Binding of a surfactant counterion to low-charge-density poly(acrylic acid) and poly(methacrylic acid)

The binding of a cationic surfactant, dodecylpyridinium (C12Py) chloride, with a low-charge-density poly (methacrylic acid) (PMA) was investigated in buffer solutions under the condition of constant pH. The binding isotherms with PMA consisted of two and three steps at a pH lower and higher than 3.2, respectively. Bindings in the first step were independent of pH and this step was considered to correspond to the solubilization of the hydrocarbon chains of C12Py into the nonpolar region of the compact form of PMA. This is the indication of the compact form from the binding isotherm. At pH higher than 3.2, the second step was discriminated and it depended on the pH. In the third step, a sharp rise in the degree of binding (β) was observed accompanying the solubilization of the precipitates of the PMA–C12Py complex. The binding with poly(acrylic acid) (PAA) and PMA in conventional unbuffered NaCl solutions was also examined and the pH profile of the solution during the binding process was determined. In the case of unbuffered NaCl solutions, the binding with PAA took place cooperatively at the critical association concentration (cac). The binding isotherm consisted of two steps and the pH decreased with the increase in β. The binding isotherm of PMA, on the other hand, consisted of three steps: the pH decreased slightly in the first step and considerably in the second step with the increase in β but it increased with β in the third step, exhibiting a pH minimum around 3.2. The binding in the first step coincided with that obtained in the buffered solutions. Linear relationships between β and the pH were found for both polymers. In the case of PMA, no cac was observed in both buffered and unbuffered NaCl solutions. Received: 24 January 2001 Accepted: 23 May 2001     

Interlaboratory comparison of actinides in human tissue239Pu and240Pu

An international laboratory intercomparison of actinides in human tissues was organized by the United States Transuranium Registry and the National Institute of Standards and Technology. Five laboratories from the United States, United Kingdom, and Japan participated in the intercomparison. The laboratories were requested to analyze Standard Reference Materials 4351 (Human Lung) and 4352 (Human Liver) for²³⁹Pu and²⁴⁰Pu concentration. Approximately equivalent measurement capabilities were generally found among the participants. The results of this intercomparison were statistically comparable to those used for the original certification of the SRM's and were combined for a re-evaluation of the certified values. The combined data sets provide a better characterization of the inhomogeneity of these reference materials and result in a better basis for certification.Deceased.     

Chemoselective N-acetylation of primary aliphatic amines promoted by pivalic or acetic acid using ethyl acetate as an acetyl donor

The combination of pivalic or acetic acid as a promoter and EtOAc as a solvent and acetyl donor proved to be efficient for the chemoselective N-acetylation of primary aliphatic amines to afford the corresponding acetamides. We developed a simple and convenient approach, which requires mild reaction conditions. Competitive inter- and intramolecular reactions between aliphatic amines, alcohols, and aromatic amines were examined, and chemoselectivity was achieved by adjusting the conditions of the reaction.     

Influence of the solvent on nature of gate effect in molecularly imprinted membrane

The solute diffusive permeability in a thin layer of a molecularly imprinted polymer (MIP) is affected by specific binding of the MIP with a template. This phenomenon, termed the "gate effect," would be widely applicable for the development of novel biomimetic sensors. However, the mechanism underlying the gate effect is not totally understood. We present here investigation of the role of specific adsorption of a template and solution content in MIPs on the gate effect. A molecularly imprinted self-supporting membrane was formed by copolymerization of methacrylic acid, 2-vinylpyridine, and triethyleneglycol dimethacrylate in the presence of L- (or D-) phenylalanine as a template. The template adsorbed by membrane with degree of enantio-selectivity in a mixed solvent of methanol and water. The amount of adsorption and binding selectivity showed little sensitivity to the solvent composition. The solution content in the membrane increased with increasing the methanol concentration of the solvent following a sigmoid curve with an inflection point at methanol concentration of 20 wt.%. The content increased in the presence of the template at methanol concentrations higher than the inflection point, and decreased at lower methanol concentrations. The creatinine permeability across the membrane estimated by batchwise dialysis increased in the presence of the template at 50 wt.% methanol in the solvent, and did not change at 20 wt.%. There was no permeability for creatinine in the pure water solvent. Both the solution content and the permeability were not affected by the presence of the enantiomer of the template. The results show that the choice of solvent controls more strongly the nature of the gate effect than the specific binding of the template.     

Corrosion and passivation behavior of Mg-Zn-Y-Al alloys prepared by cooling rate-controlled solidification

Highly corrosion-resistant nanocrystalline Mg-Zn-Y-Al multi-phase alloys have been prepared by consolidation of rapidly solidified (RS) ribbons. The relation between corrosion behavior and microstructure evolution of Mg-Zn-Y-Al alloys with a long period stacking ordered phase has been investigated. In order to clarify the influence of rapid solidification on the occurrence of localized corrosion such as filiform corrosion, several Mg_96.75Zn_0.75Y₂Al_0.5 (at.%) alloys with different cooling rates are fabricated by the gravity casting, copper mould injection casting and melt-spinning techniques and their corrosion behavior and microstructures are examined by the salt water immersion test, electrochemical measurements, GDOES, XRD, SEM and TEM. To clarify the effect of aluminium addition on the improvement in corrosion resistance of the alloys, several Mg_97.25−xZn_0.75Y₂Al_x alloys with different aluminium contents are fabricated by consolidating RS ribbons and the formation of corroded films on the Mg-Zn-Y-Al alloys have been investigated. Rapid solidification brings about the grain refinement and an increase in the solid solubility of zinc, yttrium and aluminium into the magnesium matrix, enhancing microstructural and electrochemical homogeneity, which in turn enhanced corrosion resistance. The addition of aluminium to magnesium can modify the structure and chemical composition of surface films and improves the resistance to local breakdown of the films.     

Electrochemically stable fluorohydrogenate ionic liquids based on quaternary phosphonium cations

Fluorohydrogenate ionic liquids of quaternary phosphonium cations, tri-n-butylmethylphosphonium (P₄₄₄₁) fluorohydrogenate, tetra-n-butylphosphonium (P₄₄₄₄) fluorohydrogenate, and tri-n-butyl-n-octylphosphonium (P₄₄₄₈) fluorohydrogenate, have been synthesized by the metatheses of anhydrous hydrogen fluoride and the corresponding phosphonium chloride precursors. All the obtained salts have melting points below room-temperature with a vacuum-stable composition of P_444m(FH)_2.3F (m = 1, 4, and 8) and were characterized by density, conductivity, and viscosity measurements. Linear sweep voltammetry with a glassy carbon working electrode shows that the P_444m(FH)_2.3Fs have wide electrochemical windows exceeding 5.2 V. In particular, P₄₄₄₁(FH)_2.3F has an electrochemical window of 6.0 V, which is the widest among fluorohydrogenate ionic liquids reported to date. The thermal stability of these ionic liquids is also improved compared to the salts of N-heterocyclic ammonium cations.     

Synthesis of hyperolactones A and C

Hyperolactones A ( 1 ) and C ( 3 ) have been synthesized starting from (S)‐malic acid by a straightforward route. The unique spirolactone skeleton was efficiently constructed by one‐pot reaction as a key step. The absolute stereochemistry of hyperolactones was unambiguously established by this synthesis.     

The Rasmussen invariants and the sharper slice-Bennequin inequality on knots

Rasmussen introduced a knot invariant based on Khovanov homology theory, and showed that this invariant estimates the four-genus of knots. We compare his result with the sharper slice-Bennequin inequality for knots. Then we obtain a similar estimate of the Rasmussen invariant for this inequality.