Use of microcoil probehead for determination of the structure of oriented silk fibers by solid-state NMR

A microcoil probehead for solid-state NMR was developed with a two-channel radio-frequency circuit, and 13C observation with a proton-decoupling probehead was performed to obtain information on the distribution of the orientation of silk fibroin molecules in the fiber. The coil (1 mm (diameter) x 5 mm (length)) of the probehead was placed at the angles 90 degrees and 30 degrees , relative to the static magnetic field. Only 70 mug of [1-13C]Gly silk fibroin fiber was used in a magnet of 9.4 T (400 MHz for proton channel).     

Effects of poly(ethylene glycol) (PEG) concentration on the permeability of PEG-grafted liposomes

Poly(ethylene glycol)-grafted liposomes (PEG-liposomes) were prepared from dipalmitoylphosphatidylcholine (DPPC) with various amounts of distearoyl-N-monomethoxy poly(ethylene glycol)-succinyl-phosphatidylethanolamines (DSPE-PEG) with PEG molecular weights of 1000, 2000, 3000 and 5000. The effects of DSPE-PEG concentration on the permeability of PEG-liposomes were investigated using carboxyfluorescein (CF). In the gel state, the CF leakage from PEG-liposomes was decreased with increasing mole fractions of DSPE-PEG for all PEG molecular weights. In the liquid-crystalline state, the CF leakage from PEG-liposomes containing DSPE-PEG1000 gradually increased with increasing mole fractions of DSPE-PEG, while that of PEG-liposomes whose molecular weight in PEG units was above 2000 rapidly decreased by the addition of DSPE-PEG. Furthermore, no effect of PEG molecular weight on CF leakage was observed. The relationship between the fluorescence polarization of 1,6-diphenyl-1,3,5-hexatriene (DPH) (or 1-(4-trimethylammoniumphenyl)-6-phenyl-1,3,5-hexatriene (TMA-DPH)) and the mole fraction of DSPE-PEG for PEG-liposomes was also investigated. No significant changes in fluorescence polarization of DPH for liposomal bilayer membranes was observed in the gel and liquid-crystalline states due to the addition of DSPE-PEG, while that of TMA-DPH was decreased compared with that of liposomes without DSPE-PEG in both states.     

Enantioselective total synthesis of antiangeogenic pentaketide dimers, epoxyquinols A and B, through an asymmetric aldol approach to their common monomeric precursor

A new enantioselective total synthesis of epoxyquinols A and B possessing unique pentaketide dimeric structures and potent antiangeogenic activity was achieved by oxidative dimerization of a monomeric pentaketide precursor obtained by the Evans asymmetric aldol reaction and a series of operationally simple transformations.     

Soluble polymer-supported catalysts containing pendant quaternary onium salts for the addition reaction of oxiranes with carbon dioxide

The addition reaction of oxiranes ( 15a-d ) with carbon dioxide (CO₂) was carried out using 1 mol % of soluble polymer-supported quaternary onium salts as catalysts under atmospheric pressure. The reaction of 15a-d with CO₂ proceeded very smoothly to give the corresponding five-membered cyclic carbonates ( 16a-d ) in high yields at 90-100°C. The catalytic activity of the soluble polymer-supported quaternary onium salts was strongly affected by the following factors: kind of reaction solvent, degree of introduction of the pendant onium salt residues in the polymer chain, and type of alkyl group on the onium salts due to the balance between lipophilicity and steric hindrance of the onium salt residue. Furthermore, these soluble polymer-supported quaternary onium salts were found ordinarily to have higher catalytic activity than low molecular weight quaternary onium salts under the same reaction conditions. It was also found that the rate of reaction was proportional both to catalyst concentration and to oxirane concentration. © 1995 John Wiley & Sons, Inc.     

Proteome analysis of Oncorhynchus species during embryogenesis

To understand the molecular mechanisms underlying normal and abnormal development of two salmonids, masu salmon (Oncorhynchus masou) and rainbow trout (O. mykiss), we used two-dimensional (2-D) electrophoresis to construct a series of 2-D maps during the embryonic period. We identified all visible protein spots on the 2-D map by assigning numbers for masu salmon and rainbow trout, and we determined N-terminal sequences of proteins for one hundred of the spots, that appear at very high concentrations in the whole embryos of masu salmon and rainbow trout. We also characterized embryonic stages according to the periods of appearance of spots. Most of the N-terminal sequences were identical or at least highly similar to partial sequences reported for vitellogenin (Vtg) of O. mykiss. A potential proteolytic processing of Vtg for rainbow trout is discussed in relation to the time of appearance and relative position of Vtg fragments within the complete protein sequence.     

Enantioselective addition of ketene silyl acetals to nitrones catalyzed by chiral titanium complexes. Synthesis of optically active beta-amino acids

A chiral titanium complex, Ti(O-i-Pr)(4)/BINOL/tert-butylcatechol, catalyzes enantioselective addition reaction of ketene silyl acetals to nitrones to give optically active beta-amino acid derivatives which are biologically active compounds and useful synthetic intermediates of natural products and pharmaceuticals such as beta-lactam antibiotics. The combined process of catalytic oxidation of secondary amines and enantioselective carbon-carbon bond formation of nitrones thus obtained with ketene silyl acetals provides a useful two-step method for the synthesis of optically active beta-amino acid derivatives and related nitrogen compounds.     

Analysis of phenothiazines in human body fluids using disk solid-phase extraction and liquid chromatography

Seven phenothiazine derivatives, perazine, perphenazine, prochlorperazine, propericiazine, thioproperazine, trifluoperazine, and flupentixol, have been found to be extractable from human plasma and urine samples using disk solid-phase extraction (SPE) with an Empore C18 cartridge. Human plasma and urine (1 mL each) containing the 7 phenothiazine derivatives were mixed with 2 mL of 0.1M NaOH and 7 mL distilled water and then poured into the disk SPE cartridges. The drugs were eluted with 1 mL chloroform- acetonitrile (8 + 2) and determined by liquid chromatography with ammonium formate/formic acid-acetonitrile gradient elution. The detection was performed by ultraviolet absorption at 250 nm. The separation of the 7 phenothiazine derivatives from each other and from impurities was generally satisfactory using a SymmetryShield RP8 column (150 x 2.1 mm id, 3.5 microm particle size). The recoveries of the 7 phenothiazine derivatives spiked into plasma and urine samples were 64.0-89.9% and 65.1-92.1%, respectively. Regression equations for the 7 phenothiazine derivatives showed excellent linearity, with detection limits of 0.021-0.30 microg/mL for plasma and 0.017-0.30 microg/mL for urine. The within-day and day-to-day coefficients of variation for both samples were commonly below 9.0 and 14.9%, respectively.     

Novel synthesis of zerumbone-pendant derivatives and their biological activity

Zerumbone 1, having powerful latent reactivity and containing two conjugated double bonds and a double conjugated carbonyl group is the major component of the essential oil of wild ginger, Zingiber zerumbet Smith. The conjugation system plays an important role in the expression of biological activity. N-Bromosuccinimide (NBS) reaction of 1 gave high reactive intermediate 2 with an exo-methylene group, which was obtained from 1 quantitatively. Treatment of 2 with nucleophiles gave various zerumbone-pendant derivatives, including C–H, C–O, C–N, and C–C bond formation, maintaining the conjugation system through S_N2′-type reaction. Almost all zerumbone-pendant derivatives showed a good value of IC₅₀ against the suppressive effect of NO generation. Among them, amine derivative 5, binding with 2 mol of zerumbone, showed the strongest activity (IC₅₀: 0.24 μM).