Kinetic analysis of distribution of weak acid in an oil-gelatin microcapsule/water system studied by microcapillary injection and microabsorption methods.

The distribution of anthracene-9-carboxylic acid across dibutyl phthalate/gelatin-membrane/water interface of a single microcapsule was analyzed using microcapillary manipulation and microabsorption methods. The partitioning ratio and the distribution rate in the microcapsule/water system were measured for various pH values in the water phase. Results were compared with those in the dibutyl phthalate/water system in the absence of the gelatin membrane. The distribution rate could be analyzed on the basis of a first-order type reaction. The observed rate constant was linearly proportional to the inverse of the microcapsule radius, indicating that the distribution rate is limited by interfacial mass transfer. Analysis of the pH dependence of the interfacial mass transfer rate suggests that the mass transfer of the neutral species of anthracene-9-carboxylic acid (AnH) competes with the ion transfer of the dissociated species (An-) at the liquid/liquid interface in the gelatin membrane of the microcapsule.     

Statistical mechanics of thermal diffusion

Expressions of the flows of atoms A and B of a binary system in a crystal are derived as the response to the imposed gradients of temperature and chemical potentials. The formulation is done using the pair approximation of the Path Probability Method of irreversible statistical mechanics and atomic migration is assumed to be via the vacancy mechanism. The energy carried by photons (and electrons) under the temperature gradient is assumed to be independent of the atomic flux. For the case near equilibrium, linear relations are derived among the atomic fluxes, the energy flux (associated with atomic flux) and the gradients. The Onsager reciprocal relations are proved to hold among the coefficients, including those related to energy flows. The heat of transport (energy carried by a diffusing atom) and the heat conduction due to atomic flux are thus unambigously derived.     

Scanning tunneling microscopy study on initial stage of atomic hydrogen adsorption on the Si(1 1 1) 7 × 7 surface

Initial hydrogen adsorption on the Si(1 1 1) 7 × 7 surface was studied by scanning tunneling microscopy (STM) in an ultrahigh vacuum. Room temperature adsorbed hydrogen on the adatom in the 7 × 7 reconstruction led to depression of adatoms in the STM images. The hydrogen uptake curve at the adatom site as a function of hydrogen exposure time was well represented by Langmuir adsorption. No preferential adsorption was seen among four inequivalent adatoms in the 7 × 7 reconstruction. Adsorption of the adjacent center and corner adatoms respectively showed ∼10% higher adsorption. Even though the number of reacted adatoms in the half unit of the 7 × 7 reconstruction was statistically random, the number of reacted adatoms in the nearest neighbor half unit was enhanced as the number of reacted sites increased in the half unit.     

Cross-coupling of benzylic acetates with arylboronic acids: one-pot transformation of benzylic alcohols to diarylmethanes

Benzylic acetates reacted with arylboronic acids in the presence of a DPEphos-[Pd(eta3-C3H5)Cl]2 catalyst when tert-amyl alcohol was used as a solvent, and the catalytic cross-couplings produced diarylmethanes in high yields (up to 94% isolated yield).     

Determination of 1-hydroxypyrene in human urine by high-performance liquid chromatography with fluorescence detection using a deuterated internal standard

A high-performance liquid chromatographic method has been developed for the quantification of 1-hydroxypyrene (1-OHP) in human urine using deuterated 1-hydroxypyrene ([2H9]1-OHP) as an internal standard with fluorescence detection. [2H9]1-OHP was prepared enzymatically from deuterated pyrene ([2H10]Pyr) with cytochrome P450 1A1. It eluted immediately prior to non-deuterated 1-OHP on alkylamide-type reversed-phase columns and had nearly the same fluorescence characteristics as non-deuterated 1-OHP. The detection limit was 0.1 microg/L and the calibration range was from 1 to 100 nmol/L. Urine sample treatment involved enzymatic hydrolysis followed by solid-phase extraction using Sep-Pak C18 cartridges. The proposed method was used to determine urinary 1-OHP in smokers and non-smokers.     

Monolayer studies of single-chain polyprenyl phosphates

The monolayer properties of some single-chain polyprenyl phosphates (phytanyl, phytyl, and geranylgeranyl phosphates), which we regard as hypothetical primitive membrane lipids, were investigated at the air-water interface by surface pressure-area (pi-A) isotherm measurements. The molecular area/ pressure at various pH conditions dependence revealed the acid dissociation constants (pKa values) of the phosphate. The pKa values thus obtained at the air-water interface (pKa1 = 7.1 and pKa2 = 9.4 for phytanyl phosphate) were significantly shifted to higher pH than those observed in the bilayer state in water (pKa1 = 2.9 and pKa2 = 7.8). The difference in pKa values leads to a stability of the phosphate as both monolayer and bilayer states in a pH range of 2-6. In addition, the presence of ions such as sodium, magnesium, calcium, and lanthanum in the subphase significantly altered the stability of the polyprenyl phosphate monolayers, as shown by the determination of monolayer collapse and compression/expansion hysteresis. Although sodium ions in the subphase showed only a weak effect on the stabilization of the monolayer, addition of magnesium ions or of a small amount of calcium ions significantly suppressed the dissolution of the monolayer into the subphase and increased its mechanical stability against collapse. In contrast, the presence of larger amounts of calcium or of lanthanum ions induced collapse of the monolayers. Based on these experimental facts, a plausible scenario for the formation of primitive cell membrane by transformation of a monolayer to vesicle structures is proposed.     

Inequalities for a distribution with monotone hazard rate

Summary LetX be a positive random variable with the survival function and the densityf. LetX have the moments μ=E(X) and μ₂=E(X ²) and put ε=|1-μ₂/2μ²|. Put and . It is proved that the following inequalities hold: , for allx>0, ifq(x) is monotone and that , ifq ₁ (x) is monotone. It is also shown that Brown's inequality which holds wheneverq ₁ (x) is increasing is not valid in general whenq ₁ is decreasing. The Institute of Statistical Mathematics