Photoinduced reconfiguration cycle in a molecular adsorbate layer studied by femtosecond inner-shell photoelectron spectroscopy.

A time-resolved study of core-level chemical shifts in a monolayer of aromatic molecules reveals complex photoinduced reaction dynamics. The combination of electron spectroscopy for chemical analysis and ultrashort pulse excitation in the extreme ultraviolet allows performing time-correlated 4d-core-level spectroscopy of iodine atoms that probe the local chemical environment in the adsorbate molecule. The selectivity of the method unveils metastable molecular configurations that appear about 50 ps after the excitation and are efficiently quenched back to the ground state.

ESR spectroscopy of the C60 cation produced by photoinduced electron transfer

In this study the existence of the C60 cation produced by photochemically induced electron transfer in the presence of different sensitising molecules is proved for the first time by using ESR spectroscopy. It is demonstrated for triphenylpyryliumtetrafluoroborate (TPP) by this spectroscopic method that the electron transfer from C60 to TPP occurs without an application of a cosensitiser. Furthermore it is shown that the addition of alcohols causes a new radical in the system C60/TPP. The stationary concentration of the C60 cation diminishes even in the presence of a cosensitiser to such a low concentration that it is not detectable by ESR spectrosopy. The spectroscopic study of the sensitiser/C60 system is also extended to the reaction products.

Large-scale homogeneous molecular templates for femtosecond time-resolved studies of the guest-host interaction.

Self-assembled monolayer films based on iodobenzoyloxy-functionalized resorc[4]arenes were prepared on gold substrates to serve as model systems for future time-resolved studies of molecular recognition, a mechanism of outstanding importance in bioorganic systems. The film properties were tested using X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and imaging ellipsometry. An apparatus for time-resolved electron spectroscopy utilizing femtosecond soft X-ray pulses is capable of detecting iodine core-level photolines and the photoinduced dissociation after ultraviolet illumination. The developed technique holds promise for tracking the temporal evolution of chemical shifts of atomic markers as local probes for the dynamics of the guest-host interaction.

A new type of calixarene: octahydroxypyridin.

A new type of calixarene has been synthesised. Like resorcinol and a number of resorcinol derivatives, 2,6-dihydroxypyridine has been proven to form cyclic tetramers in moderate yields with a number of aliphatic and two aromatic aldehydes in acidic media. The problem of the formation of configurational isomers can be reduced by increasing the reaction temperature and time. With electron-rich aromatic aldehydes, 2,6-dihydroxypyridine unexpectedly yields deep-coloured acyclic quinoid systems. The octahydroxypyridine[4]arenes may have a high potential as receptors for molecular recognition and self organisation.

Modeling productivity and transpiration of Pinus radiata: climatic effects.

Climatic effects on annual net carbon gain, stem biomass and annual transpiration were simulated for Pinus radiata D. Don at Canberra and Mt. Gambier. Simulations were conducted with an existing process-based forest growth model (BIOMASS, Model 1) and with a modified version of the BIOMASS model (Model 2) in which response functions for carbon assimilation and leaf conductance were replaced with those derived from field gas exchange data collected at Mt. Gambier. Simulated carbon gain was compared with a published report stating that mean annual stem volume increment (MAI) at Mt. Gambier was 1.8 times greater than at Canberra and that the difference could be the result solely of differences in climate. Regional differences in climate resulted in a 20% greater simulated annual transpiration at Canberra than at Mt. Gambier but only small differences in simulated productivity, indicating that climatic differences did not account for the reported differences in productivity. With Model 1, simulated annual net carbon gain and annual increase in stem biomass were greater at Canberra than at Mt. Gambier, whereas Model 2 indicated a similar annual net carbon gain and annual stem biomass increase in both regions.