Synthesis of 2-O-(4-coumaroyl)-3-(4-hydroxyphenyl)lactic acid, an important intermediate of rosmarinic acid biosynthesis.

A simple method to synthesize (+/-)-2-O-(4-coumaroyl)-3-(4-hydroxyphenyl)lactic acid (1), a key intermediate in rosmarinic acid biosynthesis in higher plant cells, was established by condensation of protected 4-coumaric acid and (+/-)-3-(4-hydroxyphenyl)lactic acid followed by deprotection. A stable supply of 1 thus attained will lead to biochemical and molecular biological characterization of later steps of rosmarinic acid biosynthesis.     

Metabolic fate of [14C]triglyceride-entrapped lactosylceramide-bearing liposomes after intravenous injection into mouse.

We investigated the distribution and fate of liposomes after their intravenous injection into a mouse. Liposomes were composed of dimyristoylphosphatidylcholine, cholesterol and dicetylphosphate (7:2:1, molar ratio) with or without lactosylceramide. They were characterized as small unilamellar vesicles, approximately 100 nm in diameter, using gel-exclusion chromatography on a Sephacryl S-1000, freeze-fracture electron microscope and dynamic light scattering method. Liposomes were very stable in serum as seen by the results of leakage of the entrapped marker and electrophoresis experiments. We demonstrated that liposomes were internalized by way of an endocytotic process via coated vesicles detected in the electron microscope. The increase in liver uptake of lactosylceramide-bearing liposomes was mostly accounted for by enhanced uptake in the parenchymal cells, while uptake by non-parenchymal cells was only slightly increased. This observation supported the notion that a galactose-specific receptor was involved in liver uptake of lactosylceramide liposomes. The lactosylceramide-bearing liposomes were preferentially recovered in the liver and were found to first be predominantly localized in the mitochondria-lysosomal fraction. They were then decomposed by lysosomal enzymes, and the hydrolyzed components were reincorporated into membrane phospholipids in the microsomal fraction. At the same time, a rapid and reversible exchange of phosphatidylcholine between microsomes and mitochondria was demonstrated.     

Molecular macrocluster formation on silica surfaces in phenol-cyclohexane mixtures

The adsorption of phenol, an aromatic compound with a hydrogen-bonding group, onto a silica surface in cyclohexane was investigated by colloidal probe atomic force microscopy (AFM), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), and adsorption isotherm measurements. ATR-FTIR measurements on the silica surface indicated the formation of surface macroclusters of phenol through hydrogen bonding. The ATR-FTIR spectra were also measured on the H-terminated silicon surface to observe the effect of the silanol groups on the phenol adsorption. The comparison of the ATR-FTIR spectra for both the silicon oxide and H-terminated silicon surfaces proved that the silanol groups are necessary for the formation of phenol clusters on the surface. The surface force measurement using colloidal probe AFM showed a long-range attraction between the two silica surfaces in phenol-cyclohexane mixtures. This long-range attraction resulted from the contact of the adsorbed phenol layers for the phenol concentrations below 0.6 mol %, at which no significant phenol clusters formed in the bulk solution. The attraction started to decrease at 0.6 mol % phenol due to the exchange of the phenol molecules between the clusters in the bulk phase and on the surface. The surface density of phenol in the adsorbed layer was calculated on the basis of the long-range attraction and found to be much smaller than the liquid phenol density. The plausible structure of the adsorbed phenol layer was drawn by referring to the crystal structure of the bulk phenol and orientation of the phenol molecules on the surface, estimated by the dichroic analysis of ATR-FTIR spectroscopy. The investigation of the phenol adsorption on the silica surface in a nonpolar solvent using this novel approach demonstrated the effect of the aromatic ring on the surface packing density.     

根霉胞外羧甲基纤维素酶和β－葡糖苷酶的纯化研究

采用柱层析等步骤纯化了根霉Ｇ７的羧甲基纤维素酶及β－葡糖苷酶，回收率分别为４．５％和１９．６％．二种酶的最适酶反应温度都为５５°Ｃ，并都能在较大ｐＨ范围内保持稳定，其中羧甲基纤维素酶具有很高的耐热性，在１００°Ｃ水浴中保持１ｈ也仍可检测出约２０％的酶活性，最适反应ｐＨ为７．０～７．５；而β－葡糖苷酶的热稳性较差，其最适反应ｐＨ为５．０．该两种酶的分子量分别为２．５×１０４和９．５×１０４，而Ｋｍ值则分别为７．４０ｍｇｍＬ－１和０．２１３ｍｇｍＬ－１．     

Thermal properties and solubility of ordered aromatic polyamides containing a methyl-substituted phenylene linkage

Ordered aromatic polyamides and copolyamides were prepared by the polycondensation of terephthaloyl and isophthaloyl dichlorides with symmetrical diamines containing preformed amide linkages derived from unsymmetrical methyl—substituted aromatic diamines at low temperature. Thermal properties and solubilities of the ordered polyamides were compared with those of the corresponding random polyamides. There was little difference between thermal stabilities of the ordered polyamide and the corresponding random one, while the former was less soluble in organic solvents than the latter, depending on the extent of hydrogen bonding of the amide groups. The thermal stability of the alternating copolyamides containing both terephthaloyl and isophthaloyl groups as acid components was less than that of the corresponding homopolymers having either a terephthaloyl or an isophthaloyl group, and the solubility of the former resembled that of the corresponding ordered homopolysiophthalamides in accord with the extent of hydrogen bonding of the amide groups in both polymers.     

Tandem five membered-ring selective Prins reaction and Friedel–Crafts reaction

A tandem reaction consisting of five membered-ring selective Prins cyclization and subsequent Friedel–Crafts cyclization was developed. The reactions of phenyl homoallylic alcohol 3 and benzaldehyde derivatives 6 afforded tetrahydroindenofurans 7 or pentacyclic products 8, depending upon the quantity of 6. Also homoallylic alcohol 12 having an alkyne–cobalt moiety reacted with 6 to give rise to tetrahydroindenofurans 13 in good yields.     

The fast signal diffusion limit in a chemotaxis system with strong signal sensitivity

This paper gives an insight into making a mathematical bridge between the parabolic‐parabolic signal‐dependent chemotaxis system and its parabolic‐elliptic version. To be more precise, this paper deals with convergence of a solution for the parabolic‐parabolic chemotaxis system with strong signal sensitivity to that for the parabolic‐elliptic chemotaxis system where Ω is a bounded domain in () with smooth boundary, is a constant and χ is a function generalizing In chemotaxis systems parabolic‐elliptic systems often gave some guide to methods and results for parabolic‐parabolic systems. However, the relation between parabolic‐elliptic systems and parabolic‐parabolic systems has not been studied except for the case that . Namely, in the case that Ω is a bounded domain, it still remains to analyze on the following question: Does a solution of the parabolic‐parabolic system converge to that of the parabolic‐elliptic system as ? This paper gives some positive answer in the chemotaxis system with strong signal sensitivity.     

A new mechanism for the addition of alcohols to disilenes revealed by DFT and ONIOM calculations

Density functional and ONIOM calculations of alcohol and phenol additions to two (tetramethyl and tetramesityl) disilenes were carried out. The dimer of MeOH adds to Me₂SiSiMe₂ more readily than the monomer. The trimer does not afford the adduct, but a zwitter-ionic intermediate. In the (CF₃OH)₂ addition to Me₂SiSiMe₂, H?Si bond formation is more advanced than O?Si bond formation in the transition state (TS). Addition of seven phenol derivatives to Me₂SiSiMe₂ was examined, and the dimer reactions were found to be superior to the monomer reaction regardless of the substituents on the benzene rings. (MeOH)₂ reacts also with Mes₂SiSiMes₂ favorably, and an isomer of the reactant-like complex (precursor) may afford an adduct of different stereochemistry via internal rotations. Generally, the dimer of the alcohol or phenol is the reactant toward the disilenes. Exceptionally, a monomer of p-(dimethylamino)phenol reacts with Mes₂SiSiMes₂ owing to steric congestion by the four mesityl groups.     

Multifunctional Core–Shell Silica Nanoparticles for Highly Sensitive 19F Magnetic Resonance Imaging

¹⁹F magnetic resonance imaging (¹⁹F MRI) is useful for monitoring particular signals from biological samples, cells, and target tissues, because background signals are missing in animal bodies. Therefore, highly sensitive ¹⁹F MRI contrast agents are in great demand for their practical applications. However, we have faced the following challenges: 1) increasing the number of fluorine atoms decreases the solubility of the molecular probes, and 2) the restriction of the molecular mobility attenuates the ¹⁹F MRI signals. Herein, we developed novel multifunctional core–shell nanoparticles to solve these issues. They are composed of a core micelle filled with liquid perfluorocarbon and a robust silica shell. These core–shell nanoparticles have superior properties such as high sensitivity, modifiability of the surface, biocompatibility, and sufficient in vivo stability. By the adequate surface modifications, gene expression in living cells and tumor tissue in living mice were successfully detected by ¹⁹F MRI.     

The β‐silicon effect. 4: substituent effects on the solvolysis of 1‐alkyl‐2‐(aryldimethylsilyl)ethyl trifluoroacetates

Solvolysis rates of 2‐(aryldimethylsilyl)‐1‐methylethyl and 2‐(aryldimethylsilyl)‐1‐tert‐butylethyl trifluoroacetates were determined conductimetrically in 60% (v/v) aqueous ethanol. The effects of aryl substituents at the silicon atom on the solvolysis rates at 50 °C were correlated with parameters of r⁺ = 0.15 with the Yukawa–Tsuno equation, giving ρ values of ?1.5 for both secondary α‐Me and α‐tert‐Bu systems. The ρ values for those secondary systems are less negative than ?1.75 for the 2‐(aryldimethylsilyl)ethyl system that proceeds by the Eaborn (non‐vertical) mechanism, while they are distinctly more negative than ?0.99 for 2‐(aryldimethylsilyl)‐1‐phenylethyl system that should proceed by the Lambert (vertical) mechanism. There was a fairly linear relationship between the reaction constants (ρ) for the β‐silyl substituent effects and the solvolysis reactivities for a series of β‐silyl substrates. The solvolyses of the α‐Me and tert‐Bu substrates proceed through the transition state (TS) with an appreciable degree of the β‐silyl participation, close to the Eaborn (non‐vertical) TS rather than to the Lambert (vertical) TS. Copyright © 2010 John Wiley & Sons, Ltd.