A photoactive isoprenoid diphosphate analogue containing a stable phosphonate linkage: synthesis and biochemical studies with prenyltransferases

A number of biochemical processes rely on isoprenoids, including the post-translational modification of signaling proteins and the biosynthesis of a wide array of compounds. Photoactivatable analogues have been developed to study isoprenoid utilizing enzymes such as the isoprenoid synthases and prenyltransferases. While these initial analogues proved to be excellent structural analogues with good cross-linking capability, they lack the stability needed when the goals include isolation of cross-linked species, tryptic digestion, and subsequent peptide sequencing. Here, the synthesis of a benzophenone-based farnesyl diphosphate analogue containing a stable phosphonophosphate group is described. Inhibition kinetics, photolabeling experiments, as well as X-ray crystallographic analysis with a protein prenyltransferase are described, verifying this compound as a good isoprenoid mimetic. In addition, the utility of this new analogue was explored by using it to photoaffinity label crude protein extracts obtained from Hevea brasiliensis latex. Those experiments suggest that a small protein, rubber elongation factor, interacts directly with farnesyl diphosphate during rubber biosynthesis. These results indicate that this benzophenone-based isoprenoid analogue will be useful for identifying enzymes that utilize farnesyl diphosphate as a substrate.     

Vibrational overtone spectroscopy of three-membered rings

We have recorded vapor-phase photoacoustic spectra of cyclopropane, ethylene oxide, and ethylene sulfide in the third, fourth, and fifth CH-stretching overtone regions. We have used a harmonically coupled anharmonic oscillator local mode model to facilitate analysis of the spectra. Fermi resonance between the CH-stretching and HCH-bending vibrations is essential to explain the observed wide and multistructured CH-stretching overtone bands. A number of weak combination bands can account for the remaining experimental features observed to the blue of the CH-stretching regions. We have reassigned the fundamental spectra of these three-membered rings.     

Production of carrier-free 188Re in the past ten years in Taiwan

Twenty clinical scale alumina-based ¹⁸⁸W/¹⁸⁸Re generators and carrier-free ¹⁸⁸Re has been produced at the Institute of Nuclear Energy Research (INER-Taiwan) for over ten years. 2845.6 GBq (76.9 Ci) of ¹⁸⁸Re-perrhenate solution has been eluted from generators during the past ten years. We have used the harvesting ¹⁸⁸Re solution for labeling radiopharmaceuticals, such as ¹⁸⁸Re-HEDP, ¹⁸⁸Re-MDP, ¹⁸⁸Re-microsphere, ¹⁸⁸Re-lipiodol, and ¹⁸⁸Re-sulfur colloid, etc. The average eluting yield of ¹⁸⁸Re is 78.6±5.8% that was investigated at 1115 harvesting times from 20 generators. Each generator can be used more than six months but the Millipore needs to be changed every two months for smooth harvesting and high yield of ¹⁸⁸Re solution.     

The 1 ħω spectra of mass 15, 16 and 17 nuclei

Tamm-Dancoff calculations including the complete 1p and 2s-1d shells are presented for non-normal parity states of nuclei with mass 15, 16 and 17. The basis is confined to ?ω excitations. Spurious states have been eliminated. The particle-particle and hole-hole interactions were taken from previous work. The particle-hole interaction was represented by 80 matrix elements from Kuo, eight of which were varied to fit 30 selected levels with a rms deviation of 310 keV. Spectroscopic factors and electromagnetic transition rates generally agree quite well with the experimental data. It is shown that the inclusion of the 1p_{$\text{3}\text{2}$} and 1d_{$\text{3}\text{2}$}. shells is essential even at low excitation energies in these nuclei.     

Determination of the orbital moment and crystal-field splitting in LaTiO3

Utilizing a sum rule in a spin-resolved photoelectron spectroscopic experiment with circularly polarized light, we show that the orbital moment in LaTiO3 is strongly reduced from its ionic value, both below and above the Ne el temperature. Using Ti L2,3 x-ray absorption spectroscopy as a local probe, we found that the crystal-field splitting in the t2g subshell is about 0.12-0.30 eV. This large splitting does not facilitate the formation of an orbital liquid.     

Electron spin resonance studies on quantum tunneling in spinel ferrite nanoparticles

The electron spin resonance (ESR) spectrometer, a very sensitive instrument with fast detecting window to explore quantum phase transitions for magnetic nanoparticles, was exploited to study the fascinating interplay between thermal and quantum fluctuations in the vicinity of a quantum critical point. We have measured ESR in ferrofluid samples containing nanosize particles of Fe₂O₃. The evolution of the ESR spectrum with temperature suggests that quantum tunneling of spins occurs in single domain magnetic particles in the low temperature regime. The effects of various microwave fields, particle sizes, and temperatures on the magnetic states of single domain spinel ferrite nanoparticles are investigated. We can consistently explain experimental data assuming that, as the temperature decreases, the spectrum changes from superparamagnetic (SPR) to blocked SPR and finally evolves quantum superparamagnetic behaviour as the temperature lowers down further. A nanoparticle system of a highly anisotropic magnetic material can be qualitatively specified by a simple quantum spin model, or by the Heisenberg model with strong easy-plane anisotropy.Received: 29 August 2003, Published online: 15 October 2003PACS: 76.30.-v Electron paramagnetic resonance and relaxation - 75.40.Cx Static properties (order parameter, static susceptibility, heat capacities, critical exponents, etc.) - 05.30.-d Quantum statistical mechanics - 75.50.Dd Nonmetallic ferromagnetic materials     

Volume contents

Volume Contents

Volume contents     

Mean-field HP model, designability and alpha-helices in protein structures

Analysis of the geometric properties of a mean-field HP model on a square lattice for protein structure shows that structures with a large number of switchbacks between surface and core sites are chosen favorably by peptides as unique ground states. Global comparison of model (binary) peptide sequences with concatenated (binary) protein sequences listed in the Protein Data Bank and the Dali Domain Dictionary indicates that the highest correlation occurs between model peptides choosing the favored structures and those portions of protein sequences containing alpha helices.     

High-order kinetic flux vector splitting schemes in general coordinates for ideal quantum gas dynamics

A class of high-order kinetic flux vector splitting schemes are presented for solving ideal quantum gas dynamics based on quantum statistical mechanics. The collisionless quantum Boltzmann equation approach is adopted and both Bose–Einstein and Fermi–Dirac gases are considered. The formulas for the split flux vectors are derived based on the general three-dimensional distribution function in velocity space and formulas for lower dimensions can be directly deduced. General curvilinear coordinates are introduced to treat practical problems with general geometry. High-order accurate schemes using weighted essentially non-oscillatory methods are implemented. The resulting high resolution kinetic flux splitting schemes are tested for 1D shock tube flows and shock wave diffraction by a 2D wedge and by a circular cylinder in ideal quantum gases. Excellent results have been obtained for all examples computed.