Phase Conjugation in Saturable Absorbing Dye Films by Degenerate Four-Wave Mixing and Holographic Processes Using Nanosecond Pulse and CW Lasers

We report on the simultaneous generation of phase-conjugate signals by degenerate four-wave mixing (DFWM) and holographic processes using a nanosecond pulse and a CW lasers in polyvinyl alcohol (PVA) films doped with four kinds of saturable absorbing dyes. For the pulse laser, of the four kinds of dye-doped PVA films, the erythrosine B-doped PVA and uranine doped-PVA films generate PC signals only by the DFWM process, while the other dye-doped PVA films generate PC signals simultaneously by not only the DFWM process but also the holographic process. Especially, the safranin T-doped PVA film generates strong PC signals by the holographic process. In contrast, all of the dye-doped PVA films generate the two types of PC signals for the CW laser. The fading of dye molecules is found to result in the generation of the holographic component of PC signals which governs the temporal behavior of the total PC signals.     

WIDE RANGE DETECTOR USING PARABOLIC CYLINDRICAL MIRROR FOR THz APPLICATIONS

A new, wide-band, high-speed and high-sensitivity THz detector has been developed. The prototype detector consists of a parabolic cylindrical mirror, a long wire antenna and a Schottky barrier diode. Direct detection measurements have shown a stable sensitivity of 150 ± 50 V/W for 1–2 THz without any adjustments. The long wire antenna was fixed at the focus of parabolic cylindrical mirror then it has been realized less operation steps, easy coupling to the external THz signals and a dramatic enhancement in the practicality of this system. The optically polished mirror and frosted surface one showed comparable sensitivities, thus easy polishing and less cost mirror fabrication can be applied for this system. The radiation pattern showed a maximum radiation angle of approximately 23° with its dominant main lobe, which was attributed to the wire antenna character and confirmed good agreements with classical antenna theory.     

X-ray structural study of a zinc(II) inclusion complex of a phenolate-pendant cyclam

The molecular structure of phenol-pendant cyclam-zinc(II) complex,4a, has been determined by X-ray structure analysis. Crystals of4a · ClO₄ · CH₃OH (C₁₆H₂₇N₄OZn · ClO₄ · CH₃OH) are monoclinic, space groupP2₁/nn, with four molecules in the unit cell of dimensionsa=31.198(2) Å,b=8.426(1) Å,c=8.214(1) Å, and=93.96(1)°. The structure was solved by the heavy atom method and refined anisotropically toR=0.044,R _w=0.062 for 1551 independent reflections. The complex assumes a five-coordinate, square pyramidal geometry, where zinc(II) is surrounded by the cyclam moiety in a planar fashion with the pendant phenolate anion occupying an axial position. An extremely short Zn-O(phenolate) bond distance of 1.983(5) Å, in conjunction with the 0.288 Å displacement of Zn(II) above the cyclam N₄ plane toward the phenolate, accounts for the extremely low pK _a value of 5.8 for the pendant phenol. These facts about4a, in comparison with the previous findings for the Ni(II) (4b) and Cu(II) complexes (4c) with the same ligand, illustrate well the characteristics of zinc(II) ion coordination properties.This paper is dedicated to the memory of the late Dr C. J. Pedersen.     

Structure elucidation and complete NMR spectral assignments of a new taxane glycoside from the needles of Taxus cuspidata

A new taxane glycoside was isolated from a methanol extract of the needles of Taxus cuspidata. The structure was established as 2alpha,9alpha,10beta-triacetoxytaxa-4(20),11-dien-13-one-5alpha-O-beta-D-glucopyranoside (1) on the basis of 1D- and 2D NMR and high-resolution fast atom bombardment mass spectral analyses.     

Detection of a metallo-beta-lactamase (IMP-1) by fluorescent probes having dansyl and thiol groups

A fluorescent probe for the detection of a metallo-beta-lactamase (IMP-1), N-[2-(5-dimethylaminonaphthalen-1-ylsulfonylamino)ethyl]-3- mercaptopropionamide (Dansyl-C2SH), 1, was designed based on combining the inhibitory function of mercaptocarboxylate and a fluorophore. The binding of 1 to IMP-1 was investigated by fluorescence spectroscopy. Compound 1 can act as fluorescent probe for detecting IMP-1 selectively.     

W(CO)5(L)-catalyzed formal cope rearrangement of allenyl silyl enol ethers

[reaction: see text] On treatment of 5-siloxyhexa-1,2,5-trienes with a catalytic amount of W(CO)(6) under photoirradiation, formal Cope rearrangement proceeded to give 2-siloxyhex-1-en-5-ynes in good yield. The electrophilic activation of the allenyl moiety by W(CO)(5) triggers the intramolecular attack of the silyl enol ether in a 6-endo manner to produce a cyclohexenyl tungsten species. Carbon-carbon bond cleavage occurs by electron donation from the anionic W(CO)(5) into the silyloxonium moiety to afford the products with regeneration of the W(CO)(5)(L).     

Catalytic direct 1,4-conjugate addition of aldehydes to vinylketones on secondary-amines immobilised in FSM-16 silica

Direct 1,4-conjugate addition of naked aldehydes to vinylketones is catalysed effectively by N-methyl-3-aminopropylated FSM-16 mesoporous silica, which can be regarded as a novel heterogeneous catalysis for a practical C-C bond formation reaction.     

A convenient stereoselective synthesis of β-lactams from β-hydroxy-α-thioalkylesters prepared from Michael/aldol tandem reaction or stereoselective addition of thiols to the Baylis-Hillman adducts

A convenient stereoselective synthesis of β-lactams from thio-Michael/aldol tandem adduct is described. syn-Selective tandem reaction followed by amidation and intramolecular S_N2 reaction provided β-lactams in diastereomerically pure form. The tandem reaction with aliphatic aldehydes, on the other hand, afforded a mixture of diastereomers of corresponding tandem adducts in about 3:1 ratio so that the conversion to β-lactams afforded a diastereomeric mixture. As an alternative approach to prepare the tandem adducts, the stereoselective Michael addition of aliphatic thiols to Baylis-Hillman adduct was developed. The stereoselectivity was sensitive to the protective group at the hydroxyl group and TBS protection brought the most successful syn-selective formation of the tandem adducts. The procedure could be applied to the ketone derivatives of the Baylis-Hillman adduct but no selectivity was observed for the nitrile-Baylis-Hillman adducts. A similar conversion of the adduct provided desired β-lactams stereoselectively.     

Indium-mediated beta-allylation,beta-propargylation,and beta-allenylation onto alpha,beta-unsaturated ketones: reactions of in-situ-generated 3-tert-butyldimethylsilyloxyalk-2-enylsulfonium salts with in-situ-generated organoindium reagents

3-tert-Butyldimethylsilyloxyalk-2-enylsulfonium salts, generated in situ from the reaction of alpha,beta-enones with dimethyl sulfide in the presence of TBSOTf, underwent a novel nucleophilic substitution with allylindiums to give silyl enol ethers of delta,epsilon-alkenyl ketones in good yields, which correspond to formal Michael addition products. In a similar manner, 1,4-propargylation of propargylindiums onto the sulfonium salts produced the corresponding silyl enol ethers of delta,epsilon-alkynyl ketones in good yields. Organoindium reagents derived from gamma-substituted propargyl bromide and indium afforded the corresponding silyl enol ethers of beta-allenyl ketones in good yields. The reaction proceeds via an addition-substitution mechanism involving the formation of allylic sulfonium salts. The presence of the intermediate sulfonium salt was confirmed by observation of the low-temperature (1)H NMR spectra.     

W(CO)5(L)-catalyzed endo-selective cyclization of allenyl silyl enol ethers: an efficient method for the cyclopentene annulation onto alpha,beta-unsaturated ketones

[reaction: see text] Indium-mediated allenylation of alpha,beta-unsaturated ketones in the presence of tert-butyldimethylsilyl triflate and dimethyl sulfide gives 6-siloxy-1,2,5-trienes, which undergo W(CO)(5)(L)-catalyzed 5-endo cyclization to give the corresponding cyclopentene derivatives in good yield. Furthermore, this novel W(CO)(5)(L)-catalyzed cyclization of allenyl silyl enol ethers proceeds in a 6-endo manner when 5-siloxy-1,2,5-trienes are employed as a substrate. In these reactions, effective electrophilic activation of allenyl compounds for attack by silyl enol ethers is achieved using a catalytic amount of W(CO)(6).