Synthesis of pyrazolo[3,4-d]pyrimidine derivatives using ketene dithioacetals

The cyclization of 5-amino-3-methylthiopyrazole-4-carbonitriles or 4-carboxamides 3a-j , which were prepared by the reaction of ketene dithioacetals 1a,b [1a : bis(methylthiomethylenemalononitrile; 1b : bis(methylthio)methylenecyanoacetamide] with hydrazines (hydrazine hydrate, phenylhydrazine, p-chlorophenylhydrazine, p-nitrophenylhydrazine), with formamide or carbon disulfide proceeded to give the corresponding 4-amino- or 4-hydroxy-3-methylthiopyrazolo[3,4-d]pyrimidines 6a-h in good yields. 3-Aminopyrazolo[3,4-d]pyrimidine derivatives 6i-1 were also obtained by the application of the cyclization reaction of 3,5-diaminopyrazoles with formamide.     

Application of Pesticide Quantification in Unpolished Rice by LC-Dopant-Assisted Atmospheric Pressure Photoionization-MS

We applied liquid chromatography-dopant-assisted atmospheric pressure photoionization-mass spectrometry to quantify four distinct pesticides (isoprothiolane, fenitrothion, fthalide, and ethophenprox) in unpolished rice flour. Although the effect of acetone as a dopant on enhancement of ionization differed among the pesticides, the analytical results by LC-DA-APPI-MS with a dopant flow rate of 50 μL min^?1 were not only repeatable (relative SD < 9%, n = 3) but also comparable to those by gas chromatography–mass spectrometry.     

A validated HPLC‐fluorescence method with a semi‐micro column for routine determination of homocysteine,cysteine and cysteamine,and the relation between the thiol derivatives in normal human plasma

A semi‐micro column HPLC‐fluorescence method for routine determination of thiol derivatives such as homocysteine (Hcy), cysteine (Cys) and cysteamine (CA) is described. The thiol derivatives labeled with ammonium‐7‐fluorobenzo‐2‐oxa‐1,3‐diazole‐4‐sulfonate (SBD‐F) were isocratically separated within 12 min on a semi‐micro ODS column (Daisopak‐SP‐120‐5‐ODS‐BP) with a mixture of 25 mm acetate buffer (pH 2.00) and CH₃CN as a mobile phase. The purity and similarity of SBD‐thiols by a multi‐wavelength fluorescence detector were more than 92.3 and 96.7%. The detection limits of Hcy, Cys and CA at a signal‐to‐noise ratio of 3 were 0.16, 0.47 and 0.03 µm , respectively. Furthermore validation parameters such as accuracy, precision and robustness of the proposed method showed satisfactory results. Almost 850 plasma sample injections (range 572–1076, n = 3) for a column could be performed without differences in retention time and peak heights of labels. As an application of the proposed method, the determination of thiol derivatives in normal human plasma (n = 103) was demonstrated. The correlation coefficients between Hcy vs Cys and Hcy vs CA were 0.38 and −0.35, respectively. Copyright © 2009 John Wiley & Sons, Ltd.     

Electronic-phase transition associated with instability of the Hartree–Fock solution of infinite one-dimensional system

Electronic-phase transition associated with the singlet instability problem of the Hartree-Fock solution of the extended system is studied employing the metallic trans-polyacetylene. Concerning the eigenstates of the stability matrix set up for the crystal orbitals at the Fermi level, classification of the electronic phases is attempted and the origin of their emergence in relation to the interelectronic interaction is discussed.     

The total synthesis of dl-coriolin

The total synthesis of dl-coriolin has been accomplished via the key intermediate (5RS, 7SR) - 7 - t-butyldimethylsilyloxybicyclo[3.3.0]oct - 8 starting from 1,3 - cyclooctadiene.     

(2S,3R,4S,5R,6S)‐6‐Benzyl­oxy­methyl‐4‐(methoxy­methyloxy)‐9‐oxo‐8‐oxa‐1‐aza­bi­cyclo­[4.3.0]­nonane‐2,3,5‐triyl tri­acetate

The relative configuration of the title compound, C₂₃H₂₉NO₁₁, prepared in a synthetic study on the natural product sphingofungin E, has been determined. The six‐membered ring adopts a chair form and the five substituents are all axial.     

Tooth enamel proteins enamelin and amelogenin cooperate to regulate the growth morphology of octacalcium phosphate crystals

To examine the hypothetical cooperative role of enamelin and amelogenin in controlling the growth morphology of enamel crystals in the post-secretory stage, we applied a cation selective membrane system for the growth of octacalcium phosphate (OCP) in the truncated recombinant porcine amelogenin (rP148) with and without the 32kDa enamelin fragment. Enamelin alone inhibited the growth in the c-axis direction more than rP148, yielding OCP crystals with the smallest aspect ratio of all conditions tested. When enamelin was added to the amelogenin "gel-like matrix", the inhibitory action of the protein mixture on the growth of OCP in the c-axis direction was diminished, while that in the b-axis direction was increased. As a result, the length to width ratio (aspect ratio) of OCP crystal was markedly increased. Addition of enamelin to amelogenin enhanced the potential of amelogenin to stabilize the amorphous calcium phosphate (ACP) transient phase. The ratio of enamelin and amelogenin was crucial for stabilization of ACP and the growth of OCP crystals with larger aspect ratio. The cooperative regulatory action of enamelin and amelogenin was attained, presumably, through co-assembling of enamelin and amelogenin. These results have important implications in understanding the growth mechanism of enamel crystals with large aspect ratio.     

Novel sequential sigmatropic rearrangements of allylic diols: application to the total synthesis of (-)-kainic acid

Sequential sigmatropic rearrangements (Claisen/Claisen and Claisen/Overman) of enantiopure allylic diols are described. The reactions proceeded in complete diastereoselectivity without protecting group manipulations. The sequential Claisen/Overman rearrangement was successfully applied to the total synthesis of (-)-kainic acid.     

Synthesis of mesoporous PtCu film modified with Ru submonolayer as catalyst for methanol electrooxidation

A mesoporous PtCu catalyst modified with a Ru submonolayer is successfully synthesized by a facile electrochemical process of electrodeposition, dealloying and Ru underpotential deposition. The material has a large specific surface area comparable to nanoparticles (11 m(2) g(-1)) and exhibits a promising catalyst activity for the methanol oxidation reaction.     

Inclusion of Bisphenols by Cyclodextrin Derivatives

Complexation of various kinds of bisphenols (BPs) with cycloheptaamylose(β-cyclodextrin, β-CD) derivatives (β-CD, hydroxyethyl-β-CD (HE-β-CD), 2,6-di-O-methyl-β-CD (DM-β-CD) and polymerised β-CD (L-Poly-β-CD)) was examined fluorimetrically using2-anilinonaphthalene-6-sulfonic acid (2,6-ANS) as a probe. From the inhibitory effectof BPs on the inclusion of 2,6-ANS by the β-CD derivatives, the associationconstants (K_ass) of BPs with the β-CD derivatives were determined.The K_ass values for bisphenol B (BPB) with β-cyclodextrin derivatives except for L-Poly-β-CD were always larger than those for other BPs including bisphenol A (BPA), due to the interaction between the non-polar cavity and hydrophobic BPB. Thermodynamic parameters indicated that the entropy change was always largely negative (-90～ -120 J/mol...K in the β-CD system, for example), and the inclusion of bisphenols into the CD cavity was completely enthalpy-driven. The very largely negative entropy change might be mainly due to the tight fixation of guest molecules in the CD cavity, resulting in the loss of freedom of both CD and guest molecules. The effect of the structure of guest and host molecules on the association was also examined.