Template-directed DNA photoligation via alpha-5-cyanovinyldeoxyuridine

[reaction: see text] We describe an efficient template-directed photoligation of oligodeoxynucleotides (ODNs) using alpha-5-cyanovinyldeoxyuridine (alpha(C)U). An efficient photoligation was produced by photoirradiation of an ODN containing alpha(C)U at the 3' end with an ODN containing thymine at the 5' end in the presence of a template ODN. This photoligation method is a new and efficient way to synthesize branched ODNs.     

Adsorption of phosphate from seawater on calcined MgMn-layered double hydroxides

Adsorptive properties of MgMn-3-300 (MgMn-type layered double hydroxide with Mg/Mn mole ratio of 3, calcined at 300 degrees C) for phosphate were investigated in phosphate-enriched seawater with a concentration of 0.30 mg-P/dm3. It showed the highest phosphate uptake from the seawater among the inorganic adsorbents studied (hydrotalcite, calcined hydrotalcite, activated magnesia, hydrous aluminum oxide, manganese oxide (delta-MnO2)). The phosphate uptake by MgMn-3-300 reached 7.3 mg-P/g at an adsorbent/solution ratio of 0.05 g/2 dm3. The analyses of the uptakes of other constituents (Na+, K+, Ca(+, Cl-, and SO(2-)4) of seawater showed that the adsorbent had a markedly high selectivity for the adsorption of phosphate ions. Effects of initial phosphate concentration, temperature, pH, and salinity on phosphate uptake were investigated in detail by a batch method. The phosphate uptake increased slightly with an increase in the adsorption temperature. The adsorption isotherm followed Freundlich's equation with constants of logK(F)=1.25 and 1/n=0.65, indicating that it could effectively remove phosphate even from a solution of markedly low phosphate concentration as well as with large numbers of coexisting ions. The pH dependence showed a maximum phosphate uptake around pH 8.5. The pH dependence curve suggested that selective phosphate adsorption progresses mainly by the ion exchange of HPO(2-)4. The study on the effect of salinity suggested the presence of two kinds of adsorption sites in the adsorbent: one nonspecific site with weak interaction and one specific site with strong interaction. The effective desorption of phosphate could be achieved using a mixed solution of 5 M NaCl + 0.1 M NaOH (1 M = 1 mol/dm3), with negligible dissolution of adsorbent. The adsorbent had high chemical stability against the adsorption/desorption cycle; it kept a good phosphate uptake even after the repetition of the seventh cycle.     

Crystal structures of n-alkanes with branches of different size in the middle

We synthesized four branched n-alkane samples C35-C1, C35-C4, C35-C6, and C35-C4Ph with the same number of carbons as the main chain, n = 35, to which the methyl, butyl, hexyl, and butyl phenyl groups were respectively attached at the middle, and also the corresponding linear homologue of C35, and studied their crystalline structures from DSC, IR, and Raman spectroscopy, X-ray diffraction measurement, and computer simulation. Solid-solid phase transitions characteristic of linear alkane C35 are not observed for any branched alkanes, and their melting temperatures Tm are lowered to 325.2, 318.5, 314.3, and 314.1K, respectively. Main chains of branched alkane molecules are not folded, irrespective of length and chemical structure of branches, but are extended to take the planar zigzag form in the solid state. The branches of C35-C4 and C35-C6 are also aligned inside the crystal in the extended form. Data analyses on solution-grown crystallized samples reveal that, with increasing the branch length, their crystal structures transform from polymorphic forms of the orthorhombic (P2(1)2(1)2(1)) and the triclinic (P) for C35-C1 and C35-C4 to the unique triclinic form for C35-C6 and C35-C4Ph, so as to minimize extra surface energy invoked by introduction of long branches.     

Polymer modification of colloidal particles by spontaneous polymerization of surface active monomers

Adsorption and spontaneous polymerization of head- or tail-type surface active monomers having long methylene chains on colloidal silica and δ-alumina were investigated. Both head-type and tail-type ammonium monomers on silica in chloroform or tetrahydrofuran had the maximum adsorption on the respective adsorption isotherm. Above the monomer concentration giving the maximum adsorption, it was observed that the monomer formed micelles or clusters in bulk solution with removal of adsorbed water molecules from the silica surface. At the monomer concentration giving the maximum adsorption, heating the silica suspension containing the monomer at 40°C or 60°C in tetrahydrofuran or chloroform solution resulted in spontaneous polymerization. The composite particles formed by polymerization were observed to have many spots consisting of polymer on the surface. Therefore, it is suggested that the monomers are concentrated by micelle-like aggregation on the silica surface and consecutively spontaneous polymerization takes place. Adsorption of an anion-type monomer having a carboxyl group on δ-alumina, which exhibited a positive ζ potential in neutral aqueous solution, was higher than that on colloidal silica, but did not spontaneously polymerize on alumina. Received: 13 June 1998 Accepted in revised form: 19 August 1998     

Comparison of standard materials for the establishment of calibration curves in solid sampling graphite furnace atomic absorption spectrometry. Direct determination of copper in powdered biological samples

Summary The selection of standard materials for the establishment of calibration curves is one of the most important problems in the direct analysis of biological samples by GFAAS. Three kinds of standard materials, NBS tomato leaves, coprecipitates with magnesium oxinate and Ni/DMG/PAN were investigated. It was found that it is possible to use both the NBS-SRM and the synthetic reference material prepared by coprecipitation with magnesium oxinate as standard materials for the direct determination of copper in several biological samples issued from NBS and NIES. However, too low results are obtained when the synthetic reference material prepared by coprecipitation with Ni/DMG/PAN is used. In order to clarify this, the effects of nickel and magnesium were examined and the role of magnesium was discussed.     

Cu-Chelex as a selective adsorbent for o-nitroso derivatives of phenolic substances

Summary Chelex resins in several metal forms were tested for selective uptake of o-nitrosonaphthols and o-nitrosophenols from aqueous solution. Cu-Chelex was the most efficient resin over a wide pH range, and the taken-up nitroso compounds were effectively eluted with concentrated ammonia: acetonitrile (4:1, v/v) after washing the resin with acetonitrile to eliminate non-specific binding. The upper and lower limits of uptake capacity of the resin for 1-nitroso-2-naphthol were 0.5 mol/100 mg and 1.25 mol/100 mg, respectively. A preliminary recovery experiment using urine and cucumber juice showed that Cu-Chelex would be useful for screening of o-nitroso derivatives of phenolic substances in complicated samples such as biological fluids and foods.     

Preparation of monodispersed polymer-modified colloidal silica particles of less than 50 nm diameter

The preparation of monodisperse, ultrafine polymermodified colloidal silica, 11 or 42 nm in diameter, were studied. The reaction of the colloidal silica with polymeric silane coupler in 1,2-dimethoxyethane and removal of the unreacted polymer with granular silica gel (10–20 mesh) in acetone gave a suspension of monodisperse composite particles.     

Development of a new software for the X-ray structural analysis of polymer crystals by utilizing the X-ray imaging plate system

A software and some useful tools have been developed for identifying individual x-ray reflectional peaks recorded with an x-ray imaging plate system. These techniques were applied to analyze the crystal structure of uniaxially oriented polymer samples. Characteristic features of the present method may be summarized as follows. (1) The indexing of the observed reflections and the determination of the unit cell parameters can be made easily on the display of the computer. (2) The integrated intensity of the individual component of the overlapped reflections can be evaluated quantitatively through the curve separation technique. The R_merge's for the equivalent reflections were 5–6%, indicating the exact evaluation of the integrated intensities. (3) The thus obtained reflectional data were successfully utilized for the extraction of the initial structural models by the direct method. The actual applications have been made for orthorhombic polyethylene, trigonal polyoxymethylene, and isotactic polybutene-1, giving the refined crystal structures including even the positions of hydrogen atoms in some cases. The reliability factors were 12, 5, and 15%, respectively, for these three polymer cyrstals. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1677–1700, 1997     

An effective cross-linking of polymer layer on monodisperse, poly(maleic anhydride-styrene)-modified colloidal silica particles and properties of the composite

Summary  The cross-linkings of the surface polymer layer on mono disperse, poly(maleic anhydride-styrene)-modified silica particles by the reaction with diisocyanate were studied. The extent of cross-linking was estimated by the weight decrease by immersing the particles in the buffer solution of pH 2.0, 4.0 and 9.0 at a room temperature for 24 h. The reaction of the polymer-modified silica with 1,6-diisocyanatohexane afforded relatively stable composite particles which lost less than 5 wt% of the polymer in aqueous solution in the pH range 2.0–9.0. The diisocyanate was a preferable cross-linker to 2,4-diisocyanatotoluene in terms of stability in acidic or basic aqueous solution. The flexibility of the cross-linker molecule possibly plays an important role in the cross-linking reaction. The carboxyl and amino groups were formed by treating the cross-linked composite particles with diluted HCl solution; 5–6 and 0.5–1.1 μmol g^-1, respectively. The cross-linked composite particles exhibited the characteristic property of ζ-potential, −44 to −47 mV and −102 to −107 mV in a neutral aqueous solution and ethanol, respectively. Received: 26 May 1997 Accepted: 4 August 1997