Studies of tunable four-photon parametric fluorescence of crystals in the visible region

Tunable four-photon parametric fluorescence, which is valuable for investigating material nonlinearities and parametric devices, was studied theoretically and experimentally.Theoretical analysis leads to the conclusion that the emitted power depends directly on the focusing of the pumping beam, unlike the process of three-photon parametric fluorescence which is independent of the focusing of the pumping beam. The calculation of the phasematching conditions for nonlinear crystals such as KDP, ADP, TiO₂ and CdS shows that collinear phase-matching can be realised over the visible region using a ruby laser for pumping. Experimentally, tunable emission was observed in the visible range from 4200 Å to 5300 Å with KDP and ADP crystals pumped by a Q-switched ruby laser.     

Gas permeation through hydrogels : I. Gel cellophane membranes

Permeabilities and diffusion coefficients of various gases, Ar, N₂, O₂, CO₂, CH₄, C₂H₄, C₃H₈ and C₄H₁₀, were measured for Water-swollen gel cellophane membranes. No dependence of permeabilities on gas pressure below 1 atm was found. It was observed that the permeability coefficients were not related linearly to the coefficients in bulk water. For the two states of water in the membrane, an analytical method is presented to estimate the diffusion coefficients and the solubilities in free water and non-freezing water. It was found that the diffusion coefficients in non-freezing water were lower than those in free water, and the solubilities in non-freezing water were higher than in free water for all gases studied except CO₂ and C₂H₄, which gave reverse results.     

Preconcentration of copper,lead, cadmium and zinc ions from water with 2-mercaptobenzothiazole loaded on glass beads with the aid of collodion

2-Mercaptobenzothiazole (MBT) loaded on glass beads with the aid of collodion was prepared and used for selective preconcentration of μg l^?1 levels of copper(II) and lead from aqueous solutions. Copper and lead were quantitatively retained on the loaded beads from solutions of pH 5.0–6.0 and >5.0, respectively, while cadmium(II) and zinc(II) were retained at ? pH 6.0 and 7.0, respectively. The retention capacity of the loaded beads was ca. 108 μg Cu g^?1 (1.7 μmol g^?1) at pH 5.5 for beads of 0.3–0.4 mm diameter. The mole ratios of MBT to copper(II) and lead(II) were ca. 10 and 45, respectively, regardless of the amount of MBT loaded on the beads. Copper was completely retained on the column at a high flow rate (21.7 ml min^? cm^?2) and lead(II) at up to 12.7 ml min^? cm^?2. Cadmium(II) and zinc(II) were not retained quantitatively even at low flow rates (< 1.2 ml min^?1 cm^?2). Thus, selective preconcentration of copper and lead was achieved by passing the sample through the column at high flow rate at pH 6.5. The copper and lead retained on the column were complete eluted together with the collodion with 5 ml of MIBK by batch-mode elution, and determined directly by one-drop atomic absorption spectrometry. Copper(II) and lead(II) in several kinds of water were determined.     

Synthesis of (±)-dimethyl curvularin based on the palladium-catalyzed carbonylation of 3,5-dimethoxybenzyl chloride using a butadiene telomer as a building block

Palladium-catalyzed carbonylation of 3,5-dimethoxybenzyl chloride (13) with benzyl 7-hydroxyoctanoate (12) afforded benzyl 7-(3,5-dimethoxyphenylacetoxy)octanoate (6) in 70% yield, which is the precursor of Curvularin (4). The ester (12) was easily prepared from the butadiene telomer obtained by the palladium-catalyzed reaction of butadiene with acetic acid.     

Application of olefin metathesis to organic synthesis. Syntheses of civetone and macrolides

Diethyl 9-octadecene-1,18-dioate was obtained in 87% yield based on 50% theoretical conversion by the olefin metathesis reaction catalyzed by WOCl₄-Cp₂TiMe₂. The Dieckmann condensation of this diester using potassium hydride afforded 2-ethoxycarbonylcyclo-9-heptadecenone, which was converted by hydrolysis and decarboxylation to cyclo-9-heptadecenone (civetone) as a mixture of cis and trans isomers (1.3 : 1) in 54% yield. Also 9-octadecen-18-olide was obtained in 17.9% by the metathesis of oleyl oleate.