Selective and simultaneous determination of phosphate and silicate ions in leaching process waters for ceramics glaze raw materials of narutal origin by ion-exclusion chromatography coupled with UV-detection after postcolumn derivatization.

The selective and simultaneous ion-exclusion chromatography (IEC) with UV-detection on a weakly acidic cation-exchange resin column in the H+ -form (TSKgel Super IC-A/C) was developed and applied for the simultaneous determination of phosphate and silicate ions as the water quality parameters required for optimizing the water-leaching process for ceramics glaze raw materials of natural origin including feldspar, woods-ash, and straw-ash. Phosphate and silicate ions in these water-leaching process water samples were separated selectively from the coexisting anions such as sulfate, chloride, nitrate and carbonate ions, based on the ion-exclusion separation mechanism. They were detected selectively and simultaneously by a postcolumn derivatization with molybdenum-yellow using the UV-detector. Under the optimized separation and detection conditions (eluent, 0-1 mM sulfuric acid; reactant, 10 mM sodium molybdate-25 mM sulfuric acid; detector, UV at 370 nm; temperature, 45 degrees C), the linearity of calibration was in the range 0.1 - 10 ppm for both phosphate and silicate ions, and the detection limits at S/N = 3 were 2.58 ppb for silicate ions and 4.75 ppb for phosphate ions. The effectiveness of this method was demonstrated in practical applications to the water-leaching process for some ceramics glaze raw materials.     

Separation of fulvic acid from soil extracts based on ion-pair formation with a cationic surfactant.

A novel method for separating fulvic acid (FA) from soil extracts is proposed. The FA, defined as the acid-soluble fraction of an alkaline extract of soil, was separated based on the precipitation of an ion-pair with a cationic surfactant, such as domiphen bromide. The precipitate was dissolved in aqueous HCl to produce H+ -type FA and a surfactant chloride (SUR-Cl). SUR-Cl, in the aqueous solution, was removed by extraction with CHCl3. After the aqueous phase was passed through a cation-exchanger (H+ -type), H+ -type FA (FA-SUR) was obtained as a powder by lyophylization. The chemical characteristics of FA-SUR were compared with an FA sample separated according to the method of the International Humic Substances Society using a DAX-8 resin (FA-DAX). The oxygen content, O/C atomic ratio and total acidity of the FA-SUR were significantly larger than the corresponding values for FA-DAX. The solid-state CPMS 13C NMR spectra indicated that the higher oxygen content of the FA-SUR could be due to alcoholic hydroxyl groups and polysaccharides as well as carboxylic groups. These results show that FA-SUR is more polar and hydrophilic than FA-DAX.     

Studies on the syntheses of heterocyclic compounds. CLXXIV. An approach to the synthesis of oxyacanthine and berbamine

Schotten-Baumann reaction of the amine (X) with 4-benzyloxy-3,4′-oxydiphenylacetyl chloride (XI) gave two amides, (XIIa) and (XIIb), which were cyclized to give the corresponding 3,4-dihydroisoquinolines, respectively. Methylation of the above 3,4-dihydro-isoquinolines, followed by hydrolysis, afforded the compounds having the same composition as berbamine (Ia) and oxyacanthine (Ib), whose structures are under examination.     

Synthesis and antitumor activities of mitomycin C (1----3)-beta-D-glucan conjugate.

The conjugate of mitomycin C (MMC) with linear (1----3)-beta-D-glucan from Alcaligenes faecalis var. myxogenes IFO 13140 was synthesized and its antitumor activities investigated. The conjugate (MMC-carboxymethylated linear (1----3)-beta-D-glucan (CMPS)) was obtained by treatment of CMPS with MMC in the presence of 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide. In vitro cytotoxicity of MMC-CMPS against L1210 leukemia cells was similar to that of MMC. In i.p.-i.p. system in vivo against P388 leukemia in mice, the maximum increase of MMC-CMPS conjugate in life span (ILSmax) was higher than that of MMC but the therapeutic index was reduced. However, the antitumor activity of MMC-CMPS conjugate against subcutaneously implanted sarcoma 180 solid tumor in mice by i.p. administration was similar to that of MMC at a dose of 1.5 mg eq MMC/kg/d x 7 and the reduction of the number of leukocytes caused by MMC was suppressed by attaching MMC to CMPS. In addition, on assay using serum of sarcoma 180 solid tumor-bearing mice with injection of MMC-CMPS conjugate, a drastic loss of tumor cells and an increase in polymorphonuclear leukocytes (PMN) were observed. This result suggested that MMC-CMPS conjugate induced tumor-regressing factor similar to CMPS.     

Statistical mechanical treatment of protein conformation. III. Prediction of protein conformation based on a three-state model.

The method proposed for the evaluation of statistical weights in paper I, and the three-state model [alpha-helical (alpha), extended (epsilon), and other (c) states] formulated in paper II, have been used to develop a procedure to predict the backbone conformations of proteins, based on the concept of the predominant role played by shortrange interactions in determining protein conformation. Conformational probability profiles, in which the probabilities of formation of three consecutive alpha-helical conformations (triad) and of four consecutive extended conformations (tetrad) have been defined relative to their average values over the whole molecule, are calculated for 19 proteins, of which 16 had been used in paper I to evaluate the set of statistical weights of the 20 naturally occurring amino acids. By comparing these conformational probability profiles to experimental x-ray observations, the following results have been obtained: 80% of the alpha-helical regions and 72% of the extended conformational regions have been predicted correctly for the 19 proteins. The percentage of residues predicted correctly is in the range of 53 to 90% for the alpha-helical conformation and in the range of 63 to 88% for the extended conformation for the 19 proteins in the two-state models [alpha-helical (alpha) and other (c) states, and extended (epsilon) and other (c) states]. In the three-state model, the percentage of residues predicted correctly is in the range of 47% to 77 for 19 proteins. These results suggest that the assumption of the dominance of short-range interactions, on which the predictive scheme is based, is a reasonable one. The present predictive method is compared with that of other authors.     

Targeting of mitomycin C to the liver by the use of asialofetuin as a carrier.

Desialylated fetuin (asialofetuin) was adopted as a carrier for introducing drugs in parenchymal liver cells. Mitomycin C, as a model guest-compound, was covalently attached to asialofetuin through a spacer of the succinyl group. The asialofetuin-mitomycin C conjugate contained 4.4 w/w% of mitomycin C and liberated it gradually at physiological conditions (t1/2 = 37 h). The survival time of the conjugate in rat blood circulation was significantly smaller than that of the non-desialylated fetuin conjugate; the elimination half-life was 7.3 min after intravenous injection. At 30 min after injection of the conjugate in rats, 40% of the dose was present in the liver. Parenchymal cells in the liver selectively took up the conjugate, which was highly distributed to the lysosomal fraction in the cell. The greater uptake of the conjugate by hepatocytes reflected the increased excretion in the bile; totally 10.4% of the dose was recovered.     

Studien Über die Saponine aus der Arznei-Ginseng-Wurzel: Massenspektren von Ginsenoside-Rg1-Decaacetat und Verwandten Verbindungen

Mass spectra of ginsenoside-Rg1 deca-acetate

1 Siehe Lit.2.

and the related dammaran-type triterpene saponin acetates have been studied and a comment is given on the structure of panaxoside A (=ginsenoside-Rg1) proposed by Elyakov, et al .