Spectroscopic and microscopic investigations of tautomerization in porphycenes: condensed phases, supersonic jets, and single molecule studies

We describe various experimental approaches that have been used to obtain a detailed understanding of double hydrogen transfer in porphycene, a model system for intramolecular hydrogen bonding and tautomerism. The emerging picture is that of a multidimensional tautomerization coordinate, with several vibrational modes acting as reaction-promoters or inhibitors through anharmonic intermode coupling. Tunnelling processes, coherent in the case of isolated molecules and incoherent in condensed phases, are found to play a major role even at elevated temperatures. Single-molecule spectroscopy studies reveal large fluctuations in hydrogen transfer rates observed over time for the same chromophore. Scanning probe microscopy is employed to directly observe the structure and tautomerization dynamics of single molecules adsorbed on metal surfaces and demonstrates how the interactions of the molecules with atoms of the supporting surface affect their static and dynamic properties: different tautomeric forms are stabilized for molecules depending on the surface structure and the reaction mechanism can also change, from a concerted to a stepwise transfer. The scanning probe microscopy studies prove that tautomerization in single molecules can be induced by different stimuli: heat, electron attachment, light, and force exerted by the microscope’s tip. Possible applications utilizing tautomerism are discussed in combination with molecular architectures on surfaces, which could pave the way for the development of single-molecule electronics

A rapid method for the determination of dose equivalent in mixed radiation fields

Dose equivalent in mixed radiation fields of a extended energy range is generally determined by using a combination of several detectors. The need for a rapid evaluation of a radiation situation can be fulfilled by a rem-meter based on a combination of a tissue-equivalent ionization chamber and an organic scintillator, the latter showing a light-output depending on linear energy transfer (LET). Comparisons between results from such an instrument and those from multidetector techniques were performed in stray radiation fields around a GeV proton accelerator and are reported here. (14 refs)

Experimental equivalent cluster-size distributions in nanometric volumes of liquid water

Ionisation cluster-size distributions in nanometric volumes of liquid water were determined for alpha particles at 4.6 and 5.4 MeV by measuring cluster-size frequencies in small gaseous volumes of nitrogen or propane at low gas pressure as well as by applying a suitable scaling procedure. This scaling procedure was based on the mean free ionisation lengths of alpha particles in water and in the gases measured. For validation, the measurements of cluster sizes in gaseous volumes and the cluster-size formation in volumes of liquid water of equivalent size were simulated by Monte Carlo methods. The experimental water-equivalent cluster-size distributions in nitrogen and propane are compared with those in liquid water and show that cluster-size formation by alpha particles in nitrogen or propane can directly be related to those in liquid water

State of The Art of Instrumentation in Experimental Nanodosimetry

Nanodosimetry is a branch of dosimetry for investigation and modeling of the interaction pattern of ionizing radiation in nanometre site-sizes (at unit density), which dates back to the 1970's (Pszona S. A track ion counter. Proceedings of Fifth Symposium on Microdosimetry EUR 5452 d-e-f, Published by the Commission of the European Communities, Luxemburg, pp. 1107-1122 (1976)). To date, the different experimental approaches have lead to developing of three fully functional nanodosimeters: the Jet Counter operated at NCBJ, the Ion Counter operated at PTB and Startrack Counter operated at INFN-LNL. Descriptions of each nanodosimeter as well as of the techniques used to investigate the track structure of ionizing particles are presented