Study on decontamination of radioactive ruthenium by steel wool in waste solution (author's transl)

Tracer experiments were done in order to establish a decontamination process of 106Ru in radioactive waste solution by column method paying special attention on the solution of nitratonitrosyl complex of Ru which is often encountered as a low level radioactive waste solution. It turned out that metallic iron was the most effective decontaminating agent among the several tens of materials tested. The decontamination factor (DF) of 106Ru increased in proportion to the total surface area of iron and it sensitively depended on the oxidation state of the surface as revealed by the batchwise and columnwise tests. Iron samples with high corrosiveness gave a much larger DF than those with low corrosiveness. The decontamination process proceeded as iron was being oxidized via Fe(metal)leads toFe(II)leads toFe(III). As the results, the DF initially increased after initiating the passage of water through the column but it then decreased as the oxidation process became inactive. An excellent durability up to 10000 bed volumes was demonstrated by the column method at a high average DF of 150.     

Michael addition of stannyl ketone enolate to alpha,beta-unsaturated esters catalyzed by tetrabutylammonium bromide and an ab initio theoretical study of the reaction course

Michael addition of stannyl ketone enolates to alpha,beta-unsaturated esters was accomplished in the presence of a catalytic amount of tetrabutylammonium bromide (Bu(4)NBr). Other typical systems using lithium enolate or silyl enolate with catalysts (TiCl(4) or Bu(4)NF) failed to give the desired products. The bromide anion from Bu(4)NBr coordinates to the tin center in enolate to accelerate the conjugate addition where a five-coordinated tin species was generated. The coordination of the bromide anion significantly raises the HOMO level of tin enolate and enhances its nucleophilicity. The conjugate addition provides the intermediate Michael adduct, which has an ester enolate moiety, and the adduct immediately transforms to alpha-stannyl gamma-ketoester by keto-enol tautomerization. This step contributes to the stabilization of the product system and leads to a thermodynamically favorable reaction course. An ab initio calculation reveals that the activation energy in the reaction using the bromide anion is lower than that of the reaction without using it. The transition state in either reaction course has a linear structure, not a cyclic one. This system can be applied to a variety of tin enolates and alpha,beta-unsaturated carbonyls involving enoates, enones, and unsaturated amides.     

Solid phase extraction of lead by Chelest Fiber Iry (aminopolycarboxylic acid-type cellulose)

Aminopolycarboxylic acid-type cellulose (Chelest Fiber Iry) has been studied for its sorption efficiencies with respect to lead from acidic solution. The influence pH and other properties related to sorption kinetic, isotherm, maximum capacity, stability and the mechanism of the sorption were discussed.Lead was quantitatively retained on the proposed adsorbent in the pH range of 2.5-5.5 (studied pH range 1.5-5.5). The maximum sorption capacity was found to be 0.86±0.06 mmol/g adsorbent. The decline in the efficiency of the adsorbent was not observed for repeated adsorption-desorption cycles. It was found that the preconcentration factor of 200 can be achieved. The limit of determination was found to be about 1 μg Pb/2 l. The method was applied to the determination of lead in water samples.     

Theoretical study of the transesterification reaction of polyethylene terephthalate under basic conditions

The depolymerization reaction of polyethylene terephthalate (PET) was analyzed using a computational chemistry approach. The reaction is a type of transesterification reaction using alkoxide. In this study we employed the calculated optimum structure, electrostatic potential distribution, activation energy, electric charges and pathway to investigate the mechanism. We found that the tetrahedral intermediate produced by ring formation with alkoxide is an essential feature of the depolymerization process. Moreover, there is a possibility that a PET molecule is depolymerized by multiple alkoxides at the same time. However, the effects of degree of polymerization and the position of attack by the alkoxides do not strongly influence the reactivity.     

Attomole catechins determination by capillary liquid chromatography with electrochemical detection.

Attomole quantities of catechins were determined by a capillary liquid chromatography system with electrochemical detection (CLC-ECD) and the system is applied to the determination of catechins in human plasma. The eight catechins: catechin (C), epicatechin (EC), gallocatechin (GC), epigallocatechin (EGC), catechin gallate (Cg), epicatechin gallate (ECg), gallocatechin gallate (GCg), and epigallocatechin gallate (EGCg), were separated within 10 min using a capillary column (0.2 mm i.d.) and a mobile phase of phosphoric acid (85%)-methanol-water (0.5:27.5:72.5, v/v/v), and were detected at +0.85 V vs. Ag/AgCl. Peak heights were found to be linearly related to the amount of catechins injected, from 200 amol to 500 fmol (r > 0.998). The detection limits of the catechins were 61 amol for EGC, 75 amol for EC, 54 amol for GC, 61 amol for C, 67 amol for GCg, 75 amol for EGCg, 75 amol for ECg and 89 amol for Cg (S/N = 3). Because the present method is highly sensitive and allows facile pretreatment for plasma sample, the time courses of concentrations of catechins (GCg, EC, EGCg, ECg, and Cg) and their conjugates in human plasma obtained from a 10 microl plasma sample after ingestion of green tea could be determined.     

Indium-Catalyzed C−F Bond Transformation through Oxymetalation/β-Fluorine Elimination to Access Fluorinated Isocoumarins

Fluorinated heterocycles have attracted much attention in the pharmaceutical and agrochemical industries. Many strategies have already been developed to achieve the synthesis of fluorinated heterocycles. Formidable challenges remain, however, in the synthesis of fluorinated isocoumarin derivatives that are among the most alluring structural motifs. Herein, the indium-catalyzed C−F bond transformation of 2-(2,2-difluorovinyl) benzoates is reported, which are readily accessible compounds, to give a diverse array of fluorinated isocoumarins. The present reaction proceeds smoothly using inexpensive reagents: a catalytic amount of indium salt in the presence of zinc salt. A theoretical calculation of potential energy profiles showed that the reaction consists of oxymetalation with the elimination of alkyl halide and the β-fluorine elimination.     

Preparation of new nitrogen-bridged heterocycles 72. A new approach to 1-acyl-3-(substituted methylthio)thieno[3',4':4,5]imidazo[1,2-a]pyridine derivatives. [corrected

The alkaline treatment of the pyridinium salts, readily available from the S-alkylations of 3-amino-4-(1-pyridinio)thiophene-5-thiolates with various alkyl halides, in chloroform at room temperature afforded the corresponding thieno[3',4':4,5]imidazo[1,2-a]pyridine derivatives in low to moderate yields via the intramolecular cyclization of the resulting 1,5-dipoles followed by the aromatization of the primary cycloadducts. Interestingly, the reactions using unsymmetrical 3-amino-4-[1-(3-methylpyridinio)]thiophene-5-thiolates afforded only 8-methylthieno[3',4':4,5]imidazo[1,2-a]pyridines and the other 6-methyl derivatives were not formed at all. In addition the isolation of a byproduct in the condensation reaction of pyridinium salt with the solvent (CHCl?) is also discussed.     

Bidirectional Chemo‐Switching of Spin State in a Microporous Framework

The ins and outs of spin : Using the microporous coordination polymer {Fe(pz)[Pt(CN)₄]} ( 1 , pz=pyrazine), incorporating spin‐crossover subunits, two‐directional magnetic chemo‐switching is achieved at room temperature. In situ magnetic measurements following guest vapor injection show that most guest molecules transform 1 from the low‐spin (LS) state to the high‐spin (HS) state, whereas CS₂ uniquely causes the reverse HS‐to‐LS transition.

     

Inside Cover: Bidirectional Chemo‐Switching of Spin State in a Microporous Framework (Angew. Chem. Int. Ed. 26/2009)

Bidirectional chemo‐switching of magnetism occurs in a microporous coordination polymer containing spin‐crossover subunits, as described by M. Ohba, J. A. Real, S. Kitagawa, and co‐workers in their Communication on page 4767 ff. In situ magnetic measurements reveal that most guest molecules transform the framework spin state from diamagnetic low spin (red) to paramagnetic high spin (yellow), whereas the guest CS₂ stabilizes the low‐spin state. These induced spin states are retained as a memory effect after the release of the guest.