Determination of sulfate in river water by flow injection analysis

Sulfate ion in river water is determined by flow injection analysis at a rate of 30 samples per hour; the sulfate contents are typically less than 30 ppm. The reagent solution contains dimethylsulfonazo-III, barium chloride, potassium nitrate and chloroacetate buffer in 70% ($\text{v}\text{v}$) ethanol, and is saturated with barium sulfate. The aqueous carrier stream is also saturated with barium sulfate. The sample is filtered and treated with Amberlite IR120-B cation-exchanger before injection into the carrier stream, and the decoloration of the barium—dimethylsulfonazo-III complex by sulfate is measured at 662 nm. The calibration graph is linear over the range 0–30 μg ml^-1 for sulfate in water.     

Vinyl polymerization. CCCXXXIX. Effect of chain length of nylon 3 on the polymerization of methyl methacrylate initiated with the system of nylon 3, copper(II) ion,and water

It was found recently that the system of nylon 3, copper(II) ion, and water could initiate a radical polymerization of methyl methacrylate(MMA). In the present paper, the effect of average chain length of the molecules of nylon 3 on the rate of polymerization of MMA was studied. The rate increased with the chain length of nylon 3. This result was explained well by the fact that the shorter nylon 3 forms a complex with copper (II) ion more easily than longer nylon 3. It was assumed that the shorter nylon 3 fills three or four coordination sites of copper(II) ion and loses the ability to initiate the polymerization. The efficiency of grafting of MMA and the degree of polymerization of MMA homopolymer were independent of the chain length of nylon 3.     

Cyclopalladation of the indole ring in palladium(II) complexes of 2N1O-donor ligands and its dependence on the O-donor properties

Synthetic, structural, spectroscopic, and kinetic studies have been carried out on the Pd(II) complexes of new 2N1O-donor ligands containing a pendent indole, 3-(N-2-pyridylmethyl-N-2-hydroxy-5-methoxybenzylamino)ethylindole (HMeO-iepp), 3-(N-2-pyridylmethyl-N-2-hydroxy-5-nitrobenzylamino)ethylindole (HNO2-iepp), and (N-2-pyridylmethyl-3-indolylethylamino)acetic acid (Hiepc) (H denotes a dissociable proton). [Pd(MeO-iepp)Cl] (2), [Pd(NO2-iepp)Cl] (3), and [Pd(iepc)Cl] (4) were prepared and revealed by X-ray analysis to have a pyridine nitrogen, an amine nitrogen, a phenolate or carboxylate oxygen, and a chloride ion in the coordination plane. UV absorption and 1H NMR spectral changes indicated that all the complexes could be converted to the indole-binding complexes where the O donor was replaced by the indole C2 atom by cyclopalladation in DMSO or DMF in the temperature range of 40-60 degrees C. Formation of the indole-binding complex species obeyed the first-order kinetics, from which the activation parameters were estimated. The formation rate was dependent on the properties of the O-donor group, a lower pKa value of its conjugate acid causing faster conversion to the indole-binding species in the order 2 (methoxyphenolate) < 3 (nitrophenolate) < 4 (carboxylate). On the other hand, the ratio of the indole-binding complex to the O-donor complex as a result of the conversion was greater for the complexes with a higher pKa value of the ligand OH group, the order being 2 > 3 > 4.     

Cyclopolymerization of diallylamine derivatives in dimethyl sulfoxide

Diallyl quaternary ammonium chlorides, bromides and N-alkyldiallylamine hydrochlorides were polymerized with ammonium persulfate (APS) in dimethyl sulfoxide (DMSO). The dependences of yield and molecular weight of polymers on polymerization conditions were examined and quaternary ammonium chlorides were found to have better polymerizability than bromides. The poly(diallyl quaternary ammonium chlorides) obtained with APS—DMSO system are expected to have quite high molecular weights, as determined from the measurement of limiting viscosity numbers of the polymers in NaCl aqueous solution.     

Systematic enantiomeric separation of [60]fullerene bisadducts possessing an inherent chiral addition pattern

The optical resolution of trans-2 and trans-3 [60]fullerene bisadducts with an inherent chiral addition pattern, modified by Bingel reaction, cycloaddition by benzyne, Prato reaction, and cycloaddition by o-quinodimethane, was systematically investigated by using chiral HPLC columns (Chiralcel OD and Chiralpak AD). The chiroptical properties of enantiomers separated were also examined.     

Phylogenetic analysis of picoplankton in Lake Biwa and application to legal medicine

Three strains of picoplankton designated as brown, green, and pink belonging to the Synechococcus genus in cyanobacteria (approximately 1 microm in size) are found ubiquitously in Lake Biwa, Japan. However, they could not be morphologically discriminated from other bacteria such as Proteobacteria and Bacillus by microscopy. In this study, we attempted to use the polymerase chain reaction (PCR) analysis of the 16S ribosomal DNA (rDNA) from picoplankton for the diagnosis of death by drowning. A segment of 16S rDNA was sequenced in order to investigate their phylogenetic relationships and to design the specific primers. The PCR products from three picoplanktons were compared with those from five other cyanobacteria, Melosira (diatom), Staurastrum (green alga), bacteria from Lake Baikal, and humans. The picogram order of template DNA from picoplankton was specifically amplified by the primers. When the template of picoplankton was mixed with human tissue, at least 10 ng of template DNA was needed to obtain a PCR product. The efficiency of PCR was increased more than hundredfold by isolating the picoplankton from human lung tissue. The specific PCR products of the picoplankton were obtained from a formalin-fixed drowning body (lung and liver) that was found in a downstream river and Lake Biwa. The PCR analysis of the picoplanktion 16S rDNA is considered useful for the diagnosis of death by drowning.     

Polymers having stable radicals. II. Synthesis of nitroxyl polymers from 4-methacryloyl derivatives of 1-hydroxy-2,2,6,6-tetramethylpiperidine

Polymers having stable pendant . radicals were synthesized through their precursor polymers by oxidizing them in air or by H₂O₂–Na₂WO₄. Hydrochlorides and sulfates of 4-methacryloylamino- and 4-methacryloyloxy-1-hydroxy-2,2,6,6-tetramethylpiperidines were synthesized as precursor monomers and polymerized by using α,α′-azobisisobutyronitrile under appropriate conditions to precursor polymers of high molecular weight: poly-4-methacryloylamino-/oxy-1-hydroxy-2,2,6,6-tetramethylpiperidinehydrochlorides and sulfates. The precursor polymers were converted to polymers having nitroxyl stable radicals, i.e., poly-4-methacryloylamino-/oxy-2,2,6,6-tetramethylpiperidine-1-oxyls, by oxidation in air or with H₂O₂–Na₂WO₄ without any main-chain scission. The structure of the resultant stable radical polymers was determined by infrared, ultraviolet, and ESR spectroscopy. Based on the results of spectroscopic analysis and Kjeldahl analysis, the transformation from precursors to nitroxyl stable radical polymers was found to be quantitative. Investigations on the applicability of polymeric nitroxyl radicals to oxidation-reduction reactions were attempted by means of polarography; the reduction half-wave potential was found to be ?1.16 V for the mercury pool.     

Application of 1,2,3,5,6,7-hexahydropyrrolizinium perchlorate in the synthesis of 7a-substituted hexahydro-1h-pyrrolizines

The method for preparing 7a-substituted hexahydro-1H-pyrrolizines 2 from 1,2,3,5,6,7-hexahydropyrrol-izinium Perchlorate (3) was investigated, by which introduction of a wide variety of functionalities on C(7a) could be achieved easily.     

Coenzyme models. 32. Catalytic activity of polymer-bound thiazolium ions as estimated by flavin trapping technique

Three thiazolium-containing polymers, Th-7, Th-33, and Th-18-Py [where Th-x and Py mean x mol % thiazolium unit and pyridinium unit (54 mol %), respectively], were synthesized from partially p-chloromethylated polystyrene. The catalytic activities of these polymer catalysts in acyloin condensation of aldehydes and decarboxylation of α-keto acids were estimated kinetically by oxidative trapping of the key intermediate by flavin (flavin-trapping technique). In aqueous solution at 30°C, the catalytic activity of Th-18-Py and Th-33 in condensation of p-chlorobenzaldehyde was comparable with that of the cationic-micelle-bound thiazolium ion, whereas Th-7 and a monomeric thiazolium compound (N-benzylthiazolium bromide) scarcely exhibited any catalytic activity. The catalysis of the polymer-bound thiazolium ions was sensitively suppressed by increased ionic strength. These results suggest that the pendent thiazolium ion is activated by the relatively high charge density along the polymer chain: the cationic environment is able to facilitate dissociation of the thiazolium ion to the ylid form and deprotonation of the thiazolium-aldehyde adduct to the key intermediate.     

Temperature-induced gelation of concentrated silicon carbide suspensions

Due to the steric barrier provided by the adsorption of the dispersant hypermer KD1 (a polyester/polyamine condensation polymer), stable and low-viscosity suspensions of SiC, Y(2)O(3), and Al(2)O(3) powder mixtures could be prepared in methyl ethyl ketone (MEK)/ethanol (E) solvent with solids loading as high as 60 vol%. The solvency of the dispersant in MEK/E decreased dramatically on cooling. Steady shear viscosity and oscillatory measurements were performed as a function of temperature for suspensions with different solids loading. The viscosity and elastic modulus of suspension increased with decreasing temperature and became more sensitive with the increase of solids loading. The suspensions with solids loading higher than 40 vol% could be solidified with decreasing temperature, but gelation temperature and gelation stiffness decreased with decreasing solids loading. The 60 vol% solid-loaded suspension was a stable and free-flowing fluid at 20 degrees C and gradually transformed to a very highly viscous and elastic system upon cooling to about 13 degrees C. Complete solidification occurred when the temperature was decreased to 5 degrees C. The gelation mechanism was mainly based on the collapse of the adsorbed layer as the temperature decreases, which induced incipient flocculation and formed a stiff network. The gelled body was further strengthened by separation of the dispersant from the suspension.