Atomic and molecular spectroscopy with a continuous-wave, doubly resonant, monolithic optical parametric oscillator

Doppler-broadened atomic and molecular spectra were observed with a one octave tunable, continuous-wave, doubly resonant, monolithic optical parametric oscillator (OPO) using 5% MgO-doped LiNbO₃ as a non-linear crystal with a birefringent phase-matching configuration. By tuning the frequency of a pump laser, longitudinal mode selection over 20 successive modes, corresponding to a 60 GHz span, was possible, owing to the simple structure of the monolithic OPO. Continuous frequency tuning was achieved using an external waveguide-type electrooptic phase modulator (EOM). By changing the modulation frequency of the EOM, frequency tuning of the optical sidebands over 12 GHz was possible, which is larger than the one free spectral range of the monolithic cavity of 3 GHz. We could observe the Cs-D₁ (894 nm), Cs-D₂ (852 nm), Rb-D₁ (795 nm), acetylene R9 (1520 nm) and P9 (1530 nm) transitions with the single monolithic OPO.     

Asymmetric synthesis of axially chiral benzamides and anilides by enantiotopic lithiation of prochiral arene chromium complexes

Axially chiral benzamides and anilides were prepared by enantiotopic lithiation at the distinguished benzylic methyl of prochiral tricarbonylchromium complexes of N,N-diethyl 2,6-dimethylbenzamide (1) and N-methyl-N-acyl 2,6-dimethylaniline (14 and 21) with a chiral lithium amide base followed by electrophilic substitution in good yields with high optical purity. The resulting axially chiral chromium-complexed benzamides and anilides were oxidized under air to give chromium-free axially chiral benzamides and anilides in an enantiomerically active form without axial bond rotation at room temperature.     

Synthesis of 2-, 4- and 5-(2-alkylcarbamoyl-1-methylvinyl)-7-alkyloxybenzo[b]furans and their leukotriene B4 receptor antagonistic activity

Variable benzo[b]furan derivatives having (E)- and (Z)-2-alkylcarbamoyl-1-methylvinyl groups at the 2-, 4- and 5-positions and a carboxylpropoxy or (1-phenyl)ethoxy group at the 7-position were prepared to find novel and selective leukotriene B4(LTB4) receptor antagonists. (E)-2-(2-diethylcarbamoyl-1-methylvinyl)-7-(1-phenylethoxy)benzo[b]furan (4v) showed selective inhibition to the human BLT2 receptor (hBLT2). On the other hand, (E)-2-acetyl-4-(2-diethylcarbamoyl-1-methylvinyl)-7-(1-phenylethoxy)benzo[b]furan (7v) inhibited both human BLT(1) receptor (hBLT1) and hBLT2. The (E)-2-(2-diethylcarbamoyl-1-methylvinyl) group lay on approximately the same plane as the benzo[b]furan ring, whereas the (E)-4-(2-diethylcarbamoyl-1-methylvinyl) group had the torsion angle (45.7 degree) from the benzo[b]furan ring plane. However, the (Z)-(2-alkylcarbamoyl-1-methylvinyl)benzo[b]furans were inactive. The inhibitory activity depended on the conformation of the 2-diethylcarbamoyl-1-methylvinyl group.     

Reversible photoswitching in a cell-sized vesicle

A photosensitive amphiphilic molecule can switch the shape of an assembled vesicle as determined by microscopic observation. Photoisomerization induces a change in membrane fluctuation behavior or a morphological transition between ellipsoid and bud shapes, depending on the asymmetrical degree of the initial shape. The mechanism of this reversible photoswitching in the vesicle morphology is interpreted in terms of a change in the effective cross-sectional area of the photosensitive molecule.     

Dynamics of water in real space and time

Owing to marked advances in instrumentation in X-ray and neutron scattering the time-dependent pair correlation function, the Van Hove function, can now be determined by inelastic X-ray and neutron scattering measurements. The local dynamics of water in real space and time is visualised by this approach. We discuss how the dynamic properties, such as viscosity and diffusion, can be elucidated through the Van Hove function of water.     

Soft-landing isolation of vanadium-benzene sandwich clusters on a room-temperature substrate using n-alkanethiolate self-assembled monolayer matrixes

Gas-phase synthesized vanadium-benzene 1:2 (VBz(2)) sandwich clusters were size-selectively deposited onto bare gold and long-chain n-alkanethiolate [-S-(CH(2))(n-1)-CH(3); n = 16, 18, and 22] self-assembled monolayer (SAM)-coated gold substrates under ultrahigh vacuum (UHV) conditions. Investigation of the resulting deposited clusters was performed by infrared reflection absorption spectroscopy (IRAS) and thermal desorption spectroscopy (TDS). The IR frequencies of the soft-landed VBz(2) clusters show excellent agreement with the fundamentals reported in IR data of VBz(2) in an argon matrix. The analysis of IRAS spectra reveals that while there was no orientational preference of the VBz(2) clusters on a bare gold substrate, the VBz(2) clusters deposited onto the SAM substrates were highly oriented with the molecular axis 70-80 degrees tilted off the surface normal. In addition, analysis of TDS spectra revealed unusually large adsorption heats of the physisorbed VBz(2) clusters. The present results are explained by cluster penetration into the long-chain alkanethiolate SAM and for the first time demonstrate the matrix isolation of gas-phase organometallic clusters around room temperature.     

Nanosphere formation in copolymerization of methyl methacrylate with poly(ethylene glycol) macromonomers

Polymeric nanospheres consisting of poly(methyl methacrylate) (PMMA) cores and poly(ethylene glycol) (PEG) branches on their surfaces were prepared by free radical copolymerization of methyl methacrylate (MMA) with PEG macromonomers in ethanol/water mixed solvents. PEG macromonomers having a methacryloyl (MMA‐PEG) and p‐vinylbenzyl (St‐PEG) end group were used. It has become clear that the obtained polymer dispersions form three kinds of states, particle dispersion (milky solution), clear solution, and gel/precipitation. It was found that the reaction parameters such as MMA concentration, molecular weight, and concentration of PEG macromonomers, and water content can affect nanosphere formation in a copolymerization system. The water volume fraction of mixed ethanol/water solvents affected the particle size of the nanospheres. These differences in the formation of nanospheres were due to the solvophilic/solvophobic balance between the copolymers and solvents during the self‐assembling process of the copolymers. The sizes of nanospheres can be controlled by varying concentration of PEG macromonomer and water content in solvents. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1811–1817, 2000     

Syntheses and properties of emissive iridium(III) complexes with tridentate benzimidazole derivatives

A series of novel emissive Ir(III) complexes having the coordination environments of [Ir(N--N--N)2]3+, [Ir(N--N--N)(N--N)Cl]2+, and [Ir(N--N--N)(N--C--N)]2+ with 2,6-bis(1-methyl-benzimidazol-2-yl)pyridine (L1, N--N--N), 1,3-bis(1-methyl-benzimidazol-2-yl)benzene (L2H, N--C--N), 4'-(4-methylphenyl)-2,2':6',2' '-terpyridine (ttpy, N--N--N), and 2,2'-bipyridine (bpy, N--N) have been synthesized and their photophysical and electrochemical properties studied. The Ir(III) complexes exhibited phosphorescent emissions in the 500-600 nm region, with lifetimes ranging from approximately 1-10 micros at 295 K. Analysis of the 0-0 energies and the redox potentials indicated that the lowest excited state of [Ir(L1)(L2)]2+ possessed the highest contribution of 3MLCT (MLCT = metal-to-ligand charge transfer) among the Ir(III) complexes, reflecting the sigma-donating ability of the tridentate ligand, ttpy < L1 < L2. The emission quantum yields (phi) of the Ir(III) complexes ranged from 0.037 to 0.19, and the highest phi value (0.19) was obtained for [Ir(L1)(bpy)Cl]2+. Radiative rate constants (k(r)) were 1.2 x 10(4) s(-1) for [Ir(ttpy)2]3+, 3.7 x 10(4) s(-1) for [Ir(L1)(bpy)Cl]2+, 3.8 x 10(4) s(-1) for [Ir(ttpy)(bpy)Cl]2+, 3.9 x 10(4) s(-1) for [Ir(L1)2]3+, and 6.6 x 10(4) s(-1) for [Ir(L1)(L2)]2+. The highest radiative rate for [Ir(L1)(L2)]2+ with the highest contribution of 3MLCT could be explained in terms of the singlet-triplet mixing induced by spin-orbit coupling of 5d electrons in the MLCT electronic configurations.