Hymenosides A-F, six new hemiterpene glucosides from the Japanese fern Hymenophyllum barbatum

In the course of investigation of the bitter-tasting substances of the Japanese fern Hymenophyllum barbatum belonging to the family Hymenophyllaceae, six new hemiterpene glucosides called hymenosides A-F (1-6) have been isolated from the methanol extract, together with an acyclic bis-bibenzyl derivative, perrottetin H. This paper deals with the structure elucidation of the newly isolated glucosides.     

Measurement of Gamma-Rays from 11ΛB and 12ΛC

From the ^12 C（π^＋,K^＋）^12 AC reaction the γ -rays of 261.6±0.24 ke V（7/2^＋ →5/2^＋）and 1481.7±0.7 ke V（1/2^＋ →5/2^＋） of ^11 A B,and 2667.3±2.8 keV（1^- 2 → 2^- 1）of ^12 A C hypernuclei have been identified using a large germanium detector array Hyperball2 at K6 beam line of KEK. The observed energies of the transitions 1481.7keV and 261.6 keV are significantly different from the values predicted by the shell model using the △ and SN parameters determined from the ^7 △ Li data.     

Synthesis of substituted 3-iodopyrroles by electrophilic cyclization of propargylic aziridines

The electrophilic cyclization of propargylic aziridines is described. 3-Iodopyrroles having a variety of substituents were conveniently synthesized by the reaction of propargylic aziridines with iodine. The resulting substituted 3-iodopyrrole was further functionalized to the tri-substituted pyrroles with high efficiency.     

Stereoselective synthesis of cyclic hemiacetals from 4-formylbenzoates and α,β-unsaturated aldehydes using a sulfoalkyl-substituted N-heterocyclic carbene catalyst

N-Heterocyclic carbene-catalyzed transformation of 4-formylbenzoates and α,β-unsaturated aldehydes to cyclic hemiacetals is described. The reaction proceeded smoothly when the sulfopropyl-substituted imidazolium salt was used as the catalyst. Various substrates were converted to the corresponding cyclic hemiacetals in a stereoselective manner.     

Optical conductivity spectral anomalies in the off-center rattling system β-Ba8Ga16Sn30

We present optical conductivity studies of the type-I clathrate Ba8Ga16Sn30, using a terahertz time-domain spectrometer (0.3-3.0?THz). The lowest-lying spectral peak at 0.72?THz due to the Ba(2) ion's off-center vibration in the oversized cage shows a drastic and anomalous temperature dependence. Below about 100?K, the single broad peak splits into two subpeaks, and with further lowering of the temperature, the spectral shape of this so-called rattling phonon shows non-Boltzmann broadening to the point that the linewidth becomes comparable to the peak frequency. Whereas the initial splitting can be understood by assuming a multiwell anharmonic potential, the strong linewidth broadening toward low temperature cannot, since the Boltzmann factor generally sharpens the low-temperature spectra. The observed behavior suggests strong interaction between the local anharmonic phonons and other excitations.     

Semiempirical Pm3 Quantum Mechanics Calculations of Carbohydrate Crystals

ABSTRACT

Miniature crystal models of six small carbohydrates were examined using the PM3 semiempirical quantum mechanics method. The minicrystal structures, consisting of 27 sugar residues, were optimized by the combined procedure of partial optimization and reconstruction of the model, while maintaining the original crystal symmetries. All of the minicrystals were successfully optimized without exhibiting a great increase in an energy at any reconstruction step. Some minicrystals showed a prolonged behavior of optimization cycles. A major source of structure change appeared to arise from hydroxyl group rotations wherein the largest movements mostly occurred in an early optimization stage. No significant deformations in geometry of either residues or hydrogen bonds were observed in the final minicrystal structures. The thermodynamic values calculated for the optimized minicrystals were in reasonably good agreement with the literature data. The present study indicated that the PM3 semiempirical method successfully predicted the basic features of intermolecular hydrogen bonding involved in a condensed system.     

Direct detection of nanoparticles and components in smoke by time-of-flight mass spectrometry with soft plasma ionization

A new system combining a soft plasma ionization (SPI) source with a time-of-flight mass spectrometer (TOFMS) has been successfully developed and applied to direct and on-line analysis of nanoparticles in smoke generated during combustion of mosquito coils with no sample preparation. The mass spectra of nanoparticles in smoke were examined in conjunction with the effects of species, pressure and current of the SPI discharge on fragmentation. The results indicated that a maximum mass of m/z 1576 was detectable when the following optima SPI conditions were satisfied: a He gas pressure of 1000 Pa with an air pressure of 1600 Pa and a discharge current of 110 mA. Furthermore, considering the results for emission spectra we suppose an ionization mechanism of SPI in which excitation and ionization of nitrogen molecule is promoted by the presence of He gas, leading to promote the smoke sample ionization. The mass spectrum of nanoparticles showed specific patterns of a peak interval of 74 which were assigned to triacetylene (1,3,5-hexatriyne). The most abundant peak in the mass spectrum, at m/z 452, was assigned to triacontanoic acid.     

Soft-sputtering of insulin films in argon-cluster secondary ion mass spectrometry

In secondary ion mass spectrometry (SIMS) of organic substances, the dissociation of the sample molecules is crucial. We have developed SIMS equipment capable of bombardment, where the primary ions are argon cluster ions with kinetic energy per atom controllable down to 1 eV. We previously reported the detection of intact ions of insulin and cytochrome C using this equipment. In this paper, we present a detailed characterization of the emission of secondary ions from insulin, focusing on the difference in secondary ion yield between intact ions and fragment ions by varying the incident angle of the cluster ions. The emission intensity of the intact ions was changed drastically due to the exposed dosage and incident angle of the cluster ions in contrast to the fragment ions. We discuss these results based on the manner in which the argon-cluster ions collide with the organic solid.