Pressure and temperature effects on the excess deuteron and proton conductance

The limiting molar conductances ° of deuterium chloride DCl in D₂O were determined as a function of pressure and temperature in order to examine the proton-jump mechanism in detail. The excess deuteron conductances °_E(D ⁺), as estimated by the equation [°_E(D ⁺) = °(DCl/D ₂ O) – °(KCl/D ₂ O)], increases with an increase in the pressure and temperature as well as the excess proton conductance [°_E(H ⁺) = °(HCl/H ₂ O) – °(KCl/H ₂ O)]. The isotope effect on the excess conductances, however, depends on the pressure and temperature contrary to the model proposed by Conway et al.: °_E(H ⁺)/°_E(D ⁺) decreases with increasing pressure and temperature. The magnitude of the decrease with pressure becomes more prominent at lower temperature. These results are discussed in terms of the pre-rotation of adjacent water molecules, the bending of hydrogen bonds with pressure, and the difference in strength of hydrogen bonds between D₂O and H₂O.     

Enhanced rectal absorption of insulin in rabbits from hollow-type suppositories containing insulin and glyceryl-1-monooctanoate.

The absorption of two kinds of insulin (from porcine or bovine pancreas) from the rectum of rabbits after the administration of hollow-type suppositories containing insulin and glyceryl-1-monooctanoate (GMO) as an absorption-enhancing agent was investigated. Two types of suppositories were employed: type I containing insulin in an aqueous solution (approx. 25 IU/mg/100 microliters citric buffer solution at pH 3.0) in the cavity of the suppository and GMO mixed with a base material (Witepsol H-15), and type II containing insulin in a crystalline form in the same amount as in type I. Without GMO, the insulin and glucose levels in plasma were unchanged, whereas a marked increase in the plasma levels of insulin and a decrease of glucose concentrations were found following coadministration of insulin and GMO by the type I suppository. Similar enhancement of rectal absorption of insulin was obtained from porcine and bovine sources. In the case of the crystalline insulin, despite the use of the same amount of GMO, porcine insulin was more efficiently absorbed than bovine insulin by the type II suppository. GMO enhances the absorption of insulin in an aqueous solution or a crystalline form, and the dissolution rate of insulin may be an important factor in the rectal absorption of insulin.     

Gas-stirred solvent extraction with propylene carbonate for separation and direct polarographic determination of thallium (III)

Gas-stirred propylene carbonate (PC) extraction can be performed by bubbling nitrogen without loss of volume. This extraction technique has proved to be highly useful for the separation and subsequent direct polarographic estimation of Tl(III) in the recovered PC phase. Tl(III) can be determined by differential-pulse polarography over the concentration range of 0.4 10 g ml^–1 without any interferences due to most metal ions such as Pb(II), Bi(III), Cu(II), Sb(III) and As(III). This proposed technique would be possible to use as a simple extraction step prior to the final estimation by instrumental method of analysis such as atomic absorption spectrometry or spectrophtometry.     

Tris(1‐ethyl‐3‐methyl­imidazolium) hexa­chloro­lanthanate

In the title complex, (C₆H₁₁N₂)₃[LaCl₆], centrosymmetric octahedral hexa­chloro­lanthanate anions are located at the corners and face‐centers of the monoclinic unit cell. The ring H atoms of the cations interact with the Cl atoms of the anions via hydrogen bonding, and bifurcation of the hydrogen bonding is observed. Cation–cation interactions via hydrogen bonding between the ring H atoms and π‐electrons of aromatic rings are also observed as in other imidazolium salts.     

Copper(II)-catalyzed oxidation of d-alpha-tocopherol by oxygen in aqueous solution

alpha-Tocopherol (alpha-Toc) was solubilized in aqueous solutions using 13 solubilizing agents and the products of oxidation by oxygen in the presence and the absence of Cu(II) were analyzed by HPLC. In the presence of Cu(II), the oxidation was accelerated and 5-formyl-7,8-dimethyltocol and alpha-tocoquinone were the major oxidation products. Their yields greatly increased in the presence of Cu(II). The yields and the rates of formation of the products were dependent on the properties of solubilizing agents and other conditions as well as the presence of Cu(II) or other metal ions. It is suggested that slight changes in the structure of the solubilizing agents affect the course of the reaction.     

Borderline of hydrogen bonding of silanols

Two new silanols bearing very bulky silyl groups, (i-Pr₃ Si)₃SiOH and (t − BuMe₂Si)₃SiOH were prepared by peracidoxidation of their respective silanes. The X − ray crystallographic analysis revealed that (t − BuMe₂Si)₃ SiOH forms a dimeric structure with hydrogen bonding, while (i − Pr₃ Si)₃ SiOH exists as a monomer in the crystal. The effects of the size of the substituents as well as the reactivity of these silanols are discussed.     

Enhancement of electronic excitation energy transfer in the colloidal crystals of colloidal silica suspensions doped with fluorescent dyes

The efficiency of electronic excitation energy transfer from photo-excited rhodamine 110 (Rh110, energy donor) to rhodamine B (RhB, energy acceptor) in an exhaustively deionized colloidal silica suspension has been studied. This colloidal suspension shows Bragg reflection due to the formation of colloidal crystals and the Bragg-peak wavelength is controllable by the volume fraction of the silica spheres. When the Bragg-peak wavelength matches with the fluorescence band of Rh110, a depletion was observed in the Rh110 fluorescence spectrum. This means the fluorescence of Rh110 is partially trapped due to the Bragg reflection inside the crystal lattice. In the coexistence of RhB, the enhancement of RhB fluorescence intensity was observed. These facts clearly indicate the trapped photon energy of Rh110 is efficiently transferred to RhB within the colloidal crystals. The quantitative measurements showed that the enhancement of the transfer efficiency is 20% (or slightly more) in the present experimental conditions.     

Electrode reaction of zinc ions at a dropping mercury electrode in ammonium sulphate solutions

The electrode reaction of Zn(II) at a DME in aqueous solutions of (NH₄)₂SO₄ has been studied by d.c. and square-wave polarography at 25.0±0.1°C. The electrochemical kinetic parameters for the reaction are determined. The appearance of the second wave in the square-wave polarogram has been attributed to the low values of the rate parameter and the transfer coefficient.