The efficient direct synthesis of N,O-acetal compounds as key intermediates of discorhabdin A: oxidative fragmentation reaction of alpha-amino acids or beta-amino alcohols by using hypervalent iodine(III) reagents

Hypervalent iodine(III) reagents are readily available, easy to handle, and have a low toxicity and similar reactivities to those of heavy metal reagents, and hence they are used for various oxidative reactions. The oxidative cleavage of alkynes or carbonyl compounds by using bis(trifluoroacetoxy)iodo(III) pentafluorobenzene (C(6)F(5)I(OCOCF(3))(2)) has been reported. Herein, the efficient direct synthesis of N,O-acetal compounds as key intermediates of discorhabdin A, by the oxidative fragmentation reaction of alpha-amino acids or beta-amino alcohols by using C(6)F(5)I(OCOCF(3))(2), is described.     

Proton acceleration to 40 MeV using a high intensity, high contrast optical parametric chirped-pulse amplification/Ti:sapphire hybrid laser system

Using a high-contrast (10(10):1) and high-intensity (10(21) W/cm(2)) laser pulse with the duration of 40 fs from an optical parametric chirped-pulse amplification/Ti:sapphire laser, a 40 MeV proton bunch is obtained, which is a record for laser pulse with energy less than 10 J. The efficiency for generation of protons with kinetic energy above 15 MeV is 0.1%.     

Electrodialytic separation of potassium ions from sodium ions in the presence of crown ether using a cation-exchange membrane

The separation of potassium and sodium ions from their mixture was performed by electrodialyzing a mixed solution of potassium chloride and sodium chloride in the presence of 18-crown-6 using a commercial cation-exchange membrane. After 18-crown-6 had been impregnated in the membrane, the mixed solution containing 18-crown-6 was electrodialyzed as the desalting-side solution. The permeation of potassium ions through the membrane decreased remarkably and the electrical resistance of the membrane increased during electrodialysis with increasing concentration of 18-crown-6 in the solution. Because potassium ions form a more stable complex with 18-crown-6 than sodium ions and because the complex permeated through the membrane with difficulty, sodium ions are thought to selectively permeate through the membrane. The current efficiency in electrodialysis was greater than 97.0%. Received: 1 June 1999/Accepted in revised form: 13 August 1999     

High-resolution laser ablation inductively coupled plasma mass spectrometry used to study transport of metallic nanoparticles through collagen-rich microstructures in fibroblast multicellular spheroids

We have efficiently produced collagen-rich microstructures in fibroblast multicellular spheroids (MCSs) as a three-dimensional in vitro tissue analog to investigate silver (Ag) nanoparticle (NP) penetration. The MCS production was examined by changing the seeding cell number (500 to 40,000 cells) and the growth period (1 to 10 days). MCSs were incubated with Ag NP suspensions with a concentration of 5 μg mL⁻¹ for 24 h. For this study, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to visualize Ag NP localization quantitatively. Thin sections of MCSs were analyzed by LA-ICP-MS with a laser spot size of 8 μm to image distributions of ¹⁰⁹Ag, ³¹P, ⁶³Cu, ⁶⁶Zn, and ⁷⁹Br. A calibration using a NP suspension was applied to convert the measured Ag intensity into the number of NPs present. The determined numbers of NPs ranged from 30 to 7200 particles in an outer rim of MCS. The particle distribution was clearly correlated with the presence of ³¹P and ⁶⁶Zn and was localized in the outer rim of proliferating cells with a width that was equal to about twice the diameter of single cells. Moreover, abundant collagens were found in the outer rim of MCSs. For only the highest seeding cell number, NPs were completely captured at the outer rim, in a natural barrier reducing particle transport, whereas Eosin (⁷⁹Br) used as a probe of small molecules penetrated into the core of MCSs already after 1 min of exposure.

Fibroblast MCS could build up the barrier only for nanoparticles

     

Mixings and CP violations of theB^0 - \bar B^0 system in the four-generation model

We study the mixings and CP violations in the \(B^0 - \bar B^0 \) system together with the \(K^0 - \bar K^0 \) one in the four-generation model, taking into account the ARGUS data for the \(B_d^0 - \bar B_d^0 \) mixing. We take typical six cases of the mixing hierarchy and search for the allowed regions of three phases in the 4×4KM matrix. The CP violating parameter ? _K in the \(K^0 - \bar K^0 \) system gives a severe constraint for the phases, and the smaller mixing than that in the three-generation model is predicted for the \(B_s^0 - \bar B_s^0 \) system. The asymmetry parameters for the two-body non-leptonic decays of theB ⁰ and \(\bar B^0 \) mesons are also predicted.     

Redox-photosensitized aminations of 1,2-benzo-1,3-cycloalkadienes, arylcyclopropanes, and quadricyclane with ammonia

1,2,4-Triphenylbenzene and 2,2'-methylenedioxy-1,1'-binaphthalene successfully photosensitized the aminations of 1,2-benzo-1,3-cycloalkadienes, arylcyclopropanes, and quadricyclane with ammonia and primary amines in the presence of m- or p-dicyanobenzene, which gave the 4-amino-1,2-benzocycloalkenes, 3-amino-1-arylpropanes, and 7-amino-5-(p-cyanophenyl)bicyclo[2.2.1]hept-2-ene, respectively. A key pathway for the photosensitized amination is the hole transfer from the cation radicals of the sensitizers that were generated by photoinduced electron transfer to the electron acceptors to the substrates. Therefore, it was found that the relationships in oxidation potentials between the sensitizers and the substrates and the positive charge distribution of the cation radicals of the substrates were important factors for the efficient amination.