The local adsorption geometry and electronic structure of alanine on Cu{110}

The adsorption of alanine on Cu {110} was studied by a combination of near edge X-ray absorption fine structure (NEXAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT). Large chemical shifts in the C 1s, N 1s, and O 1s XP spectra were found between the alanine multilayer and the chemisorbed and pseudo-(3 x 2) alaninate layers. From C, N, and O K-shell NEXAFS spectra the tilt angles of the carboxylate group (approximate to 26 degrees in plane with respect to [1 (1) over bar0] and approximate to 45 degrees out of plane) and the C-N bond angle with respect to [1 (1) over bar0] could be determined for the pseudo-(3 x 2) overlayer. Using this information three adsorption geometries could be eliminated from five p(3 x 2) structures which lead to almost identical heats of adsorption in the DFT calculations between 1.40 and 1.47 eV/molecule. Due to the small energy difference between the remaining two structures it is not unlikely that these coexist on the surface at room temperature. (c) 2006 Elsevier B.V. All rights reserved.

Chemical composition and reactivity of water on hexagonal Pt-group metal surfaces

The dissociation behaviour and valence-electronic structure of water adsorbed on clean and oxygen-covered Ru{0001}, Rh{111}, Pd{111}, Ir{111} and Pt{111} surfaces has been studied by high-resolution X-ray photoelectron spectroscopy with the aim of identifying similarities and trends within the Pt-group metals. On average, we find higher reactivity for the 4d metals (Ru, Rh, Pd) as compared to 5d (Ir, Pt), which is correlated with characteristic shifts in the 1b(1) and 3a(1) molecular orbitals of water. Small amounts of oxygen (<0.2 ML) induce dissociation of water on all five surfaces, for higher coverages (>0.25 ML) only intact water is observed. Under UHV conditions these higher coverages can only be reached on the 4d metals, the 5d metals are, therefore, not passivated.

A stable pure hydroxyl layer on Pt{110}-(1x2)

The adsorption of water and coadsorption with oxygen on the missing-row reconstructed Pt{110}-(1x2) surface was studied by using temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy. Coadsorbed oxygen below saturation (<0.65 +/- 0.05 ML) leads to the formation of 014, which occupies sites near the ridge Pt atoms, In contrast to the more closely packed Pt{111} Surface, OH appears not to form hydrogen bonds with coadsorbed water molecules and is stable after the desorption of water tip to about 205 K (as determined by TPD). Because OH and atomic oxygen compete for adsorption sites, water dissociation is only observed for oxygen coverages below saturation. In the absence of coadsorbed oxygen, water stays intact at all temperatures and forms a strongly bound layer of 2 ML coverage oil the clean Pt{110}-(1x2) surface at temperatures between 140 and 175 K.

The adsorption and stability of sulfur containing amino acids on Cu{531}

The adsorption of L-CySteine and L-methionine amino acids on a chiral Cu{5 3 1} surface was investigated with high resolution X-ray photoelectron spectroscopy (XPS) and carbon K-edge near edge X-ray absorption fine structure (NEXAFS) Spectroscopy using synchrotron radiation. XPS shows that at 300 K L-cysteine adsorbs through two oxygen, a nitrogen and a sulfur atom, in a four point 'quadrangular footprint', whereas L-methionine adsorbs through only two oxygen and a nitrogen atom in a 'triangular footprint'. NEWS was used to clarify the adsorption geometry of both molecules, which suggests a binding orientation to the top layer and second layer atoms in two different orientations associated with adsorption sites on {1 1 0} and {3 1 1} microfacets; of the Cu{5 3 1} surface. (C) 2009 Elsevier B.V. All rights reserved.

Hydrogen bond-induced pair formation of glycine on the chiral Cu{531} surface

Enantio-specific interactions on intrinsically chiral or chirally modified surfaces can be identified experimentally via comparison of the adsorption geometries of similar nonchiral and chiral molecules. Information about the effects of substrate-related and in interactions on the adsorption geometry of glycine, the only natural nonchiral amino acid, is therefore important for identifying enantio-specific interactions of larger chiral amino acids. We have studied the long- and short-range adsorption geometry and bonding properties of glycine on the intrinsically chiral Cu{531} surface with low-energy electron diffraction, near-edge X-ray absorption One structure spectroscopy, X-ray photoelectron spectroscopy, and temperature-programmed desorption. For coverages between 0.15 and 0.33 ML (saturated chemisorbed layer) and temperatures between 300 and 430 K, glycine molecules adsorb in two different azimuthal orientations, which are associated with adsorption sites on the {110} and {311} microfacets of Cu{531}. Both types of adsorption sites allow a triangular footprint with surface bonds through the two oxygen atoms and the nitrogen atom. The occupation of the two adsorption sites is equal for all coverages, which can be explained by pair formation due to similar site-specific adsorption energies and the possibility of forming hydrogen bonds between molecules on adjacent {110} and {311} sites. This is not the ease for alanine and points toward higher site specificity in the case of alanine, which is eventually responsible for the enantiomeric differences observed for the alanine system.

Global and local expression of chirality in serine on the Cu{110} surface

Establishing a molecular-level understanding of enantioselectivity and chiral resolution at the organic−inorganic interfaces is a key challenge in the field of heterogeneous catalysis. As a model system, we investigate the adsorption geometry of serine on Cu{110} using a combination of low-energy electron diffraction (LEED), scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The chirality of enantiopure chemisorbed layers, where serine is in its deprotonated (anionic) state, is expressed at three levels: (i) the molecules form dimers whose orientation with respect to the substrate depends on the molecular chirality, (ii) dimers of l- and d-enantiomers aggregate into superstructures with chiral (−1 2; 4 0) lattices, respectively, which are mirror images of each other, and (iii) small islands have elongated shapes with the dominant direction depending on the chirality of the molecules. Dimer and superlattice formation can be explained in terms of intra- and interdimer bonds involving carboxylate, amino, and β−OH groups. The stability of the layers increases with the size of ordered islands. In racemic mixtures, we observe chiral resolution into small ordered enantiopure islands, which appears to be driven by the formation of homochiral dimer subunits and the directionality of interdimer hydrogen bonds. These islands show the same enantiospecific elongated shapes those as in low-coverage enantiopure layers.

Enantiospecific adsorption of alanine on the chiral Cu{531} surface

We have studied enantiospecific differences in the adsorption of (S)- and (R)-alanine on Cu{531}R using low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy, and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. At saturation coverage, alanine adsorbs as alaninate forming a p(1 4) superstructure. LEED shows a significantly higher degree of long-range order for the S than for the R enantiomer. Also carbon K-edge NEXAFS spectra show differences between (S)- and (R)-alanine in the variations of the ð resonance when the linear polarization vector is rotated within the surface plane. This indicates differences in the local adsorption geometries of the molecules, most likely caused by the interaction between the methyl group and the metal surface and/or intermolecular hydrogen bonds. Comparison with model calculations and additional information from LEED and photoelectron spectroscopy suggest that both enantiomers of alaninate adsorb in two different orientations associated with triangular adsorption sites on {110} and {311} microfacets of the Cu{531} surface. The experimental data are ambiguous as to the exact difference between the local geometries of the two enantiomers. In one of two models that fit the data equally well, significantly more (R)-alaninate molecules are adsorbed on {110} sites than on {311} sites whereas for (S)-alaninate the numbers are equal. The enantiospecific differences found in these experiments are much more pronounced than those reported from other ultrahigh vacuum techniques applied to similar systems.

Water adsorption on O-covered Ru{0001}: coverage-dependent change from dissociation to molecular adsorption

When water is coadsorbed with oxygen at coverages above 0.25ML an intact water species is observed in high resolution X-ray photoelectron spectroscopy up to 220 K, which is significantly more stable than intact water on the clean surface. The presence of this species causes a shift in the O 1s binding energy of the pre-adsorbed oxygen, which indicates the formation of hydrogen bonds between the two adsorbates. Low coverages of oxygen induce partial dissociation and recombinative desorption in the same temperature range, which illustrates that desorption temperatures alone cannot be used to determine whether water is molecularly intact or not.

Effect of oxygen adsorption on the chiral pt{531} surface

The adsorption of oxygen on the chiral Pt{531} surface was studied by high-resolution X-ray photoelectron spectroscopy (HRXPS) and low energy electron diffraction (LEED). After the surface is annealed in oxygen (3 x 10(-7) mbar), three O 1s peaks are observed in XPS. One peak, at 529.5 eV, is assigned to chemisorbed oxygen; it disappears after annealing in vacuo to temperatures above 900 K. The other two peaks at 530.8 and 532.3 eV are stable up to at least 1250 K. They are associated with oxide clusters on the surface. These clusters readily react with coadsorbed carbon monoxide at temperatures between 315 and 620 K.

Low-temperature partial dissociation of water on Cu(110)

The low-temperature reactivity of water (D2O) adsorbed on clean and oxygen pre-covered Cu(1 1 0) was studied using high resolution X-ray photoelectron spectroscopy (HRXPS) and low energy electron diffraction (LEED). On the clean surface partial dissociation to hydroxyl was observed already at 95 K. Upon annealing to 220 K hydrogen bonded water-hydroxyl chains are formed. Upon further annealing water desorbs leaving behind a layer of hydroxyl, most of which desorbs recombinatively eventually. With pre-adsorbed oxygen water reacts to hydroxyl lifting the added-row reconstruction even below 225 K. Upon annealing this adsorbate layer passes through essentially the same stages as without pre-adsorbed oxygen.

The adsorption geometry and chemical state of lysine on Cu{110}

Chemisorbed layers of lysine adsorbed on Cu{110} have been studied using X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. XPS indicates that the majority (70%) of the molecules in the saturated layer at room temperature (coverage 0.27 ML) are in their zwitterionic state with no preferential molecular orientation. After annealing to 420 K a less densely packed layer is formed (0.14 ML), which shows a strong angular dependence in the characteristic π-resonance of oxygen K edge NEXAFS and no indication of zwitterions in XPS. These experimental results are best compatible with molecules bound to the substrate through the oxygen atoms of the (deprotonated) carboxylate group and the two amino groups involving Cu atoms in three different close packed rows. This μ4 bonding arrangement with an additional bond through the !-amino group is different from geometries previously suggested for lysine on Cu{110}.

Incorporation of lead into calcium carbonate granules secreted by earthworms living in lead contaminated soils

The influence of soil organisms on metal mobility and bioavailability in soils is not currently fully understood. We conducted experiments to determine whether calcium carbonate granules secreted by the earthworm Lumbricus terrestris could incorporate and immobilise lead in lead- and calcium- amended artificial soils. Soil lead concentrations were up to 2000 mg kg-1 and lead:calcium ratios by mass were 0.5-8. Average granule production rates of 0.39 + 0.04 mgcalcite earthworm-1 day-1 did not vary with soil lead concentration. The lead:calcium ratio in granules increased significantly with that of the soil (r2 = 0.81, p = 0.015) with lead concentrations in granules reaching 1577 mg kg-1. X-ray diffraction detected calcite and aragonite in the granules with indications that lead was incorporated into the calcite at the surface of the granules. In addition to the presence of calcite and aragonite X-ray absorption spectroscopy indicated that lead was present in the granules mainly as complexes sorbed to the surface but with traces of lead-bearing calcite and cerussite. The impact that lead-incorporation into earthworm calcite granules has on lead mobility at lead-contaminated sites will depend on the fraction of total soil lead that would be otherwise mobile.

Using paint to investigate fires: an ATR-IR study of the degradation of paint samples upon heating

Fire investigation is a challenging area for the forensic investigator. The aim of this work was to use spectral changes to paint samples to estimate the temperatures to which a paint has been heated. Five paint samples (one clay paint, two car paints, one metallic paint, and one matt emulsion) have been fully characterized by a combination of attenuated total reflectance Fourier transform infrared (ATR-IR), Raman, X-ray fluorescence spectroscopy and powder X-ray diffraction. The thermal decomposition of these paints has been investigated by means of ATR-IR and thermal gravimetric analysis. Clear temperature markers are observed in the ATR-IR spectra namely: loss of m(C = O) band, >300°C; appearance of water bands on cooling, >500°C; alterations to m(Si–O) bands due to dehydration of silicate clays, >700°C; diminution of m(CO3) and d(CO3) modes of CaCO3, >950°C. We suggest the possible use of portable ATR-IR for nondestructive, in situ analysis of paints.

Guided growth of neurons and glia using microfabricated patterns of parylene-C on a SiO2 background

This paper describes a simple technique for the patterning of glia and neurons. The integration of neuronal patterning to Multi-Electrode Arrays (MEAs), planar patch clamp and silicon based ‘lab on a chip’ technologies necessitates the development of a microfabrication-compatible method, which will be reliable and easy to implement. In this study a highly consistent, straightforward and cost effective cell patterning scheme has been developed. It is based on two common ingredients: the polymer parylene-C and horse serum. Parylene-C is deposited and photo-lithographically patterned on silicon oxide (SiO2) surfaces. Subsequently, the patterns are activated via immersion in horse serum. Compared to non-activated controls, cells on the treated samples exhibited a significantly higher conformity to underlying parylene stripes. The immersion time of the patterns was reduced from 24 to 3 h without compromising the technique. X-ray photoelectron spectroscopy (XPS) analysis of parylene and SiO2 surfaces before and after immersion in horse serum and gel based eluant analysis suggests that the quantity and conformation of proteins on the parylene and SiO2 substrates might be responsible for inducing glial and neuronal patterning.

Following the creation of active gold nanocatalysts from phosphine-stabilized molecular clusters

The phosphine-stabilised gold cluster [Au6(Ph2P-o-tolyl)6](NO3)2 is converted into an active nanocatalyst for the oxidation of benzyl alcohol through low-temperature peroxide-assisted removal of the phosphines, avoiding the high-temperature calcination process. The process was monitored using in-situ X-ray absorption spectroscopy, which revealed that after a certain period of the reaction with tertiary butyl hydrogen peroxide, the phosphine ligands are removed to form nanoparticles of gold which matches with the induction period seen in the catalytic reaction. Density functional theory calculations show that the energies required to remove the ligands from the [Au6Ln]2+ increase significantly with successive removal steps, suggesting that the process does not occur at once but sequentially. The calculations also reveal that ligand removal is accompanied by dramatic re-arrangements in the topology of the cluster core.