Potential bile acid metabolites. 24. An efficient synthesis of carboxyl-linked glucosides and their chemical properties

A facile and efficient synthesis of the carboxyl-linked glucosides of bile acids is described. Direct esterification of unprotected bile acids with 2,3,4,6-tetra-O-benzyl-d-glucopyranose in pyridine in the presence of 2-chloro-1,3,5-trinitrobenzene as a coupling agent afforded a mixture of the α- and β-anomers (ca. 1∶3) of the 1-O-acyl-d-glucoside benzyl ethers of bile acids, which was separated effectively on a C₁₈ reversedphase chromatography column (isolated yields of α- and β-anomers are 4–9% and 12–19%, respectively). Subsequent hydrogenolysis of the α- and β-acyl glucoside benzyl ethers on a 10% Pd−C catalyst in acetic acid/methanol/EtOAc (1∶2∶2, by vol) at 35°C under atmospheric pressure gave the corresponding free esters in good yields (79–89%). Chemical specificities such as facile hydrolysis and transesterification of the acyl glucosides in various solvents were also discussed.     

Oxidation of unsaturated and hydroxy fatty acids by ruthenium tetroxide and ruthenium oxyanions

The reactions of ruthenium VIII tetroxide (RuO₄) and the ruthenium VII and VI oxyanions, perruthenate (RuO₄ ⁻) and ruthenate (RuO₄ ⁼) with hydroxy substituted and unsaturated fatty acids have been studied. At a 1:1 molar ratio, ruthenium tetroxide (RuO₄) and both oxyanions (RuO₄ ⁻ and RuO₄ ⁼) oxidized 12-hydroxystearic acid to 12-ketostearic acid. With 9, 10-dihydroxystearic acid, the type of oxidation products obtained depended on the amount of ruthenium oxidant used. At high ratios of oxidant to substrate, cleavage to pelargonic and azelaic acids occurred whereas at lower ratios, partial oxidation to diketo and acyloin derivatives predominated. The oxidation of oleic acid with excess ruthenium tetroxide (RuO₄) or perruthenate anion (RuO₄ ⁻) gave the cleavage products pelargonic and azelaic acid through the intermediate formation of dihydroxy and diketo intermediates. Ruthenate anion (RuO₄ ⁼) did not react with the double bond of oleic acid. Agricultural Research Service, U.S. Department of Agriculture.     

Double organic modification by 3‐chloropropyl and methyl groups on pure silica MCM‐41 and Ti‐MCM‐41: efficient catalyst for epoxidation of cyclododecene

Simultaneous surface modification by 3‐chloropropyl and methyl groups on the same Si atoms resulted in hydrophobic and highly ordered mesoporous silica with a very high surface area. ¹³C and ²⁹Si MAS NMR spectra indicate homogeneous grafting of chloropropyl and methyl groups in the silica matrix and this organically modified Ti‐MCM‐41 shows outstanding catalytic performance in the epoxidation of cyclododecene using tert‐butyl hydroperoxide as oxidant. This revised version was published online in July 2006 with corrections to the Cover Date.     

Method for correcting molecular weight from gel-permeation chromatography. I. Skewing and concentration corrections

The purpose of this paper is to present a metod to calculate real molecular weight averages of polymer samples from GPC chromatograms where the instrumental spreading functions are skewed and the concentration effect exists. In this method, it is assumed that (1) the skewed chromatograms of monodisperse polymer samples can be represented as resultant of halves of two different Gaussians, (2) the resolution factors are regarded as constant in the case of low sample loading, and (3) the peak elution volume is independent of the presence of other components in the case of low sample loading. Adequate monodisperse polystyrenes and the mixtures (binary, seven and ten components) were examined for this purpose; and the molecular weight averages calculated by this method were compared with the ones obtained by Rosen and Provder's method. From the results in our study, it is found that this method can be available for correcting molecular weight from GPC chromatograms except for very narrow high molecular weight samples.     

Hydrophobic effects on protein/nucleic acid interaction: enhancement of substrate binding by mutating tyrosine 45 to tryptophan in ribonuclease Tl

Hydrophobic effects on binding of ribonuclease Tl to guaninebases of several ribonucleotides have been proved by mutatinga hydrophobic residue at the recognition site and by measuringthe effect on binding. Mutation of a hydrophobic surface residueto a more hydrophobic residue (Tyr45 – Trp) enhances thebinding to ribonucleotides, including mononucleotide inhibitorand product, and a synthetic substrate-analog trinudeotide aswell as the binding to dinucleotide substrates and RNA. Enhancementson binding to non-substrate ribonucleotides by the mutationhave been observed with free energy changes ranging from –2.2 to – 3 .9 kJ/mol. These changes are in good agreementwith that of substrate binding, –2.3 kJ/mol, which iscalculated from Michaelis constants obtained from kinetic studies.It is shown, by comparing the observed and calculated changesin binding free energy with differences in the observed transferfree energy changes of the amino acid side chains from organicsolvents to water, that the enhancement observed on guaninebinding comes from the difference in the hydrophobic effectsof the side chains of tyrosine and tryptophan. Furthermore,a linear relationship between nucleolytic activities and hydrophobicityof the residues (Ala, Phe, Tyr, Trp) at position 45 is observed.The mutation could not change substantially the base specificityof RNase Tl, which exhibits a prime requirement for guaninebases of substrates.     

Synthesis and Magneto-mechanical Properties of Ce-TZP/La M-Type Hexaferrite Composite

An in situ composite composed of ceria-stabilized tetragonal zirconia polycrystals (Ce-TZP) and La{Co_0.5Fe_0.5(Fe_0.9Al_0.1)₁₁}O₁₉ was synthesized from a powder mixture of Ce-TZP, La(Fe_0.9Al_0.1)O₃, Fe₂O₃, Al₂O₃, and CoO. The dense Ce-TZP dispersed with platelike La{Co_0.5Fe_0.5(Fe_0.9Al_0.1)₁₁}O₁₉ crystals as a second phase were formed after sintering from 1250° to 1350°C. The saturation magnetization of the in situ composite Ce-TZP/La{Co_0.5Fe_0.5(Fe_0.9Al_0.1)₁₁}O₁₉ was proportional to the mass fraction of the hexaferrite second phase in Ce-TZP. The coercivity of the composite with a 20 mass% of second phase decreased from 9.14 to 2.52 kOe (from 728 to 201 kA/m) after the pulverization of the composite. The susceptibility (χ) increased by 15%–25% under uniaxial stress on the composite. The change of the susceptibility (Δχ/χ) value increased with decreasing the mass fraction of the second phase in the composite. The Δχ was found to increase linearly with applied stress and abruptly change on cracking, which is expected for the application in fracture sensing of the composite.     

Decomposition of Carbon Dioxide to Carbon with Active Wustite at 300°C

Active wustite (FeδO, with a δ value of 0.98) was prepared by keeping normal wustite (δ value of 0.94) in a N₂ atmosphere at 300°C for 10 min. This reaction is given by (4δ₂–3)Fe_δ1O→(4δ₁–3)Fe_δ2O + (δ₂–δ₁)Fe₃O₄ where δ₁= 0.94 and δ₂= 0.98. The equation indicates that the normal wustite undergoes eutectoid decomposition into active wustite and stoichiometric magnetite (Fe₃O₄). Carbon dioxide (1.013 × 10⁵ Pa) was almost completely (100%) decomposed into carbon (zero valence) by the active wustite at the low temperature of 300°C, which was associated with the transformation of the active wustite into the stoichiometric magnetite. The internal pressure of the reaction cell eventually became a vacuum.     

Autoxidation of ethyl eicosapentaenoate and docosahexaenoate

The extent of oxidation of ethyl esters of eicosapentaenoic (EPA) and docosahexaenoic acids (DHA) was compared quantitatively with that of ethyl linoleate (Lo) and ethyl linolenate (Ln) by oxygen uptake and formation of conjugated diene, hydroperoxide and secondary oxidation products. EPA and DHA esters were oxidized rapidly even at 5 C in the dark after an induction period of 3–4 days, while the induction periods of Ln and Lo esters were 20 days and more than 60 days, respectively. Oxygen uptake of EPA and DHA esters after the induction period was 5.2 and 8.5 times faster than that of ethyl Ln, respectively. Hydroperoxides of EPA and DHA esters are much less stable than those of ethyl Lo. The peroxide value is not necessarily a good indication of oxidation in these polyenoic acids because a considerable amount of secondary products is formed at the early stage of oxidation. Polymers were found to be major secondary products in these polyenoic esters.     

Pervaporation membranes for ethanol–water mixture prepared by plasma polymerization. III. Perfluorocarbon membranes

Pervaporation membranes for the ethanol–water mixture were prepared by plasma polymerization of tetrafluoroethylene, perfluoropropane, and perfluoropropylene onto porous substrates. The influence of the monomers on the elemental ratio (F/C) of the polymer depositions by X-ray photoelectron spectroscopy was rather small compared with that of the W/FM parameter (W = wattage for plasma excitation, FM = mass flow rate of a monomer). The optical emission spectroscopy indicated the similarity of gaseous species formed in the plasmas. The membranes were found ethanol-permselective, showing separation coefficients (α_EtOH) around 4–7 and a wide range of permeation rates (J), 10–10^?2 kg/m² h, for the 4.8 wt % ethanol solution at 40°C. The α_EtOH of the membranes with thicker depositions could be correlated to the F/C ratios as a measure of membrane hydrophobicity. It was thought that, by making a plot α_EtOH against J values for the perfluorocarbon membranes, they could be classified into three groups on thickness of deposition. The ethanol-separation mechanisms for each group, which may contain four kinds of mass transfer schemes, i.e., distillation through larger pores, flow of sorption layer at the liquid–membrane interface, and diffusions through deposition or substrate, were also discussed.     

Synthesis of diameter-controlled carbon nanotubes using centrifugally classified nanoparticle catalysts

Iron-based nanoparticles, centrifugally classified by size, with variation of subnanometer order, have been used for the growth of diameter-controlled carbon nanotubes (CNTs) for the first time via catalytic chemical vapor deposition. The centrifugal classification of nanoparticles is facilitated by fractional precipitations through the sequential addition of ethanol to a hexane solution containing the nanoparticles. Three different nanoparticle sizes were obtained, which have average diameters and standard deviations of 3.9 ± 0.8 nm, 3.3 ± 0.6 nm, and 2.8 ± 0.4 nm. By the classification process of nanoparticles, the standard deviation of the average diameter of the fractionated nanoparticles decreased by around one half of that of the as-synthesized nanoparticles. In addition, we demonstrate a technique for estimating the average diameter of each classified nanoparticle using conventional low-angle X-ray diffraction, without the need for time-consuming TEM observation and analysis. From the three classified nanoparticle sizes, with average diameters of 2.8, 3.3, and 3.9 nm, CNTs with average diameters of 3.1, 3.6, and 4.5 nm were obtained by changing growth temperatures, respectively. Therefore, centrifugally classified nanoparticles are one of the most promising ‘seeds’ for use in the diameter-selective growth of CNTs.