Voltammetric study of the transfer of polyammonium ions at nitrobenzene / water interface.

The transfer of polyammonium ions, poly[(dimethylimino)-1,6-hexanediyl] (n = 140, n being the degree of polymerization) ion and poly[(dimethylimino)(2-oxo-1,2-ethanediyl)imino-alpha,omega-alkanediylimino(1-oxo-1,2-ethanediyl)(dimethylimino)-alpha',omega'-alkanediyl] ([-N+ (CH3)2CH2CONH(CH2)x NHCOCH2N+ (CH3)2(CH2)y-]n, x = 2, 3, 4, or 6, y = 3 or 6, and n = 30-130) ions, at a polarizable nitrobenzene / water interface has been studied by normal pulse voltammetry and cyclic voltammetry. Despite the polydispersity of the preparations, by normal pulse voltammetry, an S-shaped current-potential curve with a well-defined limiting current, and, by cyclic voltammetry, a pair of anodic and cathodic peak currents due to the transfer of polyammonium ions across the interface were observed within the potential window. The voltammetric behavior is described. Also, the effect of ion-pair formation of the polyammonium ions with supporting electrolyte anions in nitrobenzene- and water-phases on the half-wave or midpoint potential of the ion-transfer, and the relation between the structure of the polyammonium ions and the transfer potentials are discussed.     

Voltammetric study of the transfer of fluoride ion at the nitrobenzene / water interface assisted by tetraphenylantimony.

The transfer of F- ion assisted by an organometallic complex cation tetraphenylantimony (TPhSb+) across the polarized nitrobenzene / water (NB / W) interface has been studied by means of ion-transfer voltammetry. A well-defined voltammetric wave was observed within the potential window at the NB / W interface when tetraphenylantimony tetrakis(4-chlorophenyl) borate and F- ion were present in NB and W, respectively. The voltammogram can be interpreted as being due to the reversible transfer of F- ion assisted by the formation of the TPhSbF complex through the coordination of F- to Sb atom in NB. The formal formation constant of TPhSbF in NB has been determined to be 10(1.95 +/- 0.2 M(-1). No voltammetric wave due to the TPhSb(+)-assisted transfer of other anions such as Cl-, Br, I-, NO3-, CH3COO- and H2PO4(-) ions has been observed within the potential window.     

Halogen-free water-immiscible ionic liquids based on tetraoctylammonium cation and dodecylsulfate and dodecylbenzenesulfonate anions, and their application as chelate extraction solvent.

The tetraoctylammonium cation forms water-immiscible room temperature ionic liquids with dodecylsulfate and dodecylbenzenesulfonate anions. The ionic liquids are halogen-free and can be considered environmentally friendly solvents. At 25 degrees C, the solubilities of water in tetraoctylammonium dodecylsulfate and tetraoctylammonium dodecylbenzenesulfonate were 2.8 and 4.0%, respectively, and the densities were 0.92 and 0.93 g cm(-3). The ionic liquids formed stable interfaces with water at 25 degrees C. The possible use of tetraoctylammonium dodecylsulfate as chelate extraction solvent was evaluated by using 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione as extractant. Tetraoctylammonium dodecylsulfate showed high extraction performance for divalent transition metal cations.     

Analysis of herbicides in water using temperature-responsive chromatography and an aqueous mobile phase

A simple and rapid method has been developed for herbicides in water using temperature-responsive liquid chromatography (LC) and a column packed with poly(N-isopropylacrylamide) (PNIPAAm), a polymer anchored on the stationary-phase surface of modified silica. PNIPAAm reversibly changes its hydrophilic/hydrophobic properties in water in response to temperature. The method was used to determine five sulfonylurea and three urea herbicides. Separation was achieved with a 10 mM ammonium acetate (pH 3.0) isocratic aqueous mobile phase, and by changing the column temperature. The analytes were extracted from water by off-line solid-phase extraction (SPE) with an N-vinyl-pyrrolidone polymer cartridge. The average recoveries of the eight herbicides from spiked pure water, tap water and river water were 70-130% with relative standard deviations (RSDs) of <10%. The limits of quantitation (LOQ) of the eight herbicides were between 1 and 4 microg l(-1).     

Calcium Control of the Sign of Phototaxis in Brown Algal Gametes of Mutimo cylindricus

Brown algal swarmers usually exhibit positive or negative phototaxis. Such behaviors influence the increasing or decreasing dispersal distance or colonization on the new substratum. We confirmed that the sign of phototaxis (negative or positive) in male gametes of Mutimo cylindricus was affected by extracellular Ca²⁺ influx through Ca²⁺ channels. Under the control condition (10^?2 m [Ca²⁺]), male gametes swimming with a helical rotation of their cell body mostly showed positive phototaxis. At 10^?3 m [Ca²⁺], more than half of the male gametes showed positive phototaxis, whereas the others showed negative phototaxis. From 10^?4–10^?5 m [Ca²⁺], the phototactic sign changed to negative. When these negative phototactic gametes were transferred back to the control condition, the phototactic sign reverted to positive. At 10^?6 m [Ca²⁺], some of male gametes showed negative phototaxis, but most showed no phototaxis or flagellar beating. Lanthanum, a Ca²⁺ channel blocker, affected the sign of phototaxis at 10^?4 m [La³⁺] under 10^?2 m [Ca²⁺], and male gametes mostly showed negative phototaxis. A further increase in [La³⁺] inhibited phototaxis and flagellar beating. These results pointed out the involvement of Ca²⁺ channels that were blocked by La³⁺ in phototaxis and flagellar beating.     

A new synthetic route to 7 α-methoxycephalosporins

Treatment of 7β-(2,2,3-trihaloalkylideneamino) cephalosporins with excess methanol in the presence of acid scavenger gave 7β-(2-haloalk-2-enylideneamino)-7α-methoxycephalosporins.     

Structure and intramolecular flexibility of beta-cyclodextrin complex with (-)-epigallocatechin gallate in aqueous solvent

The probable structure of the inclusion complex of beta-cyclodextrin (beta-CD) and (-)-epigallocatechin gallate (EGCg) in D2O was investigated using several NMR techniques. EGCg formed a 1:1 complex with beta-CD, in which the A ring and a portion of the C ring of EGCg were included at the head of the phenolic hydroxyl group attached to C7 of EGCg in the beta-CD cavity from the wide secondary hydroxyl group side. In the 1:1 complex with beta-CD, EGCg maintained the conformation in which the B and B' rings of EGCg took pseudoequatorial and pseudoaxial positions with respect to the C ring, respectively. The structure of the inclusion complexes of beta-CD and EGCg obtained from NMR experiments supported those determined from AM1 semiempirical SCF MO calculations well.