X-Shaped Cyclobutane-Linked Tetraporphyrins through a Thermal [2+2] Cycloaddition of Etheno-Fused Diporphyrins.

A nickel-mediated tandem double cyclization of ethynylene-linked dibromodiporphyrins afforded highly reactive etheno-fused diporphyrins, which undergo a thermal [2+2] cycloaddition at the fused C-C double bond to afford the cyclobutane moiety in X-shaped cyclobutane-linked tetraporphyrins. During the reaction of a Zn(II) complex precursor, the initial double cyclization product was converted into the diketodiporphyrin, which exhibits red chemiluminescence under ambient conditions.

Backscattering linear depolarization ratio measurements of mineral, sea-salt, and ammonium sulfate particles simulated in a laboratory chamber.

The backscattering linear depolarization ratios of major types of tropospheric aerosol particles (Asian and Saharan mineral dust, sea salt, and ammonium sulfate) were measured using a laboratory chamber for interpreting the polarization lidar measurement of tropospheric aerosols. The values obtained from Asian and Saharan mineral particles were 0.39 +/- 0.04 to 0.05 (mean +/- standard deviation) for a high number of concentrations in the supermicrometer range and 0.17 +/- 0.03 to 0.14 +/- 0.03 in the submicrometer range. The values were 0.08 +/- 0.01 for sea-salt crystals, 0.04 +/- 0.003 for ammonium sulfate crystals, and 0.01 +/- < or = 0.001 for both liquid droplets in the submicrometer range. These values can serve as a reference for estimating aerosol type using lidar measurement.

Development of a 1.6 microm differential absorption lidar with a quasi-phase-matching optical parametric oscillator and photon-counting detector for the vertical CO2 profile.

We have developed a 1.6 microm carbon dioxide (CO(2)) differential absorption lidar utilizing a quasi-phase-matching optical parametric oscillator (OPO) and a photon-counting detector. The operating wavelengths were chosen based on their low interference from water vapor and low temperature sensitivity. The online wavelength was in the (30012<--0001) band of CO(2), which was insensitive to atmospheric temperature. The established OPO laser achieved a 10 mJ, 200 Hz repetition rate at the online and offline wavelengths. Our observations confirmed the statistical error of 2% with 5 h of accumulation for the CO(2) density profile less than 5.2 km. Also, the statistical error of 1% at an altitude of 2 km was demonstrated. The results of the vertical CO(2) concentrations acquired using a 1.6 microm wavelength are presented.

Tropospheric ozone differential-absorption lidar using stimulated Raman scattering in carbon dioxide.

A UV ozone differential-absorption lidar (DIAL) utilizing a Nd:YAG laser and a single Raman cell filled with carbon dioxide (CO(2)) is designed, developed, and evaluated. The generated wavelengths are 276, 287, and 299 nm, comprising the first to third Stokes lines of the stimulated Raman scattering technique. The correction terms originated from the aerosol extinction, the backscatter, and the absorption by other gases are estimated using a model atmosphere. The experimental results demonstrate that the emitted output energies were 13 mJ/pulse at 276 nm and 287 nm and 5 mJ/pulse at 299 nm, with pump energy of 91 mJ/pulse and a CO(2) pressure of 0.7 MPa. The three Stokes lines account for 44.0% of the available energy. The use of argon or helium as a buffer gas in the Raman cell was also investigated, but this leads to a dramatic decrease in the third Stokes line, which makes this wavelength practically unusable. Our observations confirmed that 30 min of integration were sufficient to observe ozone concentration profiles up to 10 km. Aerosol extinction and backscatter correction are estimated and applied. The aerosol backscatter correction profile using 287 and 299 nm as reference wavelengths is compared with that using 355 nm. The estimated statistical error is less than 5% at 1.5 km and 10% at 2.6 km. Comparisons with the operational carbon-iodine type chemical ozonesondes demonstrate 20% overestimation of the ozone profiles by the DIAL technique.

Ice clouds and Asian dust studied with lidar measurements of particle extinction-to-backscatter ratio, particle depolarization, and water-vapor mixing ratio over Tsukuba.

The tropospheric particle extinction-to-backscatter ratio, the depolarization ratio, and the water-vapor mixing ratio were measured by use of a Raman lidar and a polarization lidar during the Asian dust seasons in 2001 and 2002 in Tsukuba, Japan. The apparent (not corrected for multiple-scattering effects) extinction-to-backscatter ratios (Sp) showed a dependence on the relative humidity with respect to ice (RHice) obtained from the lidar-derived water-vapor mixing ratio and radiosonde-derived temperature; they were mostly higher than 30 sr in dry air (RHice < 50%), whereas they were mostly lower than 30 sr in ice-supersaturated air (RHice > or = 100%), where the apparent extinction coefficients were larger than 0.036 km(-1). Both regions showed mean particle depolarization ratios of 20%-22%. Comparisons with theoretical calculations and the previous experiments suggest that the observed dependence of Sp on RHice is attributed to the difference in the predominant particles: nonspherical aerosols (mainly the Asian dust) in dry air and cloud particles in ice-supersaturated air.