Development of Chemical Probes for Functional Analysis of Anticancer Saponin OSW‐1

Chemical probe‐based approaches have proven powerful in recent years in the target identification studies of natural products. OSW‐1 is a saponin class of natural products with highly potent and selective cytotoxicity against various cancer cell lines. Understanding its mechanism of action is important for the development of anticancer drugs with potentially novel target pathways. This account reviews recent progress in the development of OSW‐1 derived probes for exploring the mechanism of its action. The key to the probe development is a judicious choice of functionalization sites and a selective functionalization strategy. The types of probes include fluorescent probes for cellular imaging analysis and affinity probes for target identification analysis.     

Reductive coupling of aliphatic cyclic imides and ω-amidoesters with benzophenones by low-valent titanium: Synthesis of 5-diarylmethylene-1,5-dihydropyrrol-2-ones, 6-diarylmethyl-2-pyridones,and ω-(diarylmethylene)lactams

The reductive coupling of cyclic imides and ω-amidoesters with benzophenones by Zn-TiCl₄ in THF and subsequent acid-catalyzed dehydration gave 5-diarylmethylene-1,5-dihydropyrrol-2-ones A, 6-diarylmethyl-2-pyridones B, and ω-(diarylmethylene)lactams C. In a similar manner, 3-((benzyloxy)carbonyl)amino substituted A, B, and C were synthesized from the corresponding 3-((benzyloxy)carbonyl)amino cyclic imides and ω-((benzyloxy)carbonyl)amino-ω-amidoesters prepared from L-aspartic and L-glutamic acids. In addition, 4- and 5-((benzyloxy)carbonyl)amino substituted C were also obtained by the same procedures from 2-((benzyloxy)carbonyl)amino-ω-amidoesters prepared from L-asparagine and L-glutamine, respectively.     

3-D PTV measurement of Marangoni convection in liquid bridge in space experiment

Microgravity experiments have been conducted on the International Space Station in order to clarify the transition processes of the Marangoni convection in liquid bridges of high Prandtl number fluid. The use of microgravity allows us to generate large liquid bridges, 30?mm in diameter and up to 60?mm in length. Three-dimensional particle tracking velocimetry (3-D PTV) is used to reveal complex flow patterns that appear after the transition of the flow field to oscillatory states. It is found that a standing-wave oscillation having an azimuthal mode number equal to one appears in the long liquid bridges. For the liquid bridge 45?mm in length, the oscillation of the flow field is observed in a meridional plane of the liquid bridge, and the flow field exhibits the presence of multiple vortical structures traveling from the heated disk toward the cooled disk. Such flow behaviors are shown to be associated with the propagation of surface temperature fluctuations visualized with an IR camera. These results indicate that the oscillation of the flow and temperature field is due to the propagation of the hydrothermal waves. Their characteristics are discussed in comparison with some previous results with long liquid bridges. It is shown that the axial wavelength of the hydrothermal wave observed presently is comparable to the length of the liquid bridge and that this result disagrees with the previous linear stability analysis for an infinitely long liquid bridge.     

Two-dimensional surface chirality control by solvent-induced helicity inversion of a helical polyacetylene on graphite

We report the direct evidence for the macromolecular helicity inversion of a helical poly(phenylacetylene) bearing l- or d-alanine pendants with a long alkyl chain in different solvents by atomic force microscopy observations of the diastereomeric helical structures. The diastereomeric helical poly(phenylacetylene)s induced in polar and nonpolar solvents self-assembled into ordered, two-dimensional helix bundles with controlled molecular packing, helical pitch, and handedness on graphite upon exposure of each solvent. The macromolecular helicity deposited on graphite from a polar solvent further inverted to the opposite handedness by exposure to a specific nonpolar solvent, and these changes in the surface chirality based on the inversion of helicity could be visualized by atomic force microscopy with molecular resolution, and the results were quantified by X-ray diffraction of the oriented liquid crystalline, diastereomeric helical polymer films.     

Structural basis for the phase switching of bisaminecopper(II) cations at the thermal limits of lattice stability

The structural grounds of the decrease of point and lattice symmetries coupled with switching of the exchange interaction in single crystals of a highly strained, coordinationally unsaturated bisdiaminecopper(II) cation are described. The combined magnetic susceptibility and X-ray diffraction results indicate that the interplay between the inherent vibronic instability and ligand-field strain imposed by moderately flexible, coordinationally shielding ligands enables effective switching of the pseudo-Jahn-Teller d9 centers between states with different exchange interaction in the low-temperature regime and valence orbital orientation and coordination geometry in the high-temperature regime. Within the low-temperature hysteresis region, the phase transition can also be induced by excitation of the ligand-to-metal charge-transfer bands, resulting in overall shrinkage of the lattice. The compound is a prototype of weakly electronically coupled one-dimensional Jahn-Teller systems, which can undergo phase transitions induced by light, in addition to heating, cooling, and change of pressure, and it represents a prospective basis for the design of switching materials capable of multimode external control.     

In operando quantitation of Li concentration for a commercial Li‐ion rechargeable battery using high‐energy X‐ray Compton scattering

Compton scattering is one of the most promising probes for quantitating Li under in operando conditions, since high‐energy X‐rays, which have high penetration power, are used as the incident beam and the Compton‐scattered energy spectrum has specific line‐shapes for each element. An in operando quantitation method to determine the Li composition in electrodes has been developed by using line‐shape (S‐parameter) analysis of the Compton‐scattered energy spectrum. In this study, S‐parameter analysis has been applied to a commercial coin cell Li‐ion rechargeable battery and the variation of the S‐parameters during the charge/discharge cycle at the positive and negative electrodes has been obtained. By using calibration curves for Li composition in the electrodes, the change in Li composition of the positive and negative electrodes has been determined using the S‐parameters simultaneously.     

Relativistic Mean-Field Study to Odd-A Nuclei Far from Stability

Ground state properties of recently discovered odd-A nuclei near the particle-dripline have been investigated in the relativistic mean-field model. Special emphasis is placed on the effect of the spatial component of vector meson fields on ground state properties which is due to breaking of time reversal invariance for odd-A nuclei. Calculations show that its contribution to binding energies, radii and single particle energies is small but cannot be neglected completely for some drip-line nuclei because the last nucleon in them is very weakly bound. Calculated binding energies are in reasonably good agreement with present experimental data and estimated values in mass tables. The structure of newly discovered nuclei is also discussed.     

TiO2-montmorillonite composites via supercritical intercalation

The successful preparation of TiO2-montmorillonite mesoporous composites using intercalation of titanium isopropoxide dissolved in supercritical carbon dioxide involved ion exchange of interlayer cations by hydrophobic cations.     

Synthesis of calix[4]arenes modified with germanium‐containing side chains on the upper rim

With the expectation to prepare a new type of heteroditopic host, a series of calix[4]arenes modified with germanium‐containing side chains at the upper rim was prepared. Compounds 1 and 2 bear two or four triethylgermyl moieties respectively, and compounds 3 and 4 bear two or four trimethylgermyl moieties respectively. For 1 and 2 , the hydroxy groups at the lower rim are either tosylated (series a) or kept free (series b). For reference, a carbon analog of 3 , compound 5 , was also prepared. Unfortunately, all calixarenes prepared failed to show any appreciable cation transport property, indicating that the structure designed, i.e. a calixarene with germanium‐containing side chains at the upper rim, cannot meet the requirement for an appropriate heteroditopic host. Copyright © 2004 John Wiley & Sons, Ltd.     

Relations between the Ruderman-Kittel-Kasuya-Yosida interaction electron concentration and crystal structure

The Ruderman-Kittel-Kasuya-Yosida interaction between localized magnetic spins on the basis of perfectly free conduction electron is calculated as a function of the Fermi wave vector of the conduction electrons. The expression of the interaction according to us converges rapidly, furthermore is strongly related to the detailed crystal structure. The q-dependence of exchange interaction j(q) between conduction- and localized magnetic electron is also taken into account. The result of the calculation is compared successfully with the change of magnetic structures, with θ_p and T_c or T_N of compounds having the CsCl structure, but less successfully with gadolinium compounds having the NaCl structure. These facts are discussed in conjunction with the difference of the RKKY interaction in the cscl and the NaCl structure.