Controlling the dissociative ionization of ethanol with 800 and 400 nm two-color femtosecond laser pulses

Ethanol molecules were irradiated with a pair of temporally overlapping ultrashort intense laser pulses (10(13)-10(14) Wcm(2)) with different colors of 400 and 800 nm, and the dissociative ionization processes have been investigated. The yield ratio of the C-O bond breaking with respect to the C-C bond breaking was varied in the range of 0.17-0.53 sensitively depending on the delay time between the two laser pulses, and the absolute value of the yield of the C-O bond breaking was found to be increased largely when the Fourier-transform limited 800 nm laser pulse overlaps the stretched 400 nm laser pulse, demonstrating an advantage of the two-color intense laser fields in controlling chemical bond breaking processes.     

Orientational isomerism controlled by the difference in electronic environments of a self-assembling heterodimeric capsule

Tetrakis(4-hydroxyphenyl)-cavitand 1 and tetra(4-pyridyl)-cavitand 2 self-assemble into a heterodimeric capsule 1.2 via four ArOH...pyridyl hydrogen bonds in CDCl3. The 1.2 expresses the orientational isomerism of an encapsulated unsymmetrical guest with high orientational selectivity because the electronic environment of the 1 unit is different from that of the 2 unit. For p-ethoxyiodobenzene and 2-iodo-6-methoxynaphthalene encapsulated in 1.2, the iodo group is specifically oriented to the cavity of the 2 unit. The orientational isomeric selectivity for methyl p-acetoxybenzoate and methyl p-ethoxybenzoate within 1.2 is 1:0.11 and 1:<0.05, respectively, wherein the methyl ester group is preferentially oriented to the cavity of the 2 unit. The delicate balance among electrostatic potential repulsion, CH-pi interaction, or CH-halogen (halogen-pi) interaction, in 1.2-guest assembly influences the orientational isomeric selectivity of unsymmetrical guests within 1.2.     

Unidirectional crystallization of charged colloidal silica due to the diffusion of a base

Dilute aqueous dispersions of charged colloidal silica (particle volume fraction = approximately 0.03-0.04, particle diameter = 110 nm) exhibit unidirectional crystal growth due to the diffusion of a weak base, pyridine (Py). Similar diffusion-crystallization is enabled by a salt of a weak acid and a strong base, sodium hydrogen carbonate (NaHCO3). The resulting crystals consist of columnar (or cubic) crystal grains with a maximum height of a few centimeters and a maximum width of 1 cm. The crystal growth process is attributed to a combination of (i) the diffusion of Py or NaHCO3 accompanied by a charging reaction of the silica particles and (ii) the charge-induced crystallization of the silica colloids. Theoretical growth curves based on the reaction-diffusion model for the case of Py were in good agreement with the observed curves. We also report the immobilization of the resulting large crystals by using a polymer hydrogel matrix.     

Tuning the effective width of the optical stop band in colloidal photonic crystals

The optical stop band in colloidal crystals is characterized by the central frequency and bandwidth. Although the former is known to be highly tunable by changing the lattice constant, the latter is basically determined by the refractive index contrast between the particles and the background medium that is intrinsic to the materials. In this study, we show that the effective bandwidth in gelled colloidal crystals can also be tuned by controlling the fabrication conditions. Single-domain gelled colloidal crystals were prepared by photopolymerization under various photoirradiation conditions. It was observed that the width of the stop band in the transmission or reflectance spectrum could be expanded by simply adjusting the irradiation time.     

Polymerization of methyl methacrylate with nickelocene‐methylaluminoxane catalyst

The polymerization of methyl methacrylate (MMA) catalyzed with cyclopentadienylnickel‐methylaluminoxane (Cp₂Ni‐MAO) was investigated. Polymerization readily proceeds with this catalyst, and the resulting polymer is rich in syndiotactic content. The effects of the MAO/Ni system on the polymerization activity of MMA were observed, and it was found that only small amounts of MAO are required to reach high polymerization activity.     

Temperature characteristics of small signal gain for Nd/Cr:YAG ceramic lasers

Thermal dependence on the small signal gain of Nd/Cr:YAG (yttrium aluminum garnet) ceramics was observed experimentally. Usually, Nd:YAG crystal and ceramics have remarkable gain reduction when optical pumping is performed and the temperature of the laser media is upped to 373 K. A CW laser light generated in a 1064 nm Nd:YAG laser oscillator was amplified by Nd/Cr:YAG ceramic amplifier, and the output power was measured at non-saturation level. Laser small signal gain of the ceramic disk was kept to 470 K. This property was remarkably different from one of Nd:YAG crystals or ceramics. The peak shift of the fluorescence was observed experimentally when the temperature is high.     

High repetition rate laser pulses amplified by Nd/Cr:YAG ceramic amplifier under CW arc-lamp-light pumping

Laser pulses with high repetitive rate generated from a Q-switch microchip Nd:YAG oscillator were amplified by Active mirror composed of Nd/Cr:YAG ceramic pumped by CW arc-lamp. The laser pulses were amplified, and saturation of averaged output laser power was observed. Repetitive ratio of injected laser pulses was changed from 20 to 100 kHz. Averaged output laser power and gain were measured, and gain coefficient and power-extraction efficiency were evaluated. Output laser power was calculated and compared to experimentally measured one, and the calculated results are consistent with the experimental ones. For amplification of laser pulses with high repetitive ratio, this laser material can realize very high laser gain with low pumping power density and high optical-optical conversion efficiency under CW-lamp-light pumping.     

Guest-encapsulation behavior in a self-assembled heterodimeric capsule

Tetra(4-pyridyl)-cavitand 1 and tetrakis(4-hydroxyphenyl)-cavitand 2 self-assemble into a heterodimeric capsule 1·2 via four PhOH?pyridyl hydrogen bonds in CDCl₃, wherein one molecule of 1,4-disubstituted-benzene as a guest is encapsulated to form a ternary complex, guest@(1·2). The X-ray crystallographic analysis of (methyl p-ethoxybenzoate)@(1·2) confirmed that the methyl ester and ethoxy groups of the encapsulated guest are oriented to the cavity ends of the 1 and 2 units, respectively. The scope and limitation of guest encapsulation in 1·2, including guest-binding selectivity and orientational isomeric selectivity, are described from the viewpoint of size complementarity and CH-π, CH-halogen, and halogen-π interactions between guest and the cavity of 1·2.