Application of europium(III) extraction with organophosphinic acid to liquid membrane transport

The extraction behavior of Eu(III) has been studied using di(2,4,4-trimethylpentyl)phosphinic acid (DTMPPA, HA) in kerosene. Europium was extracted as Eu(HA₂)₃ with the extraction constant of 2.0·10^–3. This extraction system was applied to the transport of Eu(III) across a DTMPPA liquid membrane supported on porous polytetrafluoroethylene. Europium was quantitatively moved through the liquid membrane containing 0.1M (HA)₂ as a mobile carrier from the feed solution of pH above 3 into the product solution of 0.1M HNO₃, yielding a concentration factor of ten. The transport rate increased with increasing pH and DTMPPA concentration.     

A temperature study on critical micellization concentration (CMC), solubility, and degree of counterion binding of α-sulfonatomyristic acid methyl ester in water by electroconductivity measurements

 For a sodium salt of α-sulfonatomyristic acid methyl ester (14SFNa), one of the α-SFMe series surfactants, critical micellization concentration (CMC), solubility and degree of counterion binding (β) were determined by means of electrocon-ductivity measurements at different temperatures (at every 5 °C) ranging from 15 to 50 °C. The phase diagram of 14SFNa in pure water was constructed from the CMC- and solubility-temperature data, in which the Krafft temperature (critical solution temperature) was found around 0 °C. The changes in the Gibbs energy, ΔG ⁰ _m, enthalpy, ΔH ⁰ _m, and entropy, ΔS ⁰ _m, upon micelle formation as a function of temperature were evaluated taking βvalues into calculation. Received: 28 August 1996 Accepted: 5 November 1996     

Multilayer vesicles and vesicle clusters formed by the fullerene-based surfactant C60(CH3)5K

The self-assembly behavior of a fullerene-based surfactant, C60(CH3)5K, in water was studied using a combination of static and dynamic light scattering, as well as transmission electron microscopy, and compared to that of the compound C60(C6H5)5K. Both fullerene surfactant systems spontaneously assemble into large vesicles consisting of closed spherical shells formed by bilayers, with critical aggregation concentrations (CAC) lower than 10(-6) g ml(-1). At low concentrations, the aggregate sizes of C60(CH3)5K (radius R approximately 26.8 nm) and C60(C6H5)5K (R approximately 17.0 nm) were found to be substantially different from each other, showing that the change of the substituents surrounding the polar cyclopentadienide head group makes it possible to control the size of the resulting aggregates. Furthermore, the C60(CH3)5K vesicles were found to exist in two qualitatively different types of aggregation with a critical reaggregation concentration (CRC) located at 3.30 x 10(-6) g ml(-1). Above the CRC, larger aggregates were observed (R approximately 37.6 nm), showing a more complex form of supramolecular aggregation, e.g., in terms of multi-bilayer vesicles and/or of clusters of bilayer vesicles.     

Regioselective syntheses of 7-nitro-7-deazapurine nucleosides and nucleotides for efficient PCR incorporation

Substitution at the C(7) position of purine nucleotides by a potent electron-withdrawing nitro group facilitates the cleavage of glycosidic bonds under alkaline conditions. This property is useful for sequence-specific cleavage of DNA containing these analogues. Here we describe the preparation of 7-deaza-7-NO(2)-dA and 7-deaza-7-NO(2)-dG using two different approaches, starting from 2'-deoxy-adenosine and 6-chloro-7-deaza-guanine, respectively. These modified nucleosides were converted to nucleotide triphosphates, each of which can replace the corresponding, naturally occurring triphosphate to support PCR amplification. [structure: see text]     

Analysis of Dns-amino acids by liquid chromatography. I. Selection of optimum mobile phase composition for separation of Dns-amino acids on polyvinyl acetate gel.

The separation of a mixture of ten Dns-amino acids (Gns-Gly, -Ala, -Val, -Leu, -Pro, -Hypro, -Met, -Ser, -Asn and -Gln) was carried out by liquid chromatography by using macroreticular polyvinyl acetate gel as a packing material. Different mobile phase systems were investigated, based mainly on mixtures of n-hexane with ethanol, methanol, chloroform, acetone, methyl ethyl ketone, ethyl acetate, dioxane and tetrahydrofuran. The solvent composition was fixed so as to elute all of the components of the sample mixture in a practical period of 2 h. Satisfactory separation of the ten components was obtained with the n-hexane-ethanol (90:10) system. The presence of methanol as a modifier in the n-hexane was effective in reducing the elution time, but the separation was not as satisfactory. Chloroform or dioxane was useful only for the separation of Ser, Asn and Gln. Acetone, methyl ethyl ketone, ethyl acetate and tetrahydrofuran were not suitable for practical separations of Dns-amino acids.     

Salt effect in the base-catalyzed polymerization of unsaturated amide compounds. III. Nature of the polymerization system

Coordination complexes of lithium chloride with polar solvents and monomers were isolated, and their physical properties were studied. The parallel between stabilities of isolated complexes and coordination function in the polymerization system is discussed. The increase of the Q and e values of p-vinylbenzamide (VBA) supports the mechanism of vinyl-type polymerization of VBA in the presence of the salt. The specific solvent effect of dimethyl sulfoxide was determined by measurement of electrical conductivity of a model system.     

Application and limitation of a mathematical distortion model of an absorbance signal in electrothermal atomic absorption spectrometry

A distortion model of instrumental function is described, based on the response signal. Its limitations are investigated by using quasi-signals generated by an oscillator and a moving carbon rod.     

Isomerization polymerization of β-propiolactones carrying side-chain ester groups

Based on our recent discovery of the isomerization polymerization of β-(2-acetoxyethyl)-β-propiolactone into poly-δ-ester,^1,2 we examined the generality of this phenomenon by using two related monomers. The catalysts were (EtAlO)_n and Et(ZnO)₂ZnEt. The side-chains in the monomers selected were the (CH₃)₂CHCOO? CH₂CH₂? (2) and (CH₃)CICHCOO? CH₂CH₂? (3) groups in which steric effects are almost identical but electronic effects are in opposition. The monomers yielded isomerized poly-δ-ester units, depending on the terminal substituent groups in the side-chain. These observations can be interpreted with the bicyclic intermediate proposed in the earlier work. Monomer (2) was reactive and produced a poly-δ-ester structure most readily, probably because of the higher electron density at the side-chain ester group which coordinated with the catalyst. In contrast, monomer (3) was less reactive, and the probability of isomerization was the lowest, i.e., the electron deficient side-chain ester group apparently interfered with the formation of the intermediate, especially in the Zn-catalysis. Equibinary random copolymers were prepared from (2) and (3) according to the catalyst and polymerization conditions chosen.     

Thermal decomposition of the solvent-extracted chloro complexes of vanadium(IV) with trioctylamine and trioctylmethylammonium chloride

The complexes (R₃NHVO(OH)Cl₂)₂ and (R₃RNVO(OH)Cl₂)₂ prepared by drying in vacuo the organic solutions from the extraction into benzene of aqueous vanadyl chloride solution with trioctylamine (TOA, R₃N) and trioctylmethylammonium chloride (TOMAC, R₃RNCl), were studied by thermogravimetry and differential thermal analysis under an atmosphere of nitrogen, and the products of their thermal decomposition, such as volatile matter and residues, by gas chromatography. X-ray diffraction and infrared spectroscopy. It was found that the complexes with TOA and TOMAC thermally decompose to V₂O₃ at 200–300° by cracking of the compounds R₃NHVO(OH)Cl₂ and R₃RNVO(OH)Cl₂ formed via dissociation of the complexes at about 150°.

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Zusammenfassung Die Komplexe (R₃NHVO(OH)Cl₂)₂ und (R₃RNVO(OH)Cl₂)₂ wurden hergestellt, indem benzolische und wässrige Vanadylchlorid-Lösungen mit Trioctylamin (TOA, R₃N) und Trioctylmethylammoniumchlorid (TOMAC, R₃RNCl) extrahiert und die erhaltenen Lösungen im Vakuum eingedampft wurden. Die Komplexen wurden in Stickstoffatmosphäre mittels TG und DTA untersucht und die thermischen Zersetzungsprodukte, und zwar sowohl die flüchtigen Verbindungen als auch die Rückstände, gaschromatographisch bzw. röntgendiffraktometrisch und IR-spektroskopisch bestimmt. Es wurde festgestellt, daß die Komplexe mit TOA und TOMAC bei 150° in die Verbindungen R₃NHVO(OH)Cl₂ und R₃RNVO(OH)Cl₂ dissoziieren, die bei 200–300° thermisch zu V₂O₃ zersetzt werden.

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(R₃NHVO(OH)Cl₂)₂ (R₃RNVO(OH)Cl₂)₂ (R₃,) ( , R₃RNCl). , , . , 200–300° V₂₃ R₃NV()l₂ R₃RNVO(OH)Cl₂, 150°.

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We wish to thank the Koei Chemical Co. Ltd. for samples of TOA and TOMAC.     

New asymmetric reactions of 2-formyl- and 2-acyl-1-[(2,4, 6-triisopropylphenyl)sulfinyl]naphthalenes via diastereomeric rotamers

Nucleophilic reactions with Grignard reagents and the Mukaiyama aldol reactions of the naphthaldehydes having the (2,4, 6-triisopropylphenyl)sulfinyl group produced products with high stereoselectivity. In these reactions, the stereochemistry of the major products changes depending on the Lewis acids used. Reduction of the 2-acyl-1-[(2,4,6-triisopropylphenyl)sulfinyl]naphthalenes also proceeds with high stereoselectivity but with a different stereochemistry depending on the reducing agents. We have demonstrated, by the mechanistic consideration based on the X-ray crystal structures as well as the (1)H and (13)C NMR spectral data, that the extremely high and specific stereoselectivities of these reactions are due to the predominant rotamer around the C(naph)-S axis. Synthesis of enantiomerically pure 2-naphthylmethanol is provided as an example.