Ferromagnetic spin alignment in head-to-tail coupled oligo(1, 4-phenyleneethynylene)s and Oligo(1,4-phenylenevinylene)s bearing pendant p-phenylenediamine radical cations

The intramolecular and long-range ferromagnetic coupling between p-phenylenediamine radical cations in head-to-tail coupled oligo(1, 4-phenyleneethynylene)s and oligo(1,4-phenylenvinylene)s between neighbors and next-nearest neighbors is described. UV/vis/near-IR experiments show that the radical cations are localized in the pendant p-phenylenediamine units of the conjugated oligomers. The ESR spectra of these oligo(1,4-phenyleneethynylene) and oligo(1, 4-phenylenvinylene) di(radical cation)s are consistent with those of a triplet state. A linear behavior is observed for the doubly integrated ESR intensity of the DeltaM(s) = +/-1 and DeltaM(s) = +/-2 signals with the inverse temperature (I approximately 1/T), consistent with Curie's law. This behavior indicates a triplet ground-state diradical with a large triplet-singlet energy gap or possibly a degeneracy of singlet and triplet states.     

Supramolecular phthalocyanine dimers based on the secondary dialkylammonium cation/dibenzo-24-crown-8 recognition motif

[formula: see text] New unsymmetrically substituted DB24C8-phthalocyanines, which are able to form complexes with suitable dialkylammonium cations, have been prepared. These complexes most probably have a pseudorotaxane geometry.     

Comparison of photosensitizer (AIPcS2) quantification techniques: in situ fluorescence microsampling versus tissue chemical extraction

A noninvasive in situ fluorescence-based method for the quantification of the photosensitizer chloroaluminum disulfonated phthalocyanine was compared to the highly accurate but nonreal time ex vivo spectrofluorometry method. Our in vivo fluorescence technique is designed to allow real-time assessment of photosensitizer in tumor and normal tissues and therefore temporally optimal light delivery. Laser-induced fluorescence was used to measure photosensitizer concentration from multiple microscopic regions of tissue. Ex vivo chemical extraction was used to quantify photosensitizer concentration in the same volume of tissue. The amount of photosensitizer in the vascular and/or parenchymal compartments of skeletal muscle and liver was determined by quantifying fluorescent signal in vivo, ex vivo and after blood removal. Confocal microscopy was used to spatially document photosensitizer localization 30 min and 24 h after delivery. While a linear correlation can exist between the fluorescence intensity measured by our fiber-optic bundle system and actual tissue concentration, temporal changes to this calibration line exist as the photosensitizer changes its partitioning fraction between the blood (vasculature) and the tissue parenchyma. In situ photosensitizer fluorescence microsampling (dosimetry) systems can be performed in real time and linearly correlated to actual tissue concentration with minimal intertissue variance. Tissue-specific differences may require temporal alterations in the calibration.     

Low temperature scanning force microscopy of the Si(111)-(7x7) surface

A low temperature scanning force microscope (SFM) operating in a dynamic mode in ultrahigh vacuum was used to study the Si(111)- (7x7) surface at 7.2 K. Not only the twelve adatoms but also the six rest atoms of the unit cell are clearly resolved for the first time with SFM. In addition, the first measurements of the short range chemical bonding forces above specific atomic sites are presented. The data are in good agreement with first principles computations and indicate that the nearest atoms in the tip and sample relax significantly when the tip is within a few A of the surface.