Stable conformations of 12-crown-O3N and its Li+ complex in aqueous solution

Stable conformations of 12-crown-O3N and its Li complexes in aqueous solution were investigated. To calculate the free energy differences of conformers of 12-crown-O3N and its Li+ complex, our procedure was to make use of two programs, CONFLEX and BOSS. The former generates conformers, and the latter calculates the differences in free energy of solvation between two conformers in aqueous solution. It was confirmed that the present procedure is applicable in solving the question of what is the most stable conformation of 12-crown-O3N in aqueous solution. Results of the calculations suggest that the order of stability for conformers in a vacuum is different from that in aqueous solution. It was also confirmed that the coordination geometry of solvent waters to Li+ changes depending on the distance between the cation and the crown ring.     

Ab initio potential energy curves for the CO+ ion and a study of the photoelectron spectra of CO

The potential energy curves for the low-lying electronic states of CO⁺ are calculated by using the ab initio full valence configuration interaction method with minimal STOs. Calculated spectroscopic parameters are given for twenty five bound states, and the compared with the experimental values for four observed bound states. The band systems, observed in the 22 eV and 27 eV region of He II photoelectron spectra of CO, are analysed by using calculated potential energy curves and spectral intensities. New assignment for the fourth band system at 22 eV ～ 23 eV is proposed.     

A caffeine-sensitive membrane electrode: previous misleading report and present approach

Although a previous study [S.S.M. Hassan, M.A. Ahmed, M.M. Saoudi, Anal. Chem. 57 (1985) 1126] had shown that a caffeine-sensitive electrode made with picrylsulfonate and 1-octanol as a cation-exchanger and a solvent mediator, respectively, had a wide working pH range (5.5–9.5) and exhibited a Nernstian response, we could not find such response in this electrode. The present result was reasonable, because the pK_a value of caffeinium ion was reported to be around 0.7 and the neutral form of caffeine was predominant in the pH range examined. Thus, we reinvestigated the response characteristics of a caffeine electrode, taking into consideration the pK_a value, and constructed a new electrode with a combination of the lipophilic cation-exchanger, tetrakis[3,5-bis(2-methoxyhexafluoro-2-propyl)phenyl]borate (HFPB), and the solvent mediator with high degree of dielectric constant, 2-fluoro-2′-nitrodiphenyl ether (FNDPE). This electrode showed a pH-dependent response to caffeinium ion and gave a detection limit of 50 μM with a slope of 55 mV per concentration decade at pH 2. The use of other solvent mediators was less effective than that of FNDPE. The electrode was applied for the determination of caffeine in some central stimulants.     

Size-exclusion SPR sensor chip: application to detection of aggregation and disaggregation of biological particles

We propose a novel surface plasmon resonance (SPR) sensor chip with a microfabricated slit array. The microslit excludes micrometre-size objects larger than its slit size from the SPR sensing area, so that it functions as an in situ filter. We demonstrated the sensing of microparticles of different diameters using the chip, and the results show a successful size-exclusion effect. As a demonstration of the biological application, we performed the detection of aggregation and disaggregation of biological particles using sugar-chain-immobilized gold nanoparticles as a test sample.     

<Emphasis Type="Italic">S,S,S</Emphasis>-Tris(2-ethylhexyl) phosphorotrithioate as an effective solvent mediator for a mexiletine-sensitive membrane electrode

S,S,S-Tris(2-ethylhexyl) phosphorotrithioate proved to be an effective solvent mediator for constructing a mexiletine-sensitive membrane electrode in combination with an ion-exchanger, sodium tetrakis[3,5-bis(2-methoxyhexafluoro-2-propyl)phenyl]borate. Among a series of phosphorus compounds containing phosphoryl (P=O) groups, this solvent mediator showed the highest sensitivity to mexiletine in phosphate-buffered physiological saline containing 0.15 mol L⁻¹ NaCl and 0.01 mol L⁻¹ NaH₂PO₄/Na₂HPO₄ (pH 7.4), giving a detection limit of 2 × 10⁻⁶ mol L⁻¹ with a slope of 58.8 mV decade⁻¹. This is the best reported detection limit of any mexiletine-sensitive electrode developed to date. Owing to its high selectivity toward inorganic cations, the electrode was used to determine the level of mexiletine in saliva, the monitoring of which is quite effective for controlling the dose of this drug noninvasively. The mexiletine concentrations determined with the mexiletine-sensitive electrode compared favorably with those determined by high-performance liquid chromatography.     

Whole-body distribution of <Superscript>14</Superscript>C-labeled silica nanoparticles and submicron particles after intravenous injection into Mice

We analyzed the whole-body distribution of ¹⁴C–ADP-labeled silica nanoparticles (¹⁴C–ADP–SiO₂ nanoparticles) and submicron particles (¹⁴C–ADP–SiO₂ submicron particles) after intravenous injection into ICR mice. The ¹⁴C–ADP–SiO₂ nanoparticles and submicron particles were synthesized before the injection and the particle size was 19.6 and 130 nm, respectively. Similarly, the shape was spherical and the crystallinity was amorphous. After the synthesis, we injected mice with the ¹⁴C–ADP–SiO₂ nanoparticles or the ¹⁴C–ADP–SiO₂ submicron particles and dissected tissues after 1, 2, 4, 8 and 24 h. The radioactivity in the tissues was measured with a liquid scintillation counter. As a result, the retention percentage in bone, skin, lymph nodes, and the digestive mixture was at least twofold higher in the ¹⁴C–ADP–SiO₂ nanoparticles-exposed mice, whereas the retention percentage in the kidney was statistically higher in the ¹⁴C–ADP–SiO₂ submicron particles-exposed mice. Both types of ¹⁴C–ADP–SiO₂ particles mainly translocated to the muscle, bone, skin, and liver, but hardly translocated to the brain and olfactory bulb. Furthermore, the ¹⁴C–ADP–SiO₂ nanoparticles had a higher retention percentage (62.4 %) in the entire body at 24-h post-injection than did the ¹⁴C–ADP–SiO₂ submicron particles (50.7 %). Therefore, we suggested that the ¹⁴C–ADP–SiO₂ nanoparticles might be more likely than the ¹⁴C–ADP–SiO₂ submicron particles to be retained in the body, and consequently they might be gradually accumulated by chronic exposure.