New oleanan-type triterpene and cincholic acid glycosides from Peruvian "Uña de Gato" (Uncaria tomentosa)

A new oleanan-type triterpene and three new cincholic acid glycosides were isolated from Peruvian "Una de Gato" (Cat's claw, plant of origin: Uncaria tomentosa), a traditional herbal medicine in Peru. Their structures were determined by spectroscopic analysis.     

Comparison in fractal dimension between those obtained from structure factor and viscoelasticity of gel networks of 1,3:2,4-bis-O-(p-methylbenzylidene)-D-sorbitol in polystyrene melt at gel point

We investigated time evolution of shear moduli in the physical gelation process of 1,3:2,4-bis-O-(p-methylbenzylidene)-D-sorbitol in polystyrene melt. At the gel point, storage and loss shear moduli, G' and G", were described by the power law of frequency omega, G' approximately G" approximately omegan, with the critical exponent n being nearly equal to 2/3, in agreement with the value predicted by the percolation theory. We also investigated the structure factor over two decades in length scale at gel point by using ultra-small-angle X-ray scattering, and small-angle X-ray scattering. We found the power-law behavior in low-q region, indicating that the gel network forms the self-similar structure with mass-fractal dimension. Comparison between the exponent of mass-fractal dimension from structure factor and that from viscoelasticity indicates that hydrodynamic interactions are completely screened out and the excluded volume effects are dominant in the gel. The gel strength was found to increase with the decrease in the lower limit length scale of fractality.     

Probes for narcotic receptor-mediated phenomena. 33. Construction of a strained trans-5,6-ring system by displacement of a nitro-activated aromatic fluorine. synthesis of the penultimate oxide-bridged phenylmorphans

The synthesis of the ortho- and para-e isomers in the oxide-bridged 5-phenylmorphan series of rigid tetracyclic compounds was accomplished via rac-5-(2-fluoro-5-nitrophenyl)-2-methyl-2-azabicyclo[3.3.1]nonan-9beta-ol ((+/-)-10), an intermediate containing an aromatic nitro-activated fluorine atom. The fluorine atom was used as the leaving group for the formation of the strained tetracyclic trans-fused 5,6-ring system in rac-(1alpha,4aalpha,9aalpha)-1,3,4,9a-tetrahydro-2-methyl-6-nitro-2H-1,4a-propanobenzofuro[2,3-c]pyridine ((+/-)-11), although preference for cis ring fusion during the formation of tricyclic tetra- and hexahydrodibenzofurans has been well-documented. Single-crystal X-ray crystallographic study of the desired para-e isomer ((+/-)-2), as well as of two intermediates in its synthesis, provided assurance of the correct structures. The e-isomers are among the last of the 12 oxide-bridged 5-phenylmorphans to be synthesized. We envisioned the syntheses of these rigid, tetracyclic compounds in order to determine the three-dimensional pattern of a ligand that would enable interaction with opioid receptors as agonists or antagonists.     

Novel stereoselective entry to 2'-beta-carbon-substituted 2'-deoxy-4'-thionucleosides from 4-thiofuranoid glycals

2'-Beta-methyl- and 2'-beta-hydroxymethyl-2'-deoxy-4'-thionucleosides have been synthesized through PhSeCl-mediated electrophilic glycosidation using 4-thiofuranoid glycals having carbon substituents at the C2-position as a glycosyl donor. Preparation of these glycals were carried out by means of the C2 lithiation of 1-chloro-4-thiofuranoid glycal with LTMP followed by the Birch reduction of the chlorine atom. [reaction: see text]     

Redox behavior of ferrocene-containing rotaxane: transposition of the rotaxane wheel by redox reaction of a ferrocene moiety tethered at the end of the axle

A rotaxane with a ferrocene moiety at the axle terminus was prepared. The redox potential of the ferrocene moiety decreased by ca. 80 mV when the rotaxane had a crown ether wheel capable of moving on the axle. Thus, the stabilization of the oxidized state of the ferrocene moiety is assumed to accompany the transposition of the wheel component on the axle toward the ferrocene moiety. [reaction--see text]     

Visible-light induced hydrophilicity on nitrogen-substituted titanium dioxide films

Nitrogen-substituted titanium dioxide thin films were found to undergo hydrophilic conversion under irradiation with visible light. The hydrophilicity was enhanced by increasing the degree of nitrogen substitution at oxygen sites. The water contact angle for the thin film with the greatest hydrophilicity, TiO1.9884N0.0116, changed from 20 degrees to 6 degrees following irradiation.     

Preliminary evaluation of electrochemical PNA array for detection of single base mismatch mutations

We report here a preliminary evaluation of a microfabricated disposable-type peptide nucleic acid (PNA) array, with a 20-channel electrode, for the detection of cancer gene c-Ki-ras. Synthetic 15-mer PNA probes complimentary to ras sequence modified with cysteine were immobilized on the gold electrodes on the array. The electrochemical PNA array was reacted with 20-mer oligonucleotide target or 128 bp PCR product for 1 h. The anodic current derived from an electrochemically active DNA binder Hoechst 33258 was measured using the PNA array in the 50 microL of reaction chamber. The anodic current from Hoechst 33258 increased with increasing the concentration of PCR product of ras gene in the range from 10(11) to 10(15) copy mL(-1). The single base mismatch mutations of c-Ki-ras/61 were also detected using the electrochemical PNA array.     

Zero-magnetization ferromagnet proven by helicity-switching Compton scattering

A single crystal of gadolinium-doped SmAl(2) has zero magnetization in the midst of the ordered temperature region, despite the probable ferromagnetic spin ordering. The asymmetry in Compton-scattering intensity when switching between right- and left-handed polarization of incident 150-keV synchrotron radiation provides decisive proof that ferromagnetic order is really there, and that spin and orbital magnetic contributions cancel. The experiments also show that the spin direction at this zero-magnetization state is rather stable against the external magnetic field and, nevertheless, reversible by a preceding control of temperature and an external field.