Adsorption and reaction of cyclohexene on a Ni(111) surface

We studied the adsorption and reaction of cyclohexene (C6H10) on Ni(111) at different temperatures with high-resolution in-situ X-ray photoelectron spectroscopy (HR-XPS). For exposure at 125 K, we find intact cyclohexene with two distinct C 1s signals at 283.3 and 284.2 eV, due to the nonequivalent carbon atoms in the molecule. The energetic separation is significantly increased relative to the gas-phase value, due to the interaction with the substrate. Upon exposure at 210 K, complete dehydrogenation of cyclohexene to benzene (C6H6) and hydrogen is observed; coverage-dependent changes of the benzene adsorption site occur in a way similar to those for pure benzene layers, which indicates a phase separation in benzene and hydrogen islands. The thermal evolution of the adsorbed layers was studied by temperature-programmed (TP-) XPS and temperature-programmed desorption spectroscopy (TPD). Upon heating, the benzene + hydrogen layer formed at 210 K shows a coverage-dependent reorientation of the benzene molecules during partial desorption. The cyclohexene layer adsorbed at 125 K only shows partial conversion of cyclohexene to benzene and hydrogen upon heating to 185 or 210 K, with the remaining cyclohexene being stable up to approximately 300 K. We propose that upon heating these molecules are stabilized by coadsorbed benzene and hydrogen; furthermore, the mobility of benzene and hydrogen in this coadsorbed layer is reduced, so that no phase separation can occur.     

Characterization of VOx-TiO2 catalysts and their activity in the partial oxidation of methyl ethyl ketone

The present work focuses on the partial oxidation of methyl ethyl ketone to acetic acid over TiO₂ supported vanadia catalysts with V loadings from 1 to 13.5 wt.%. In order to elucidate the relation between catalytic activity and the structure of the catalysts, the catalysts were also characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction with hydrogen (TPR), and temperature programmed desorption of lattice oxygen (TPD-O₂). The investigations show that with increasing V loading the MEK conversion increased whereas the turn-over frequency decreased. At lower V loading (1–4 wt.%) the total oxidation to CO_x was favoured and the selectivities to acetic acid and other oxygenated products were low. The highest selectivities to acetic acid were achieved at V loadings of 4–6 wt.%. Based on literature data and our results, a scheme of the reaction pathways for the partial oxidation of MEK to AcOH and other by-products was developed.     

Explicit Diversity Index (EDI): a novel measure for assessing the diversity of compound databases

A novel diversity assessment method, the Explicit Diversity Index (EDI), is introduced for druglike molecules. EDI combines structural and synthesis-related dissimilarity values and expresses them as a single number. As an easily interpretable measure, it facilitates the decision making in the design of combinatorial libraries, and it might assist in the comparison of compound sets provided by different manufacturers. Because of its rapid calculation algorithm, EDI enables the diversity assessment of in-house or commercial compound collections.     

Dissociative electron attachment to gas phase valine: a combined experimental and theoretical study

Using a crossed electron/molecule beam technique the dissociative electron attachment (DEA) to gas phase L-valine, (CH(3))(2)CHCH(NH(2))COOH, is studied by means of mass spectrometric detection of the product anions. Additionally, ab initio calculations of the structures and energies of the anions and neutral fragments have been carried out at G2MP2 and B3LYP levels. Valine and the previously studied aliphatic amino acids glycine and alanine exhibit several common features due to the fact that at low electron energies the formation of the precursor ion can be characterized by occupation of the pi* orbital of the carboxyl group. The dominant negative ion (M-H)(-) (m/Z=116) is observed at electron energies of 1.12 eV. This ion is the dominant reaction product at electron energies below 5 eV. Additional fragment ions with m/Z=100, 72, 56, 45, 26, and 17 are observed both through the low lying pi* and through higher lying resonances at about 5.5 and 8.0-9.0 eV, which are characterized as core excited resonances. According to the threshold energies calculated here, rearrangements play a significant role in the formation of DEA fragments observed from valine at subexcitation energies.     

Detection and identification of explosives and illicit drugs using neutron based techniques

Some methods developed in collaboration between the ATOMKI and IEP for bulk hydrogen analysis and for the detection and identification of illicit drugs are presented. Advantages and limitations of neutron techniques (reflection, transmission, elastic and inelastic scatterings, leakage spectra and angular yields of Be(d,n), Pu–Be, D–D, D–T and ²⁵²Cf neutrons transmitted from thick samples, effects of hidden materials) are discussed.     

In vivo iontophoretic delivery of calcium ions through guinea pig skin enhanced by direct and pulsating current

Studies were initiated to investigate the effect of the delivery mode of⁴⁵Ca ions through guinea pig skin in vivo. Direct current (DC), pulsating current (PC) and a Bernard current form, the “courtes periodes” current profile (CP) were applied with the same current density (0.16 mA/cm²) and for the same duration (30 minutes). The⁴⁵Ca ions were delivered from a Ca-bentonite patch radiolabeled with⁴⁵Ca (a natural mineral clay rich in calcium, 50 mgCa/g). The total quantity of applied bentonite was 1.5g×10 days=15g.⁴⁵Ca was counted in different biological samples of the animals. The delivery of⁴⁵Ca ions into the body (systemic effect) is the highest when CP current is applied (6.87±0.95·10⁻¹²g/samples). The local effect appears to be more effective in case of DC current mode (5.89±0.12·10⁻¹²g/0.5g bone). Total calcium measurements proved that the result of transdermal radiocalcium delivery is not only an ion exchange process at the surface of the bone but a deposition of calcium ions into the hydroxiapatite matrix (the net calcium introduction, which represent the difference between the total calcium into the treated bone and total calcium into untreated bone varied from 15.52±2.42·10⁻³g/0.5g bone to 44.30±3.50·10⁻³g/0.5g bone). The results suggest that iontophoresis could be used to accumulate calcium into different target tissues using the appropriate current system.     

Selective Oxygen and Hydrogen Functionalization of the h-BN/Rh(111) Nanomesh

We present detailed studies on the covalent adsorption of molecular oxygen and atomic hydrogen on the hexagonal boron nitride (h-BN) nanomesh on Rh(111). The functionalization of this two-dimensional (2D) material was investigated under ultra-high vacuum conditions using synchrotron radiation-based in situ high-resolution X-ray photoelectron spectroscopy, temperature-programmed X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy. We are able to provide a deep insight into the adsorption behavior and thermal stability of oxygen and hydrogen on h-BN/Rh(111). Oxygen functionalization was achieved via a supersonic molecular beam while hydrogen functionalization was realized using an atomic hydrogen source. Adsorption of the respective species was observed to occur selectively in the pores of h-BN leading to spatially defined modification of the 2D layer. The adsorption of the observed molecular oxygen species was found to be an activated process that requires high-energy oxygen molecules. Upon heating to 700 K, oxygen functionalization was observed to be almost reversible except for small amounts of boron oxides evolving due to the reaction of oxygen with the 2D material. Hydrogen functionalization of h-BN/Rh(111) was fully reversed upon heating to about 640 K.     

What can nano-chemistry offer to the paint industry?

Iron surface was modified by organic, self assembled nano-layer of 1,7-diphosphono heptane. The self-assembling film formation and the self-healing process of the injured layers was monitored by electrochemical methods. The morphological changes of paint and lacquer layers which was due to different pre-treatments were monitored by surface analyzing techniques.