Optimal control of ultrafast selection

Optimal laser control for ultrafast selection of closely lying excited states whose energy separation is smaller than the laser bandwidth is reported on the two-photon transition of atomic cesium; Cs(6S-->7D(J), J=5/2 and 3/2). Selective excitation was carried out by pulse shaping of ultrashort laser pulses which were adaptively modulated in a closed-loop learning system handling eight parameters representing the electric field. Two-color fluorescence from the respective excited states was monitored to measure the selectivity. The fitness used in the learning algorithm was evaluated from the ratio of the fluorescence yields. After fifty generations, a pair of nearly transform-limited pulses were obtained as an optimal pulse shape, proving the effectiveness of the "Ramsey fringes" mechanism. The contrast of the selection ratio was improved by approximately 30% from the simple "Ramsey fringes" experiment.     

A Practical Synthesis of 6-Acetylsalicylic Acid Methyl Ester

A new and efficient synthesis of the title compound is reported. The method includes a regioselective ortho-lithiation step in none polar solvents at an ambient temperature and the overall yield for 5 steps is more than 70% from a commercially available 3-hydroxyacetophenone.     

A Flow Microreactor System Enables Organolithium Reactions without Protecting Alkoxycarbonyl Groups

A flow microreactor system consisting of micromixers and microtube reactors provides an effective tool for the generation and reactions of aryllithiums bearing an alkoxycarbonyl group at para‐, meta‐, and ortho‐positions. Alkyl p‐ and m‐lithiobenzoates were generated by the I/Li exchange reaction with PhLi. The Br/Li exchange reactions with sBuLi were unsuccessful. Subsequent reactions of the resulting aryllithiums with electrophiles gave the desired products in good yields. On the other hand, alkyl o‐lithiobenzoates were successfully generated by the Br/Li exchange reaction with sBuLi. Subsequent reactions with electrophiles gave the desired products in good yields.     

Enantioselective total synthesis of (-)- and (+)-petrosin

The enantioselective total synthesis of (-)- and (+)-petrosin is described. The union of two key segments was executed by Suzuki-Miyaura coupling. The quinolizidine rings were stereoselectively constructed via a diastereoselective Mannich reaction and an aza-Michael reaction. The 16-membered ring was constructed by ring-closing metathesis with the second-generation Grubbs catalyst.     

Determination of Quality Factor for Highly Overcoupled EPR Resonators

We reported determination of the loaded quality factor (Q) of highly overcoupled (dielectric, loop-gap, and cavity) resonators used in time-domain electron paramagnetic resonance. We introduced a microwave absorber into resonators and achieved critical-coupling. Due to the deep “Q-dip” of critical-coupling, we can easily determine the loaded Q as low as 10. The loaded Q of resonators with and without the microwave absorber was examined under various overcoupling conditions. We found that the radiation Q (Q _r) can be calculated from the loaded Q of the resonator that contains the microwave absorber. We proposed a simple model that represents the loaded Q of the overcoupled resonator in terms of two parameters, Q ₀ and Q _r. Q ₀ is the effective unloaded Q of the resonator determined for the critically coupled resonator without the microwave absorber and is independent of a degree of coupling. The model can be applied to overcoupling in which the coupling parameter (Q ₀/Q _r) is in the range of 1 to ca. 20.     

Hydrogenation of N‐Acylcarbamates and N‐Acylsulfonamides Catalyzed by a Bifunctional [Cp*Ru(PN)] Complex

Awakening of the Cp one : The bifunctional complex 1 facilitates the interaction with substrates bearing less electrophilic carbon atoms than ketones, epoxides, and imides. The title reaction was applicable to the reduction of Evans' asymmetric alkylation products to the chiral alcohols along with good recovery of the chiral oxazolidinone auxiliary. EWG=electron‐withdrawing group.

     

Effects of poly(ethylene glycol) (PEG) chain length of PEG-lipid on the permeability of liposomal bilayer membranes

The effects of poly(ethylene glycol) (PEG) chain length of PEG-lipid on the membrane characteristics of liposomes were investigated by differential scanning calorimetry (DSC), freeze-fracture electron microscopy (FFEM), fluorescence polarization measurement and permeability measurement using carboxyfluorescein (CF). PEG-liposomes were prepared from mixtures of dipalmitoyl phosphatidylcholine (DPPC) and distearoyl phosphatidylethanolamines with covalently attached PEG molecular weights of 1000, 2000, 3000 and 5000 (DSPE-PEG). DSC and FFEM results showed that the addition of DSPE-PEG to DPPC in the preparation of liposomes caused the lateral phase separation both in the gel and liquid-crystalline states. The fluidity in the hydrocarbon region of liposomal bilayer membranes was not significantly changed by the addition of DSPE-PEG, while that in the interfacial region was markedly increased. From these results, it was anticipated that the CF leakage from PEG-liposomes is accelerated compared with DPPC liposomes. However, CF leakage from liposomes containing DSPE-PEG with a 0.060 mol fraction was depressed compared with regular liposomes, and the leakage decreased with increasing PEG chain length. Furthermore, the CF leakage from liposomes containing DSPE-PEG with a 0.145 mol fraction was slightly increased compared with that of liposomes containing DSPE-PEG with a 0.060 mol fraction. It is suggested that the solute permeability from the PEG-liposomes was affected by not only properties of the liposomal bilayer membranes such as phase transition temperature, phase separation and membrane fluidity, but also the PEG chain of the liposomal surface.     

Transition of free-surface flow modes in taylor-couette system

This paper presents our numerical and experimental results of the bifurcation found in Taylor-Couette system with a free surface. The lengths of the two concentric cylinders are finite and their axes are parallel to the direction of the gravitational force. When the end walls of the cylinders are fixed and stationary, numerical and experimental studies have shown that the flow has multiple patterns depending on the cylinder lengths and the Reynolds numbers. Experimental studies on flows with free surfaces also gave various flow modes. Our result shows that the measured and predicted time-dependent displacements of the free surface are in favorable agreement. In case of the cylinder length comparable with the gap width between the cylinders, gradual accelerations of the inner cylinder bring the normal mode flows with one, three and five toroidal vortices. The exchanges of stabilities between these flow modes are summarized in a phase diagram.     

Epoxidation with an electrocatalytic p-450 model system in an acidic solution

An electrochemical P-450 model system using meso-tetraphenylporphyrinatomanganese(III) chloride (MnTPP), imidazole and acetic acid was tested in an acetonitrile solution, and epoxide was obtained with a good current efficiency. The results of cyclic voltammetry revealed that acid plays an important role in the second electron transfer.