Photoelectron kinetic energy dependence in near threshold ionization of NO from A state studied by time-resolved photoelectron imaging

Photoelectron angular distributions in the laboratory frame (LF-PADs) from the A((2)sigma(+)) state of NO molecule were measured by femtosecond time-resolved photoelectron imaging with (1 + 1(')) resonance enhanced multiphoton ionization via the A state. High-precision measurements of the anisotropy parameters of LF-PADs were performed for the photoelectron kinetic energy from 0.03 to 1.05 eV as a function of the pump-probe delay time. The revival feature of the rotational wave packet on the A state was clearly observed in the time dependence of the photoelectron anisotropy parameters. By approximating the phase shifts of the photoelectron partial waves by the quantum defects in the high-lying Rydberg states using the multichannel quantum defect theory, the energy-dependent photoionization transition dipole moments were determined, for the first time, from time-dependent LF-PADs measured by time-resolved photoelectron spectroscopy.     

Study on transport of molecules in gel by surface-enhanced Raman spectroscopy

Cellulose - Surface-enhanced Raman spectroscopy (SERS)-based biosensors have recently been extensively developed because of their high sensitivity and nondestructive nature. Conventional SERS...     

Manganese‐Corrole Complexes as Versatile Catalysts for the Ring‐Opening Homo‐ and Co‐Polymerization of Epoxide

Manganese‐corrole complexes in combination with a co‐catalyst [PPN]X ([PPN]⁺=bis(triphenylphosphoranylidene)iminium) were found to be new versatile catalysts for the polymerization of epoxides, copolymerization of epoxides with CO₂, and copolymerization of epoxides with cyclic anhydrides affording a wide range of polymeric materials. This work should allow the synthesis of new types of improved innovative (co)polymers with original properties and would clearly increase the number of applications for polyesters, polycarbonates, and polyethers.     

Heat-generating property of a local plasmon resonator under illumination

We have investigated the heat generation from gold nanoparticles resulting from their local plasma resonance. We have demonstrated the self-assembly of Au nanoparticle arrays/dielectric layer/Ag mirror sandwiches, i.e., a local plasmon resonator, using a dynamic oblique deposition technique. The thicknesses of the Au and dielectric layers were changed combinatorially on a single substrate. As a result, local plasmon resonator chips were successfully fabricated. Because of strong interference, their optical absorption can be controlled between 0.0% and 97% in the near-IR region, depending on the thickness of the dielectric layer. We evaluated the heat generation from Au nanoparticles by measuring the temperature of water with which a cell prepared on a chip is filled under laser illumination. The change in the water temperature is proportional to the optical absorption of the local plasmon resonator chips. This suggests that the photothermal conversion efficiency can be controlled by interference. These features make the application of the local plasmon resonator to nanoheaters, which can spatiotemporally control heat generation, suitable.     

Diastereoselective addition of allyltitanocenes to cyclic enones

The reaction of allyltitanocenes with five- to seven-membered cyclic enones proceeded with good to high diastereoselectivity depending on the ring size of enones. The stereochemistry of the major isomers produced by the reaction of cinnamyltitanocene was opposite to that of crotyltitanocene.     

Cyclopropanation and carbonyl olefination utilizing 2-(Alk-1-yn-1-yl)-2-(trialkylsilyl)-1,3-dithianes via regioselective generation of titanium alkynylcarbene complexes

Cp(2)Ti[P(OEt)(3)](2)-promoted reactions of 2-(alk-1-yn-1-yl)-2-(trialkylsilyl)-1,3-dithianes (RS)(2)C(Si)CCR with terminal olefins and carbonyl compounds produced (trialkylsilylethynyl)cyclopropanes and 1-(trialkylsilyl)alk-3-en-1-ynes, respectively. These compounds were suggest to be produced via the formation of intermediary titanium alpha-(trialkylsilylethynyl)carbene complexes Cp(2)Ti=C(R)CCSi in preference to their regioisomers, alpha-(trialkylsilyl)alkynylcarbene complexes Cp(2)Ti=C(Si)CCR.     

Diversity oriented synthesis of conjugate dienes and alkenylcyclopropanes utilizing silyl group-substituted titanium carbene complexes as bimetallic synthetic reagents

Diversity oriented synthesis of conjugate dienes and alkenylcyclopropanes by the sequential reactions using silyl group-substituted titanium carbene complexes was studied. Dienylsilanes were obtained by the olefination of carbonyl compounds with γ-silylvinylcarbene complexes. Cyclopropanation of 1-alkenes with the vinylcarbene complexes produced (E)-(β-silylvinyl)cyclopropanes with high stereoselectivity. The reaction of β-(trialkylsilyl)carbene complexes with zinc alkoxides of homopropargyl alcohols produced 6-silyl-3,5-hexadien-1-ols with high regio- and stereoselectivity. The (E)-alkenylsilanes thus obtained were transformed into a range of unsaturated compounds by the palladium-catalyzed or copper(I)-promoted cross-coupling with organic halides with retention of configuration.     

Synthesis of 1,4-dihydro-2-methyl-4-oxo-3-quinolineglyoxylic acid and related compounds

The synthesis of 1,4-dihydro-1-methoxy or ethyl -2-methyl-4-oxo-3-quinolineglyoxylic acid derivatives are described. α-Acetoxy-1,4-dihydro-1-hydroxy-2-methyl-4-oxo-3-quinolineacetic acid esters ( 7a, 7a ), which are key intermediates, were prepared by catalytic hydrogenation of 2-acetoxy-3-acetyl-4-hydroxy-4-(2-nitrophenyl) crotonic acid lactone ( 6 ) in methanol or ethanol.     

Structure-activity relationship (SAR) studies on oxazolidinone antibacterial agents. 2. Relationship between lipophilicity and antibacterial activity in 5-thiocarbonyl oxazolidinones

5-Thiourea and 5-dithiocarbamate oxazolidinones were synthesized as a continuation of research on 5-thiocarbonyl oxazolidinone antibacterial agents considering the hydrophobic parameters of the molecule. The structure-activity relationship (SAR) study revealed that the antibacterial activity on 5-thiocarbonyl oxazolidinones was significantly affected by the lipophilicity, especially the calculated log P value and the balance between 5-hydrophilic (or hydrophobic) substituent and hydrophobic (or hydrophilic) substituents on the benzene ring. Some of 5-thiocarbonyl oxazolidinones were found to have good in vitro antibacterial activity against gram-positive bacteria including methicillin-resistant Staphylococcus aureus (MRSA) and vancomycin-resistant enterococci (VRE).