Two-dimensional self-assembly of benzotriazole on an inert substrate.

The ultra-high vacuum (UHV) room temperature adsorption of benzotriazole (BTAH), a well-known corrosion inhibitor for copper, has been investigated on the pristine Au(111) surface using a combination of surface sensitive techniques. The dimensionality of the molecule is reduced from the 3D crystal structure to a 2-dimensional surface confinement, which induces the formation of hydrogen bonded 1-dimensional molecular chains consisting of alternating pro-S and pro-R enantiomers mainly. The 0-dimensional system is characteristic of gas-phase BTAH, which undergoes a tautomeric equilibrium, with consequences for the resulting adsorbed species. The balance between hydrogen bonding, inter-chain van der Waals interactions and surface-molecule interactions, and the correlation with the dimensionality of the system, are discussed in light of the experimental results and a computational description of the observed features.

Driving forces underlying the formation of chiral domains of fluorinated diacids on graphite.

The role of intermolecular interactions, molecule-substrate interactions, and molecular chirality in the construction of 2-D surface architectures is the subject of much current interest. A racemic mixture of long chain hydrocarbons was synthesized with terminal carboxylic acid functionalities at each end and two amide linkages in the central region of the molecule on either side of two F-containing chiral centers. Using scanning tunnelling microscopy (STM), we have examined how the functionality of these molecules influences their self-assembly on a highly oriented pyrolytic graphite (HOPG) surface. The key factors determining the nature of ordered domains have been identified.

Formation of hydrogen-bridged cytosine dimers on Cu(110).

Cytosine was adsorbed onto a Cu(110) surface under UHV conditions. Annealing to 370 K resulted in the formation of a (6 x 6)gg low energy electron diffraction (LEED) pattern, even at submonolayer coverages. Examination of this structure with scanning tunneling microscopy (STM) revealed islands of zigzag chains at low coverages and large ordered domains at monolayer saturation. Further annealing to 480 K initiated a phase transition to a (6 x 2)gg structure observed both by LEED and STM. High resolution electron energy loss spectroscopy spectra for both overlayer structures exhibited mainly in-plane modes suggesting upright/tilted species on the surface. Based on the experimental data and supported by density functional theory calculations, a model is proposed for the (6 x 2)gg structure, which involves the formation of deprotonated hydrogen bridge-bonded cytosine dimers, adsorbed through the oxygen atoms.

The growth of perylene on Ru(0001).

The structure of perylene adsorbed on Ru(0001) surface has been studied by ultraviolet photoemission spectroscopy (UPS) and low-energy electron diffraction. An ordered p(4x4) structure is observed from a monolayer (about 4 A thickness) of the perylene on Ru(0001) surface. UPS measurements show the molecular features, from the perylene multiplayer, between 2 and 10 eV below the Fermi level. Angle-resolved ultraviolet photoemission spectroscopy measurements suggest that the perylene molecular plane is parallel to the substrate. Temperature dependent UPS measurements show that the perylene multilayer is stable on Ru(0001) surface up to 125 degrees C. The desorption of the multilayer and the decomposition of the monolayer are observed above 125 degrees C.

Enantiomeric interactions between nucleic acid bases and amino acids on solid surfaces.

Molecular interaction between nucleic acid bases and amino acids is a fundamental process in biology. The adsorption of the molecules on surfaces provides the opportunity to study such interactions in great detail by exploiting the high-resolution imaging capabilities of scanning tunnelling microscopy (STM). The chemisorption of prochiral molecules, such as adenine, on a metal surface causes the adsorbed species to become chiral. Subsequent interactions with inherently chiral molecules may then lead to the formation of diastereoisomers, if the enantiomeric interaction process is sufficiently strong. In the case of adenine adsorption on Cu[110], the chiral adsorbates form homochiral chains. Here, we show that the adenine chain direction is fully correlated with the chirality, and that the alpha-amino acid, phenylglycine, shows a strong chiral preference in its interaction with these chains. STM images clearly demonstrate that S-phenylglycine (R-phenylglycine) binds only to chains rotated 19.5 degrees (anti-) clockwise from the [001] direction. Closer examination reveals that the enantiomeric interaction involves double rows of phenylglycine molecules and the adenine chains. This is the first observation at the molecular level of diastereoisomeric interaction, and demonstrates that STM is a powerful method for studying the details of these interactions.

Effect of carbon dioxide in acute mountain sickness: a rediscovery.

The effect of adding CO2 to inhaled air in six subjects with acute mountain sickness was investigated during a medical expedition to 5400 m.3% CO2 in ambient air increased ventilation and resulted in a rise in PaO2 of between 24% and 40%. There was a 9-28% increase in PaCO2 and a reduction of the respiratory alkalosis normally seen at high altitude. Symptoms of acute mountain sickness were rapidly relieved. In three subjects cerebral blood flow increased by 17-39%, so that oxygen delivery to the brain would have been considerably improved. This study confirms earlier suggestions of the beneficial effect of CO2 inhalation at high altitude.

Effect of acetazolamide on exercise performance and muscle mass at high altitude.

The effect of acetazolamide (Az) on exercise performance and muscle mass in acclimatised subjects at an altitude of 4846 m was assessed in 11 subjects and compared with the effect of placebo on 10 other subjects. Exercise performance at 85% maximum heart rate fell by 37% in the Az group and by 45% in controls (p less than 0.05). Weight loss was greater in the placebo group at high altitude (p less than 0.01) and this correlated with the fall in exercise performance (p less than 0.001). During the expedition anterior quadriceps muscle thickness fell by 12.9% in the control group and 8.5% in the Az group (p less than 0.001), while biceps muscle thickness fell by 8.6% in controls and 2.3% in the Az group (p less than 0.001). Measurements of skin-fold thickness indicated a loss of 18% of total body fat in the placebo group and 5% in the Az group by the end of the expedition (p less than 0.001). Calorie intakes at altitudes above 3000 m were low and similar for the two groups. The Az group had fewer symptoms of acute mountain sickness but differences between the two groups were not statistically significant. Acetazolamide is therefore useful for climbers and trekkers who are acclimatised to high altitudes. It could be most useful at extreme altitudes, where maintenance of exercise performance and muscle mass are important.