) as a prediction tool and image segmen- tation as a filter for reducing the number of incorrect predic- tions. Topographical variables reflecting relief properties at different scales were used as surrogates for environmental conditions in combination with spectral band values from infrared orthophotographs. Coupling topographic correlation using CCA and image analysis proved practicable to map the distribution of alpine plant communities. Although plant com- munities often showed similar spectral response, they were mapped according to their specific topographical niches. Gen- erally, topographic variables, indicative of environmental gra- dients controlling plant distribution, provided this information in most cases. The importance of spectral vs topographic variables varied among plant communities. Whereas the cor- relation between topography and plant species distribution was particularly significant for mapping alpine grasslands, spectral texture measures proved to be of major importance in discriminating between pioneer communities. Post-process- ing by image segmentation improved overall accuracy by 12%. A total of 17 plant communities and their mosaics were mapped, with an overall accuracy of 69.4% and a κ value of 0.64. Inaccuracy resulted from insufficient resolution of the available digital elevation model and confounding effects of additional controls like land use history, which could not be accounted for by topographic descriptors.

This article describes the construction of the Conformity to Masculine Norms Inventory (CMNI), and 5 studies that examined its psychometric properties. Factor analysis indicated 11 distinct factors: Winning, Emotional Control, Risk-Taking, Violence, Dominance, Playboy, Self-Reliance, Primacy of Work, Power Over Women, Disdain for Homosexuals, and Pursuit of Status. Results from Studies 2-5 indicated that the CMNI had strong internal consistency estimates and good differential validity comparing men with women and groups of men on health-related questions; all of the CMNI subscales were significantly and positively related to other masculinity-related measures, with several subscales being related significantly and positively to psychological distress, social dominance, aggression, and the desire to be more muscular, and significantly and negatively to attitudes toward psychological help seeking and social desirability; and CMNI scores had high test-retest estimates for a 2-3 week period.

Harald Pauli et al. 10 páginas, 2 figuras, [EN] In mountainous regions, climate warming is expected to shift species’ ranges to higher altitudes. Evidence for such shifts is still mostly from revisitations of historical sites. We present recent (2001 to 2008) changes in vascular plant species richness observed in a standardized monitoring network across Europe’s major mountain ranges. Species have moved upslope on average. However, these shifts had opposite effects on the summit floras’ species richness in boreal-temperate mountain regions (+3.9 species on average) and Mediterranean mountain regions (–1.4 species), probably because recent climatic trends have decreased the availability of water in the European south. Because Mediterranean mountains are particularly rich in endemic species, a continuation of these trends might shrink the European mountain flora, despite an average increase in summit species richness across the region., Baseline data were collected within the European Union FP-5 project GLORIA-Europe (EVK2-CT-2000–0006) and with the support of Switzerland (OFES 00.0184-1). Resurvey was supported by the Swiss MAVA Foundation for Nature Conservation and by a number of national funding agencies, and analysis was supported by the Austrian Federal Ministry of Science and Research; the Austrian Academy of Sciences (Institute of Mountain Research); and the University of Vienna, where data are archived in the central GLORIA database and are available from the authors upon request. We thank the European Topic Centre on Biological Diversity for ambituos discussions in the early stage, C. Klettner for data compilation, S. Laimer for administration assistance, 17 GLORIA-Europe field teams with more than 80 fieldworkers for species recording, and protected-area authorities for logistic support. We also thank three anonymous referees for their valuable comments and suggestions.

The redox reaction of superoxide (KO2) with highly charged iron porphyrins (Fe(P4+), Fe(P8+), and Fe(P8-)) has been investigated in the ionic liquids (IL) [EMIM][Tf2N] (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) and [EMIM][B(CN)4] (1-ethyl-3-methylimidazolium tetracyanoborate) by using time-resolved UV/vis stopped-flow, electrochemistry, cryospray mass spectrometry, EPR, and XPS measurements. Stable KO2 solutions in [EMIM][Tf2N] can be prepared up to a 15 mM concentration and are characterized by a signal in EPR spectrum at g = 2.0039 and by the 1215 cm(-1) stretching vibration in the resonance Raman spectrum. While the negatively charged iron porphyrin Fe(P8-) does not react with superoxide in IL, Fe(P4+) and Fe(P8+) do react in a two-step process (first a reduction of the Fe(III) to the Fe(II) form, followed by the binding of superoxide to Fe(II)). In the reaction with KO2, Fe(P4+) and Fe(P8+) show similar rate constants (e.g., in the case of Fe(P4+): k1 = 18.6 ± 0.5 M(-1) s(-1) for the first reaction step, and k2 = 2.8 ± 0.1 M(-1) s(-1) for the second reaction step). Notably, these rate constants are four to five orders of magnitude lower in [EMIM][Tf2N] than in conventional solvents such as DMSO. The influence of the ionic liquid is also apparent during electrochemical experiments, where the redox potentials for the corresponding Fe(III)/Fe(II) couples are much more negative in [EMIM][Tf2N] than in DMSO. This modified redox and kinetic behavior of the positively charged iron porphyrins results from their interactions with the anions of the ionic liquid, while the nucleophilicity of the superoxide is reduced by its interactions with the cations of the ionic liquid. A negligible vapor pressure of [EMIM][B(CN)4] and a sufficient enrichment of Fe(P8+) in a close proximity to the surface enabled XPS measurements as a case study for monitoring direct changes in the electronic structure of the metal centers during redox processes in solution and at liquid/solid interfaces.

Fractals, being "exactly the same at every scale or nearly the same at different scales" as defined by Benoit B. Mandelbrot, are complicated yet fascinating patterns that are important in aesthetics, mathematics, science and engineering. Extended molecular fractals formed by the self-assembly of small-molecule components have long been pursued but, to the best of our knowledge, not achieved. To tackle this challenge we designed and made two aromatic bromo compounds (4,4″-dibromo-1,1':3',1″-terphenyl and 4,4‴-dibromo-1,1':3',1″:4″,1‴-quaterphenyl) to serve as building blocks. The formation of synergistic halogen and hydrogen bonds between these molecules is the driving force to assemble successfully a whole series of defect-free molecular fractals, specifically Sierpiński triangles, on a Ag(111) surface below 80 K. Several critical points that govern the preparation of the molecular Sierpiński triangles were scrutinized experimentally and revealed explicitly. This new strategy may be applied to prepare and explore various planar molecular fractals at surfaces.

Induced by global warming, mountain Nival species will lose area and become restricted to specific topographical situations. Alpine and subnival plant species are migrating upwards. Species inhabiting the nival zone of today are threatened by competitors grassland species are predicted to expand their area, mainly along stable surface situations. Whether the which move from the alpine zone towards the summits. The manner in which species move depends on their migration will take place as a filling or a moving process is specific to the particular species. Overall, biodiversity abilities to cope with microtopographical situations. We present a spatially explicit predictive model which is apparently not threatened on the decadal scale. In special cases, however, genetic losses are likely both draws scenarios of future species distribution patterns at a typical high mountain of the European Alps. The on a local and on a regional scale. altitudinal temperature gradient is examined. Based on the lapse rate and on definitions of topographical niches Key words. Climate change, mountain vegetation, altitudinal gradient, predictive model, digital elevation of species, a +1∞C- and a +2∞C-warming scenario are modelled using a fine-scaled digital elevation model. model, European Alps.

We demonstrate that adsorbed meso-tetraphenylporphyrin molecules can coordinate Zn atoms that are pre-deposited on an Ag(111) surface, forming a complex that is identical to directly deposited tetraphenylporphyrinato-zinc(II); this reaction, which we studied with XPS, is the first example of an oxidative dissolution of a metal by a large organic ligand under ultrahigh vacuum conditions.

Ferrocenyl-1,2-diketones FcCOCOR, 3, [Fc = (C5H5)Fe(C5H4)] can be prepared by oxidation of acylferrocenes FcCOCH2R or, more efficiently, by oxidation of the isomeric ketones FcCH2COR, 2. The ketones 2 are in turn readily synthesized from the salt (FcCH2PPh3)+I− via the acylated salts [FcCH(COR)PPh3]+I−. The haloacylferocenes FcCOCClx H3−x (x = 1, 2, 3, of which the x = 2 example is synthetically equivalent to a diketone) are synthesized by Friedel—Crafts acylation of ferrocene using CClxH3−xCOCl/AlCl3, but the reaction proceeds via two parallel pathways, one giving the normal acyl derivatives FcCOCClxH3−x and the other giving the reduced products FcCOCClx−1H4−x. Two diketones FcCOCOFc 3b and FcCOCOC6H4Ph 3c have been structurally characterised by single-crystal X-ray diffraction.

The formation, structure, and dynamics of planar organometallic macrocycles (meta-terphenyl-Cu)n and zigzag-shaped one-dimensional organometallic polymers on a Cu(111) surface were studied with scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). Vapor deposition of 4,4″-dibromo-meta-terphenyl (DMTP) onto Cu(111) at 300 K leads to C-Br bond scission and formation of C-Cu-C bonds, which connect neighboring meta-terphenyl fragments such that room-temperature stable macrocycles and zigzag chains are formed. The chains self-assemble to form islands, which are elongated in the direction of the chains. If DMTP is deposited onto Cu(111) held at 440 K, the island size is drastically increased (200 × 200 nm(2)). STM sequences show the formation of ordered structures through reversible scission and reformation of the C-Cu-C bonds. The cyclic organometallic species such as the hexamer (meta-terphenyl-Cu)6 may represent intermediates in the surface-confined Ullmann synthesis of hydrocarbon macrocycles such as the recently discovered hyperbenzene.

A hexagonal macrocycle consisting of 18 phenylene units (hyperbenzene) was synthesized on a Cu(111) surface in ultrahigh vacuum by Ullmann coupling of six 4,4''-dibromo-m-terphenyl molecules. The large diameter of 21.3 A and the ability to assemble in arrays makes hyperbenzene an interesting candidate for a nanotrough that could enclose metallic, semiconducting, or molecular quantum dots.

Aim: High mountains in the Mediterranean region of Europe are particularly rich in endemic vascular plants. We aimed to compare the altitudinal patterns of vascular plant species richness and the proportion of endemic species in two Mediterranean region: Lefka Ori on the island of Crete (Greece) and Sierra Nevada on the Iberian peninsula. Location: Sierra Nevada, Granada (Spain); Lefka Ori, Crete (Greece). Methods: Data from standardised permanent plots settings on summit sites (comprising eight plot sectors, covering the upeermost 10 altitudinal metres) of different elevations were used (GLORIA Multi-Summit approach; www.gloria.ac.at). Species numbers, rates of endemic species, and soils temperature were compared by means of ANCOVA and linear regression. Results: The two regions, though climatically similar, showed strikingly different patterns: In Sierra Nevada, the proportion of endemic vascular plants (species restricted to Sierra Nevada) showed a stepwise increase from the lowest to the highest summit. In contrast, the proportion of endemic species restricted to Crete was not significantly different between the four summits in Lefka Ori. In both regions the observed trends were largely consistent with the altitudinal distribution of the endemic species obtained from standard floras. Main conclusions: The geographic positions of the two regions, i.e. island versus mainland and the higher elevation of Sierra Nevada are suggested to be the primary causes of the observed differences. The high degree of endemism in the cold environments of Mediterranean mountains’ upper bioclimatic zones indicates a pronounced vulnerability to the impacts of climate change. A continued and intensified species monitoring in the mountains around the Mediterranean basin, therefore, should be considered as a priority research task., Objetivo: Las zonas de alta montaña en la región mediterránea europea son particularmente ricas en plantas vasculares endémicas. Nuestro objetivo es comparar los modelos altitudinales para la riqueza de plantas vasculares y la proporción de endemismos en dos regiones mediterráneas: Lefka Ori en la isla de Creta (Grecia) y Sierra Nevada en la Península Ibérica. Localización: Sierra Nevada, Granada (España); Lefka Ori, Creta (Grecia). Método: Los datos proceden de un muestreo estandarizado en varias cimas situadas a diferentes altitudes (GLORIA Multi-Summit approach; www.gloria.ac.at). El número de especies, tasas de endemicidad, y temperatura del suelo se compararon por medio de ANCOVA y regresión lineal. Resultados: Las dos regiones objeto de análisis, aunque similares climáticamente, muestran patrones llamativamente diferentes: en Sierra Nevada, la proporción de plantas vasculares endémicas (especies restringidas a Sierra Nevada) muestra un incremento gradual desde la cima más baja a la más alta. En contraste, la proporción de endemismos restringidos a Creta no fue significativamente diferente entre las cuatro cimas de Lefka Ori. Las tendencias observadas en ambas regiones fueron en gran parte consistentes con la distribución de las especies endémicas obtenida de las floras para cada región. Conclusiones principales: La posición geográfica de ambas regiones, por ejemplo. isla frente a continente, y la mayor elevación de Sierra Nevada se sugieren como las principales causas de las diferencias observadas. El alto grado de endemicidad en los ambientes fríos de las zonas bioclimáticas superiores de las montañas mediterráneas evidencia una marcada vulnerabilidad a los impactos del cambio climático. Por lo tanto, el seguimiento continuado e intensivo de las especies de montaña alrededor de la cuenca mediterránea, debería considerarse como una tarea investigadora prioritaria.

The focus of this chapter is single-crystal adsorption calorimetry, which is used for the direct measurement of adsorption energies on well-defined surfaces, both single- and poly-crystalline. The method was pioneered in the 1990s mainly by D.A. King and C.T. Campbell and is based on earlier work by S. Cerny. Especially in recent years, the technique has seen increasing proliferation and development. In contrast to desorption-based methods, such as temperature-programmed desorption and isosteric measurements, calorimetry is also well suited for irreversible reactions. The systems studied range from simple adsorption of small molecules, such as CO and NO, to surface reconstructions, reaction intermediates, hydroxyl group formation, metal adsorption and diffusion into polymers, particle-size dependent adsorption energies on model catalysts and even electrochemical reactions on electrode surfaces in the liquid phase.

The 21st century is often called the “age of talent.” Globalization has influenced both organizational processes and employee training, creating an increased need for educated, skilled, and adaptable employees. Training and development has become an integral part of most organizations’ efforts to develop and maintain competitive advantage, with an emphasis on creating learning organizations. These changes in the methods, modes and quantity of training have made it challenging to quantify the amount of training occurring across workplaces. This paper takes the view that in order to understand the impact of training on organizations, it is important to conceptualize where and through whom training activities occur. We can think of the training and development profession as consisting of a series of four tiers, with the T&D function occurring less centrally within each tier. Tier I members of the training and development profession occupy jobs in which training and development are paramount to their roles and occupy the vast majority, if not all, of their time. Tier II professionals may be the primary person within the organization responsible for training and development, but the training is often limited to a particular focal area. A whole host of supervisory occupations might be considered Tier III jobs because of the close relation supervisors often have with the employees they supervise. Tier IV training and development professionals may come from any occupational background, and this is where much of informal training occurs.

Both research and practice of value-added models (VAM) have been growing in recent years due to the widespread effort to quantify teacher effectiveness. The existing VAM literature has not yet tested the sensitivity of value-added estimates to the rules that define which students contribute to each teacher’s value-added estimate. Student-teacher linkages are often a complex network due to various transfers, students taking multiple courses in the same subject, and students receiving special education or other “pull-out” services. Complex linkages are often considered as among the main threats to the validity of VAM. In this paper we conducted a case study to examine the sensitivity of VAM to the alternative link definitions. We examined three popular VAM approaches and applied alternative rules for linking students to teachers with each method. We found no overall sensitivity of estimated teacher effects to the linking rules. Even though more teachers had value-added estimates under more inclusive rules, for a teacher with estimates under all three rules, the correlation among pairs of estimates created using different linking rules was always above 0.95 and generally above 0.98 for each VAM approach. The value-added estimates of a small number of teachers were affected by highly different link definitions and these tended to be teachers with small numbers of students. Restricting the minimal sample size for calculating individual teachers’ value-added largely reduced the sensitivity in link definition.

Alpine plants contribute considerably to the overall biodiversity. About 20% of the total European vascular plant flora is centred close to and/or above treelines. This high floral diversity for a cold environment depends predominantly on the pronounced heterogeneity of the terrain beyond the treeline. Alpine environments are also rich in endemics.