Adsorption and keto-enol-tautomerisation of butanal on Pd(111).

Microscopic-level understanding of the interaction of hydrocarbons with transition metal surfaces is an important prerequisite for rational design of new materials with improved catalytic properties. In this report, we present a mechanistic study on the keto-enol tautomerisation of butanal on Pd(111), which was theoretically predicted to play a crucial role in low-barrier hydrogenation of carbonyl compounds. These processes were addressed by a combination of reflection-absorption infrared spectroscopy, molecular beam techniques and theoretical calculations at the density functional theory level. Spectroscopic information obtained on Pd(111) suggests that butanal forms three different aldehyde species, which we indicate as A1-A3 as well as their enol counterpart E1. The electronically strongest perturbed and strongest binding species A1 is most likely related to the η2(C,O) adsorption configuration, in which both C and O atoms are involved in the bonding with the underlying metal. The species A2 weakly binds and is less electronically perturbed and can be associated with the η1(O) adsorption configuration. The third type of aldehyde species A3, which is nearly unperturbed and is found only at low temperatures, results from the formation of the butanal multilayer. Importantly, the enol form of butanal was observed on the surface, which gives rise to a new characteristic band at 1104 cm-1 related to the stretching vibration of the C-O single bond (ν(C-O)). With increasing temperature, the multi-layer related species A3 disappears from the surface above 136 K. The population of aldehyde species A1 and the enol species E1 noticeably increases with increasing temperature, while the band related to the aldehyde species A2 becomes strongly attenuated and finally completely disappears above 120 K. These observations suggest that species E1 and A1 are formed in an activated process and - in view of the strongly anti-correlated population of the species E1 and A2 - it can be concluded that enol species E1 is most likely formed from the weakly bound aldehyde species A2 (η1(O)). Finally, we discuss the possible routes to enol stabilization via intermolecular bonding and provide the possible structure of the enol-containing stabilized complex, which is compatible with all spectroscopic observations. The obtained results provide important insights into the process of keto-enol tautomerisation of simple carbonyl compounds.

Competing Reaction Pathways in Heterogeneously Catalyzed Hydrogenation of Allyl Cyanide: The Chemical Nature of Surface Species.

We present a mechanistic study on the formation of an active ligand layer over Pd(111), turning the catalytic surface highly active and selective in partial hydrogenation of an α,ß-unsaturated aldehyde acrolein. Specifically, we investigate the chemical composition of a ligand layer consisting of allyl cyanide deposited on Pd(111) and its dynamic changes under the hydrogenation conditions. On pristine surface, allyl cyanide largely retains its chemical structure and forms a layer of molecular species with the CN bond oriented nearly parallel to the underlying metal. In the presence of hydrogen, the chemical composition of allyl cyanide strongly changes. At 100 K, allyl cyanide transforms to unsaturated imine species, containing the C=C and C=N double bonds. At increasing temperatures, these species undergo two competing reaction pathways. First, the C=C bond become hydrogenated and the stable N-butylimine species are produced. In the competing pathway, the unsaturated imine reacts with hydrogen to fully hydrogenate the imine group and produce butylamine. The latter species are unstable under the hydrogenation reaction conditions and desorb from the surface, while the N-butylimine adsorbates formed in the first reaction pathway remain adsorbed and act as an active ligand layer in selective hydrogenation of acrolein.

Understanding Ligand-Directed Heterogeneous Catalysis: When the Dynamically Changing Nature of the Ligand Layer Controls the Hydrogenation Selectivity.

We present a mechanistic study on the formation and dynamic changes of a ligand-based heterogeneous Pd catalyst for chemoselective hydrogenation of α,ß-unsaturated aldehyde acrolein. Deposition of allyl cyanide as a precursor of a ligand layer renders Pd highly active and close to 100 % selective toward propenol formation by promoting acrolein adsorption in a desired configuration via the C=O end. Employing a combination of real-space microscopic and in-operando spectroscopic surface-sensitive techniques, we show that an ordered active ligand layer is formed under operational conditions, consisting of stable N-butylimine species. In a competing process, unstable amine species evolve on the surface, which desorb in the course of the reaction. Obtained atomistic-level insights into the formation and dynamic evolution of the active ligand layer under operational conditions provide important input required for controlling chemoselectivity by purposeful surface functionalization.

Adsorption geometry and self-assembling of chiral modifier (R)-(+)-1-(1-naphthylethylamine) on Pt(111).

A mechanistic study on interaction of a chiral modifier - (R)-(+)-1-(1-naphthylethylamine) (R-NEA) - with a single crystalline Pt(111) surface is reported. The details of the adsorption geometry of individual R-NEA molecules and their intermolecular interactions are addressed by combination of infrared reflection absorption spectroscopy (IRAS) and scanning tunneling microscopy (STM). The spectroscopic observations suggest that the molecules are tilted with respect to the underlying metal substrate with the long axis of the naphthyl ring being parallel and the short axis tilted with respect to the surface. In the medium coverage range, formation of directed 3-5 membered chains was observed by STM for the first time, which points to intermolecular bonding between individual molecules and might account for an unusual tilted adsorption geometry deduced from the IR spectra. Based on the STM images revealing the atomic structure of the Pt grid close to the R-NEA chains, we propose the adsorption configuration of NEA fitting both the IRAS and STM data. The obtained results suggest that this strong intermolecular interaction energetically stabilizes the tilted adsorption geometry of the naphthyl ring, which otherwise would be expected to lie flat on the metal to maximize the dispersive interactions. At the coverage close to saturation, R-NEA builds a self-assembled overlayer with hexagonal symmetry, exhibiting intermolecular distances larger than in the directed chains.

Development of visual pursuit in the first 6 years of life.

BACKGROUND: There are few previous investigations on the development of smooth visual pursuit in children. The aim of this study was to determine normative values for the development of horizontal and vertical smooth pursuit in a large number of normal children. METHODS: Eye movements of 358 healthy children aged 6 weeks through 6 years were recorded using infrared photo-oculography. Visual pursuit was elicited with colored squares of 1.2 degrees of visual angle. The stimulus moved horizontally or vertically with constant velocities of 7.5, 15, or 30 degrees/s. RESULTS: Attention time increased with increasing age from 0.54 to 0.77 (P<0.01) and decreased with increasing stimulus velocities (P<0.01). The ratio of time of smooth pursuit to time of smooth pursuit plus saccades increased with increasing age from 0.63 to 0.78 (P<0.01) and decreased with increasing stimulus velocities (P<0.01). For stimulus velocities of 7.5 degrees/s, no significant difference was found between horizontal and vertical gain values. For stimulus velocities of 15 degrees/s and 30 degrees/s, gains for horizontal movements were larger that for vertical (P<0.05). Increasing stimulus speeds were associated with decreasing gains (P<0.05). CONCLUSIONS: This study provides the following normative values for photo-oculography in healthy children aged 6 weeks through 6 years of age: attention time, smooth pursuit time, and gain for three stimulus velocities presented horizontally and vertically. This normative database should help to diagnose pathologic ophthalmological or neuropediatric conditions, to perform screening interventions, and to initiate therapies.

Influence of the Pulfrich phenomenon on driving performance.

BACKGROUND: The Pulfrich stereoillusion occurs spontaneously in diseases inducing asymmetric visual pathway delays. Its influence on driving performance has never been investigated and was, therefore, assessed using a three-dimensional (3D) computer driving simulation. METHODS: A 3D driving scenery of a road with obstacles was visualised on an autostereoscopic 3D display. Seven normal subjects drove at a speed of 6 m/s using a steering wheel and three angles of view of the scenery (0 degrees, 45 degrees to left, and 90 degrees to left) with different interocular delays (25 ms on the right, 25 ms on the left, and no delay). One subject drove the scenery at an angle of 90 degrees without delay and with a delay of 8 ms, 16 ms, and 25 ms on the right and left, respectively, at speeds of 6 m/s, 12 m/s and 18 m/s. RESULTS: Stereo-illusion only influenced car position if the angle of view was 90 degrees (p<0.05). At this angle, increasing car speeds were associated with larger car displacements (delay on right p<0.001, on left p<0.01) and smaller delays with smaller car displacements (p<0.001). CONCLUSIONS: This study showed that Pulfrich phenomenon has an influence on car position only if the viewing angle is 90 degrees. No influence could be found if the driving direction corresponded to the visual axis of the driver. These findings are in agreement with reports of patients with spontaneous Pulfrich phenomenon who indicate that while driving, distances are only misjudged when looking sideways.

Automated analysis of eye tracking movements.

OBJECTIVE: To present a quick algorithm to automatically analyze the raw data acquired by a photo-oculography (POG) system. METHODS: We developed a simple algorithm for POG data analysis based on an extrapolation of missing values due to blinking and on exclusion of outliers using the robust mean and standard deviation. RESULTS: POG curves of 4 children aged between 1.5 and 7 years are shown before and after automatic analysis. After applying our algorithm, the curves are much smoother. CONCLUSION: Our algorithm allows a quick data analysis and will help to better interpret and analyze POG data.