Isothermal differential scanning calorimetry on an exothermic phenomenon during thermal decomposition of hydromagnesite 4 MgCO3 · Mg(OH)2 · 4 H2O

An exothermic phenomenon and a simultaneous rapid evolution of a small amount of carbon dioxide at ?500°C during thermal decomposition of hydromagnesite 4 MgCO₃ · Mg(OH)₂ · 4 H₂O was studied by isothermal DSCTG in a carbon dioxide atmosphere. It was quantitatively confirmed that the exothermic phenomenon was due to crystallization of MgCO₃ from the amorphous phase and that the evolution of carbon dioxide was due to decomposition of the MgCO₃ by the heat of crystallization (?3.4 kcal mole^?1.     

Stereoselective synthesis of procyanidin B3-3-O-gallate and 3,3″-di-O-gallate, and their abilities as antioxidant and DNA polymerase inhibitor

A simple method for the synthesis of procyanidin B3 substituted with a galloyl group at the 3 and 3″ position is described. Condensation of a benzylated catechin-3-O-gallate electrophile with a nucleophile, catechin and catechin-3-O-gallate, proceeded smoothly and stereoselectively to afford the corresponding dimer gallates, procyanidin B3-3-O-gallate and procyanidin B3-3,3″-di-O-gallate, in good yields. Further, their antioxidant activities on UV-induced lipid peroxide formation, DPPH radical scavenging activity and inhibitory activity of DNA polymerase were also investigated. Among three procyanidin B3 congeners (procyanidin B3, 3-O-gallate and 3,3″-di-O-gallate), the 3,3″-di-O-gallate derivative showed the strongest antioxidant and radical scavenging activity. Interestingly, the 3-O-gallate derivative was the strongest inhibitor of mammalian DNA polymerase with IC₅₀ value of 0.26 μM, although it showed the weakest antioxidant and radical scavenging activity. It became apparent that the presence of a galloyl group at the C-3 position in the proanthocyanidin oligomer was very important for biological activity, however, the antioxidant activity of these compounds was not parallel to the DNA polymerase inhibitory activity.     

Development of a certified reference material for the determination of perfluorooctanoic acid

A certified reference material (CRM) for the determination of perfluorooctanoic acid (PFOA) has been issued as NMIJ CRM 4056-a by the National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology (NMIJ/AIST). Purity (kg kg^?1) based on a titration method was determined by subtracting the mass fractions of impurities measured using liquid chromatography/mass spectrometry (LC/MS) from those of acids expressed as PFOA measured by a neutralization potentiometric titration. To validate an obtained result, purity based on a mass balance method was determined by subtracting the mass fractions of impurities, measured using LC/MS, Karl-Fischer titration (KFT), and vacuum evaporation, from 1 kg kg^?1. Results from both titration and mass balance methods were in agreement within the accepted limits of uncertainty. The certified purity of NMIJ CRM 4056-a was determined to be 0.959 kg kg^?1, calculated as the mean of the results obtained with the two methods. The standard uncertainty of the certified purity was evaluated from purity evaluations as well as from sample homogeneity and stability obtained from LC/MS and KFT analyses. Consequently, the expanded uncertainty was estimated to be 0.005 kg kg^?1 with a coverage factor of k = 2.     

Electron transport with mobility above 10–3 cm2/Vs in amorphous film of co‐planar bipyridyl‐substituted oxadiazole

We demonstrate that a bipyridyl substituted oxadiazole (Bpy‐OXD) shows high electron mobility that reached above 10^–3 cm²/Vs. We believe that the high mobility results from both the hybrid molecular structure of the two electron‐accepting units: bipyridyl and oxadiazole, and the planar molecular structure based on its lack of sterically hindered bulky substituent. The computational analysis elucidates that the amorphous nature of Bpy‐OXD in thin‐film state probably results from the polymorphic effect in isolated state and the volume effect in solid state. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Mass balance method for purity assay of phthalic acid esters: development of primary reference materials as traceability sources in the Japan Calibration Service System

Purity assay of high-purity materials (HPMs) of phthalic acid esters (PAEs) was carried out by means of a mass balance method. In this method, chromatographic methods such as gas chromatography-flame ionization detector (GC-FID) and/or high-performance liquid chromatography (HPLC) in combination with other methods such as Karl-Fischer (KF) titration and vacuum evaporation (VE) were applied. The sum of the impurities estimated by these methods allowed the estimation of the purity of the main component by difference. Seven PAEs with varying side chain structures and levels of impurities were analysed on a systematic way in which impurities were classified into several groups in terms of their abundance, availability of qualitative information and availability of authentic compounds, etc. The absolute quantity of each impurity was determined by GC-FID and/or HPLC based on the calibration made by the authentic compounds of impurities whenever available. The purities in mass fraction of these PAEs were certified at the National Metrology Institute of Japan (NMIJ), and the PAEs were registered as primary reference materials playing an essential role in linking the metrological traceability of the Japan Calibration Service System (JCSS) to the International System of Units (SI).     

Reaction of O6-methylguanosine with nitrite in the presence of carboxylic acid: synthesis of the purin-2-yl carboxylate

O6-Methylguanosine derivative was treated with sodium nitrite or isoamylnitrite in the presence of carboxylic acid to give the purin-2-yl carboxylate, an unusual product bearing a carboxylic group at the 2-position of the purine moiety.     

Differences in the yields of polycyclic aromatic hydrocarbons by pressurized liquid extraction and the Japanese official method

To improve the extraction of polycyclic aromatic hydrocarbons (PAHs) from sediment samples, we optimized the conditions of pressurized liquid extraction (PLE). The yields increased as the extraction temperature increased from 100 to 190 degrees C, but the effect of increasing pressure (from 15 to 20 MPa) was small. Parameters of 190 degrees C and 20 MPa, near the maximum of the equipment, gave the highest yield. Under these conditions, the yields of 17 PAHs were 1.5 - 34 times those obtained by the Japanese official method (shaking and ultrasonic extraction with acetone at room temperature).     

Accurate Quantification of Polycyclic Aromatic Hydrocarbons in Environmental Samples Using Deuterium-labeled Compounds as Internal Standards

For the accurate quantification of polycyclic aromatic hydrocarbons (PAHs) in environmental samples by isotope-dilution mass spectrometry (IDMS) and gas chromatography-mass spectrometry (GC-MS), we used deuterium-labeled PAHs (D-PAHs) as internal standards for microg g(-1)-level certified reference materials and corresponding calibration solutions. Although pressurized liquid extraction (PLE) causes significant biases in the analytical results for ng g(-1)-level samples (2.4 - 15%), biases in the analytical results by PLE (190 degrees C, 20 MPa, 2 cycles) were small (<2.3%) and negligible for microg g(-1)-level samples when expanded uncertainty (coverage factor k = 2) was considered.     

Application of the cd homoallylic benzoate method as a chiroptical tool for determination of absolute configuration

After the conformation I was clarified to 5α-,10α,-cis-solidagolactones by ¹H NMR measurement with Eu(dpm)₃ and chemical transformations, the CD homoallylic benzoate chirality method was applied to the homoallylic alcohol system of solidagolactone IV ($\text{1a}$) for a chiroptical determination of the absolute configuration. The result agreed with absolute configuration elucidated by x-ray analysis, indicating the usefulness of the cd method.     

Asymmetric Total Synthesis of (−)‐Englerin A through Catalytic Diastereo‐ and Enantioselective Carbonyl Ylide Cycloaddition

An asymmetric total synthesis of the guaiane sesquiterpene (?)‐englerin A, a potent and selective inhibitor of the growth of renal cancer cell lines, was accomplished. The basis of the approach is a highly diastereo‐ and enantioselective carbonyl ylide cycloaddition with an ethyl vinyl ether dipolarophile under catalysis by dirhodium(II) tetrakis[N‐tetrachlorophthaloyl‐(S)‐tert‐leucinate], [Rh₂(S‐TCPTTL)₄], to construct the oxabicyclo[3.2.1]octane framework with concomitant introduction of the oxygen substituent at C9 on the exo‐face. Another notable feature of the synthesis is ruthenium tetraoxide‐catalyzed chemoselective oxidative conversion of C9 ethyl ether to C9 acetate.