Application of the 19F NMR technique to observe binding of the general anesthetic halothane to human serum albumin.

19F NMR techniques were employed to characterize the binding property of the widely used general anesthetic halothane with human serum albumin (HSA). It was found that 19F(1H) NOE and 2D 1H-19F HOESY experiments detected intermolecular NOEs between halothane 19F and HSA protons. Measurements of the diffusion coefficients for halothane were also carried out by 1H and 19F NMR, indicating the interaction of halothane with HSA. The present results indicate that these techniques are very suitable to identify a fluorine-containing ligand binding with a protein receptor in the drug-discovery process.     

Development and features of hydro-membrane gas chromatography.

Hydro-membrane gas chromatography (HMGC) is achieved by the annular condensation of water in a capillary column at less than 70 degrees C. The annular membrane of water is formed as a result of the wettability of the stationary phase, which is induced at a water contact angle ranging from 75 degrees to 79 degrees, as derived from a solubility parameter (delta) range of 15.7 +/- 0.3 MPa(1/2) of the coated resin. The range of the liquid to gas volume ratio (beta) required to support the annular membrane should be kept between 0.00005 and 0.0003. In the case of a 0.25-mm i.d. column, the ratio can be set by the combination of a 0.1 to 0.2 microl min(-1) water supply rate and helium gas flow rate. Separation by HMGC develops not only a gas-solid partition but also a focusing effect on the water membrane. One feature of HMGC is that it gives a non-adsorption chromatogram based on the blocking effect of pre-adsorbed water; furthermore, despite the presence of a relatively large quantity of water, the electron impact ionization efficiency is kept the same as in the usual GC/MS condition. The detection limit with the injection of 1 microl of aquatic solution was estimated to be less than 0.1 ppb of low-molecular-weight fatty acids with s/n = 5 on a mass chromatogram at m/z 45. The HMGC/EI-MS system can be applied to the trace analysis of C1 to C3 volatile acids, volatile inorganic acids, and halogenated organic acids in water.     

Senecicannabine,a new pyrrolizidine alkaloid from senecio cannabifolius

The structure of senecicannabine($\text{1}$), a new mcrocyclic pyrrolizidine alkaloid isolated from $\text{Senecio cannabifolius}$, has been established by chemical study and X-ray analysis.     

Vacuum fusion determination of micro-quantities of bulk gases in low carbon iron without an effect of surface gases

Summary Vacuum Fusion Determination of Micro-quantities of Bulk Gases in Low Carbon Iron Without an Effect of Surface Gases Micro-quantities of bulk and surface oxygen and hydrogen in low carbon iron was simultaneously determined by the surface-area-variation method using vacuum fusion analysis. Among the difference of three surface treatments, silicon carbide abrasive, electropolishing and hydrogen reduction methods, bulk oxygen and hydrogen were in agreement within their errors, however, surface oxygen and hydrogen were influenced from the surface treatments. Even in the case of electropolishing, which gave the smallest surface oxygen value, bulk oxygen less than 10g/g is needed to discriminate from the surface oxygen. Bulk hydrogen of 0.03g/g was determined without the effect of surface hydrogen in the hydrogen reduction treatment.     

The interface of the Ising model and the Brownian sheet

We study the limit theorem related to the interface of the three-dimensional Ising model. Dobrushin proved that the interface does not fluctuate and becomes rigid for sufficiently large. We define the random fieldX ^L (t, s), 0t, s1, on the interface, and prove that X^L(t, s) converges to the Brownian sheet as L for sufficiently large, whereL denotes the size of the system. This result does not mean that the interface itself converges to the Brownian sheet.     

Crystal structures of n-alkanes with branches of different size in the middle

We synthesized four branched n-alkane samples C35-C1, C35-C4, C35-C6, and C35-C4Ph with the same number of carbons as the main chain, n = 35, to which the methyl, butyl, hexyl, and butyl phenyl groups were respectively attached at the middle, and also the corresponding linear homologue of C35, and studied their crystalline structures from DSC, IR, and Raman spectroscopy, X-ray diffraction measurement, and computer simulation. Solid-solid phase transitions characteristic of linear alkane C35 are not observed for any branched alkanes, and their melting temperatures Tm are lowered to 325.2, 318.5, 314.3, and 314.1K, respectively. Main chains of branched alkane molecules are not folded, irrespective of length and chemical structure of branches, but are extended to take the planar zigzag form in the solid state. The branches of C35-C4 and C35-C6 are also aligned inside the crystal in the extended form. Data analyses on solution-grown crystallized samples reveal that, with increasing the branch length, their crystal structures transform from polymorphic forms of the orthorhombic (P2(1)2(1)2(1)) and the triclinic (P) for C35-C1 and C35-C4 to the unique triclinic form for C35-C6 and C35-C4Ph, so as to minimize extra surface energy invoked by introduction of long branches.     

Total synthesis of brevetoxin-B

Brevetoxin-B (BTX-B), produced by the red tide organism, Gymnodium breve Davis, is the first member of marine polycyclic ethers to be structurally elucidated and one of the most potent neurotoxins. The structural feature is a trans-fused polycyclic ether ring system with 23 stereocenters. Its unique, complex structure and potent biological activity have attracted the attention of synthetic organic chemists. Total synthesis of BTX-B has been accomplished via the coupling of the ABCDEFG and IJK-ring segments, each ether ring of which was stereoselectively and efficiently constructed on the basis of SmI2-induced intramolecular cyclization, 6-endo-cyclization of hydroxy epoxide, ring-closing olefin metathesis, and SmI2-induced intramolecular Reformatsky-type reaction. Several kinds of double reactions at the left and right sides were efficiently used through the synthesis.     

The electrochemical behavior of ad-atoms and their effect on hydrogen evolution: Part II. Arsenic ad-atoms on platinum

The state of an arsenic layer electrodeposited at various potentials on platinum electrodes has been examined electrochemically. The relation between the state and the electrocatalytic activity for hydrogen evolution has been investigated. The number of vacant sites have been found to increase with lowering of the deposition potential. The activity has been found to depend not on the amount of deposited arsenic but on the number of vacant sites. The difference in the effects of arsenic and of copper on hydrogen evolution is pointed out. This is attributed to the difference in the affinity of the ad-atoms for hydrogen.     

Enteric solid dispersion of ciclosporin A (CiA) having potential to deliver CiA into lymphatics

Solid dispersions composed of three components, ciclosporin A (CiA), surfactant (HCO-60) and a pharmaceutical additive, were prepared. As an additive, cellulose acetate phthalate (CAP), methacrylic acid and methacrylic acid methylester copolymer (Eudragit L-100) and hydroxypropylmethylcellulose phthalate (HP-55), which are generally used as enteric coating materials, were employed. The dissolution behavior of CiA from these enteric solid-dispersion system was studied according to the paddle method of JP XI in comparison with that of Sandimmun, an olive oily CiA solution as a reference. Solid dispersion of CiA preparation did not dissolve in the 1st test fluid (pH 1.2) in 2 h. In the 2nd fluid (pH 6.8), about 80% of CiA was dissolved within 12 min, though the dissolution rate was dependent on both the quality and quantity of the additives. An in vivo systemic and lymphatic availability study was performed with rats whose carotid artery and thoracic lymph duct were cannulated. After intrastomach administration of each CiA preparation to rats at a dose of 7 mg/kg, blood and lymph samples were collected for 6 h. One of the HP-55 preparations gave the highest plasma CiA level, Cmax = 0.99 +/- 0.20 (S.E., n = 4) micrograms/ml, and also showed the highest lymphatic availability, the percentage of dose delivered to the lymphatics in 6 h was 1.98 +/- 0.10% and the maximum lymph CiA level was 76.8 +/- 12.86 micrograms/ml. Lymphatic availability of CiA from Sandimmun was 0.78 +/- 0.11% and the peak plasma CiA level was 0.46 +/- 0.10 microgram/ml.(ABSTRACT TRUNCATED AT 250 WORDS)     

Remarkable reactivity enhancement with Sb?N inter-coordination of ethynyl-1,5-azastibocines in Pd-catalyzed cross-coupling reactions with organic halides

The reaction of 12-arylethynyl-6-methyl-5,6,7,12-tetrahydrodibenzo[c,f][1,5]-azastibocines with organic halides such as acyl halides and aryl halides in the presence of PdCl₂(PPh₃)₂ as a catalyst led to the formation of cross-coupling products, alkynyl ketones and diaryl acetylenes, in good yields. The reactivity of the ethynyl group on the 1,5-azastibocines was far superior to that on diphenyl(phenylethynyl)stibane, which brought about marked improvement in the reaction conditions (lower temperature and shorter reaction time) and in the yields of the cross-coupling products. Single-crystal X-ray analysis of the ethynyl-1,5-azastibocine showed the presence of intramolecular Sb?N interaction which should be responsible for the remarkable reactivity enhancement of the 1,5-azastibocines for this type of reaction.