Studies on antiatherosclerotic agents. Synthesis of 5-substituted derivatives of 7-ethoxycarbonyl-6,8-dimethyl-1(2H)-phthalazinone.off.

Several 5-substituted derivatives of 7-ethoxycarbonyl-6,8-dimethyl-1(2H)- phthalazinone were prepared by means of nitration, reductive amination, and diazonium decomposition. The substituents introduced included NO2, NH2, F, Cl, CN. Among the derivatives, the fluorine compound was obtained only in poor yield because intramolecular cyclization occurred predominantly.     

Ion chromatography–inductively coupled plasma mass spectrometry determination of arsenic species in marine samples

Arsenic speciation analysis in marine samples was performed using ion chromatography (IC) with inductively coupled plasma mass spectrometry (ICP‐MS) detection. The separation of eight arsenic species, viz. arsenite, monomethyl arsonic acid, dimethylarsinic acid, arsenate, arsenobetaine, tetramethylarsine oxide, arsenocholine and tetramethylarsonium ion was achieved on a Dionex AS4A (weaker anion exchange column) by using a nitric acid pH gradient eluent (pH 3.3 to 1.3). The entire separation was accomplished in 12 min. The detection limits for the eight arsenic species by IC–ICP‐MS were in the range 0.03–1.6 µ g l^?1, based on 3σ of the blank response (n = 6). The repeatability and day‐to‐day reproducibility were calculated to be less than 10% (residual standard deviation) for all eight species. The method was validated by analyzing a certified reference material (DORM‐2, dogfish muscle) and then successfully applied to several marine samples, e.g. oyster, fish muscle, shrimp and marine algae. The low power microwave digestion was employed for the extraction of arsenic from seafood products. Copyright © 2004 John Wiley & Sons, Ltd.     

Interpreting Kullback-Leibler divergence with the Neyman-Pearson lemma

Kullback-Leibler divergence and the Neyman-Pearson lemma are two fundamental concepts in statistics. Both are about likelihood ratios: Kullback-Leibler divergence is the expected log-likelihood ratio, and the Neyman-Pearson lemma is about error rates of likelihood ratio tests. Exploring this connection gives another statistical interpretation of the Kullback-Leibler divergence in terms of the loss of power of the likelihood ratio test when the wrong distribution is used for one of the hypotheses. In this interpretation, the standard non-negativity property of the Kullback-Leibler divergence is essentially a restatement of the optimal property of likelihood ratios established by the Neyman-Pearson lemma. The asymmetry of Kullback-Leibler divergence is overviewed in information geometry.     

Fragmentation in doubly charged ion mass spectra of anhydropisatin and related compounds

The doubly charged ion mass spectra of anhydropisatin, 4-methoxyanhydropisatin, 3, 8, 9-trimethoxypterocarpen and 3, 4, 8, 9-tetramethoxypterocarpen were determined, and the fragmentation was explained by assuming that the paired electrons were partially localized in the fragmentations and by comparing the spectra with that of 3-(CD₃)-anhydropisatin. Conventional mass spectra of these compounds were very simple, but the doubly charged ion spectra were sufficiently characteristic for the reliable identification.     

Characteristics of hyaluronate-hydroxyethyl acrylate blend gel and release of cationic amphiphilic solutes

Hyaluronate-hydroxyethyl acrylate blend gel (HA-PHEA) were prepared to modify the brittleness of hyaluronate gel (HA) and the characteristics of HA-PHEA gel were compared with those of HA and polyhydroxyethyl acrylate (PHEA) gels. These gels were high in water content and transparent. HA-PHEA gel was improved in viscoelastic properties due to the elasticity and the high affinity with water of PHEA, and the drying-swelling cycles became reversible. The effective charge densities theta of the gels estimated from membrane potentials were -0.002, -0.008 and 0 mol dm(-3) for HA-PHEA, HA and PHEA gels. Effects of electro- static and nonelectrostatic interactions on absorptions and releases were studied using sodium benzoate (NaBA) as an anionic solute, and methylene blue (MB), chlorpromazine (CPHCl) and benzethonium chloride (BZTCl) as cationic solutes, in which CPHCl and BZTCl are cationic amphiphilic solutes. The releases of MB, CPHCl and BZTCl from HA-PHEA and HA gels were suppressed comparing with those of NaBA. By adding salts, the releases of MB and CPHCl were enhanced but those of BZTCl were suppressed due to enhancement of the intra- and intermicelle formation. In the releases of the cationic solutes from HA-PHEA gel, electrostatic and nonelectrostatic interactions with HA were found to play important roles. Behaviors of the releases from HA-PHEA gel were found to possess the features of HA gel.     

Importance of the isopropylidene terminal of geranylgeranyl group for the formation of tetraether lipid in methanogenic archaea

Labeling experiments using several deuterated lipids were pursued to study the biosynthesis of macrocyclic isoprenoidal lipids of thermophilic methanogenic archaea, Methanothermobacter thermautotrophicus. The isopropylidene terminal of geranylgeranyl group of monomeric precursor appeared to be important for the CC bond formation at the hydrophobic end in the macrocyclic lipids. A mechanism involving a radical trigger at the allylic methyl group is proposed for this CC bond formation.     

On-line column preconcentration for the determination of cobalt in sea water by flow-injection chemiluminescence detection

A flow-injection method for the determination of dissolved cobalt(II) in sea water has been studied based on a combination of column preconcentration using 8-quinolinol immobilized on silica gel, fluoride containing metal alkoxide glass (8HQ-MAF) and chemiluminescence detection with a gallic acid-hydrogen peroxide system. Co(II) is selectively recovered from an acidified sample with 8-quinolinol immobilized on silica gel. After elution with dilute hydrochloric acid the resultant eluent is mixed with the reagent solutions, heated to 60^°C and then introduced into the CL cell. The analysis time including the 2-min sample load was 8 min per sea water sample with a corresponding detection limit of 0.62 ngl^-1 (3). The average standard deviation calculated for 10 replicate measurements of artificial sea water samples with a concentration of 10 ngl^-1 cobalt was ±2.1%. The method has been tested with the standard reference sea waters NASS and CASS.