Monitoring of water content and water distribution in ischemic hearts

We determined water content and water distribution by fitting dielectric spectra of ischemic canine hearts between 5 MHz and 3 GHz with a newly developed model which describes heart cells and subcellular organelles as rotational ellipsoids filled with electrolyte enclosed by an isolating membrane. The fraction of dry material is modelled by spherical particles with a small dielectric permittivity. Free model parameters were water content, cell volume fraction, and the conductivity of the electrolytes. Resulting model parameters were compared to data from tissue desiccation and to conductivity changes produced by protons and lactate ions. We investigated hearts in two states: during ischemia after interruption of blood flow (pure ischemia, PI, n=5) and during ischemia after resuscitation with Tyrode's solution (IAR, n=14).The difference between water content determined by tissue desiccation and by dielectric spectroscopy was less than 0.5%. During 360 min of ischemia, water content in IAR decreased from 85+/-1.6% to 83+/-2.2% and in PI from 80+/-0.8% to 78+/-1.5%. Cellular volume fraction in IAR increased from 0.47+/-0.045 to 0.63+/-0.031 and in PI from 0.62+/-0.014 to 0.73+/-0.013, which is consistent with published morphometric data. After 180 min of ischemia, the increase of the cytosolic conductivity was 0.14+/-0.02 S/m as calculated from the dielectric spectrum and was similar to the conductivity increase which was roughly estimated on the basis of tissue lactate concentration.In conclusion, dielectric spectroscopy combined with our model analysis facilitates the monitoring of water content and distribution by means of nondestructive surface probes.     

Modeling the competitive dissociation of protonated 2,3-butanedione. The enthalpy of formation of methylhydroxycarbene

The enthalpy of formation of methylhydroxycarbene, CH(3)COH, has been determined from measurements of the threshold energy for collision-induced dissociation of protonated 2,3-butanedione in a flowing afterglow-triple quadrupole mass spectrometer and found to be 16 +/- 4 kcal/mol, 57 +/- 4 kcal/mol higher than that of acetaldehyde. From the measured enthalpy of formation, the difference between the first and second C-H BDEs in ethanol is found to be 17 kcal/mol, which implies a singlet-triplet splitting of 28 kcal/mol in the carbene. The activation energies for loss of ketene and carbon monoxide from protonated butanedione are found to be 60 +/- 4 and 50 +/- 4 kcal/mol, respectively. On the basis of experimental and computational results, the loss of carbon monoxide is proposed to proceed through a tight transition state. Although calculations also suggest a tight transition state for loss of ketene, the experimental data indicate that it occurs via a loose transition state, possibly forming by proton transfer along the direct dissociation pathway.     

Tetrathiafulvalene-acetylene scaffolding: new pi-electron systems for advanced materials

Novel extended tetrathiafulvalenes (TTFs) with hexa-2,4-diyne-1,6-diylidene spacers between the two 1,3-dithiole rings and laterally appended alkynyl moieties for one- and two-dimensional scaffolding were synthesised and investigated for their electronic properties.