Photochemical charge separation in closely positioned donor-boron dipyrrin-fullerene triads

A series of molecular triads, composed of closely positioned boron dipyrrin-fullerene units, covalently linked to either an electron donor (donor(1)-acceptor(1)-acceptor(2)-type triads) or an energy donor (antenna-donor(1)-acceptor(1)-type triads) was synthesized and photoinduced energy/electron transfer leading to stabilization of the charge-separated state was demonstrated by using femtosecond and nanosecond transient spectroscopic techniques. The structures of the newly synthesized triads were visualized by DFT calculations, whereas the energies of the excited states were determined from spectral and electrochemical studies. In the case of the antenna-donor(1)-acceptor(1)-type triads, excitation of the antenna moiety results in efficient energy transfer to the boron dipyrrin entity. The singlet-excited boron dipyrrin thus generated, undergoes subsequent energy and electron transfer to fullerene to produce a boron dipyrrin radical cation and a fullerene radical anion as charge-separated species. Stabilization of the charge-separated state in these molecular triads was observed to some extent.     

Simultaneous generation of helical beams with linear and radial polarization by use of a segmented half-wave plate

Simultaneous generation of helical beams with linear and radial polarization is demonstrated by use of a segmented half-wave plate in a Ti:sapphire laser cavity. A linearly polarized Laguerre-Gaussian beam is converted to a radially polarized beam with a spiral phase shift and vice versa. In addition, these two beams coexist in the cavity, and the cavity emits one of these two beams from an output coupler.     

Lensless high-resolution photoacoustic imaging scanner for in vivo skin imaging

We previously launched a high-resolution photoacoustic (PA) imaging scanner based on a unique lensless design for in vivo skin imaging. The design, imaging algorithm and characteristics of the system are described in this paper. Neither an optical lens nor an acoustic lens is used in the system. In the imaging head, four sensor elements are arranged quadrilaterally, and by checking the phase differences for PA waves detected with these four sensors, a set of PA signals only originating from a chromophore located on the sensor center axis is extracted for constructing an image. A phantom study using a carbon fiber showed a depth-independent horizontal resolution of 84.0 ± 3.5 µm, and the scan direction-dependent variation of PA signals was about ± 20%. We then performed imaging of vasculature phantoms: patterns of red ink lines with widths of 100 or 200 μm formed in an acrylic block co-polymer. The patterns were visualized with high contrast, showing the capability for imaging arterioles and venues in the skin. Vasculatures in rat burn models and healthy human skin were also clearly visualized in vivo.     

Reversible 1,3‐dipolar cycloaddition of dimethyl 2‐thiono‐1,3‐dithiole‐4,5‐dicarboxylate with dimethyl acetylenedicarboxylate

It was shown that dimethyl 2‐thiono‐1,3‐dithiole‐4,5‐dicarboxylate ( 2 ) and dimethyl acetylenedicarboxylate (DMAD) undergo a 1,3‐dipolar cycloaddition to produce a short‐lived ylide intermediate ( 3 ). The 1,3‐dipolar cycloaddition took place even at room temperature, although sluggishly, but took place much more rapidly under application of a high pressure of 500 MPa. The 1,3‐dipolar cycloaddition is reversible and the ylide 3 immediately splits into 2 and DMAD. When the reaction of 2 with DMAD was carried out at room temperature without solvent, a spiro‐1,3‐dithiole ( 11 ) was formed in 11% yield, whereas the reaction at 150°C provided a thiophene derivative ( 13 ) in 41% yield. It was found that 11 undergoes a thermal rearrangement to 13 . Results of attempted chemical trapping of the ylide 3 are also reported. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:434–440, 2000