Stereoselective sulfur extrusion reaction of syn- and anti-10,20-dibromo-2,3,12,13-tetrathia[4.4]metacyclophanes to the corresponding syn- and anti-dithia[3.3]metacyclophanes

A new cyclophane, 10,20-dibromo-2,3,12,13-tetrathia[4.4]metacyclophane (1) , has been synthesized by the oxidative coupling reaction of 2,6-bis(mercaptomethyl)-1-bromobenzene with I₂. Both syn and anti isomers of 1 can be isolated at room temperature. The thermal sulfur extrusion reaction of anti- 1 with (Et₂N)₃P afforded anti-9,18-dibromo-2,11-dithia[3.3]metacyclophane, while syn- 1 gave 9,19-dibromo-2,11,12-trithia[3.4]metacyclophane. syn-9,18-Dibromo-2,11-dithia[3.3]metacyclophane was produced from the photochemical sulfur extrusion of syn- 1 with (MeO)₃P.     

A finite element/volume method model of the depth‐averaged horizontally 2D shallow water equations

Analysis of surface water flows is of central importance in understanding and predicting a wide range of water engineering issues. Dynamics of surface water is reasonably well described using the shallow water equations (SWEs) with the hydrostatic pressure assumption. The SWEs are nonlinear hyperbolic partial differential equations that are in general required to be solved numerically. Application of a simple and efficient numerical model is desirable for solving the SWEs in practical problems. This study develops a new numerical model of the depth‐averaged horizontally 2D SWEs referred to as 2D finite element/volume method (2D FEVM) model. The continuity equation is solved with the conforming, standard Galerkin FEM scheme and momentum equations with an upwind, cell‐centered finite volume method scheme, utilizing the water surface elevation and the line discharges as unknowns aligned in a staggered manner. The 2D FEVM model relies on neither Riemann solvers nor high‐resolution algorithms in order to serve as a simple numerical model. Water at a rest state is exactly preserved in the model. A fully explicit temporal integration is achieved in the model using an efficient approximate matrix inversion method. A series of test problems, containing three benchmark problems and three experiments of transcritical flows, are carried out to assess accuracy and versatility of the model. Copyright © 2014 John Wiley & Sons, Ltd.     

Diluent effects on molecular motions and glass transition in polymers. I. Polystyrene–toluene

The effects of diluent on molecular motions and glass transition in the polystyrene–toluene system was studied by means of dielectric, thermal, and NMR measurements. Three dielectric relaxations were observed between 80 and 400°K. On the basis of NMR measurements on solutions in toluene and in deuterated toluene, relaxation processes were assigned to segmental motions of polystyrene, rotations of toluene, and the local motions of polystyrene and toluene in order of appearance from the high-temperature side. The concentration dependence of the relaxation strength and of the activation energy for the primary relaxation (that at the highest temperature) show a step increment at about 50% by weight. The activation plots for the primary process were expressed by the Vogel–Tamman equation. With this equation, the temperatures at which the mean dielectric relaxation time becomes 100 sec is determined. This agrees well with the glass-transition temperature T_g and hence T_g in concentrated solution is expressed by in terms of the parameters A, B, and T₀ of the Vogel–Tamman equation. The values of A and B are, respectively, about 12 and 0.65 and independent of the concentration. The physical meaning of these parameters is discussed.     

New method for facile synthesis of amphiphilic thiol-stabilized ruthenium nanoparticles and their redox-active ruthenium nanocomposite

The one-phase reduction of RuCl3 with lithium triethylborohydride as a reductant in tetrahydrofuran in the presence of 1-octanethiol, 1-octadecanethiol, 1,1'-binaphthalene-2,2'-dithiol, or oligoethyleneoxythiol gave organic solvent- and water-soluble thiol-stabilized ruthenium nanoparticles. The oligoethyleneoxythiol-stabilized ruthenium nanoparticles were soluble in both water and organic solvents. The ruthenium nanoparticles were stable in the solid state and did not aggregate in solution. Transmission electron microscope images of the ruthenium nanoparticles reveal small dispersed particles with a narrow size distribution. The ligand-exchange reaction of octadecanethiol-stabilized ruthenium nanoparticles (2.0 nm) with phenothiazine-linked decanethiol afforded redox-active phenothiazine-functionalized ruthenium nanoparticles (1.9 nm) that showed a reversible redox peak at +0.51 V (vs Ag/0.1 M AgNO3) in the cyclic voltammogram.     

GENETIC TOXICOLOGY OF THE PHOTOSENSITIZATION OF CHINESE HAMSTER CELLS BY PHTHALOCYANINES

Chloroaluminum phthalocyanine (CAPC) was recently shown to photosensitize cell killing in culture and tumor destruction in vivo. Because this compound is potentially useful in the photodynamic therapy of cancer, its properties as a genotoxic agent were evaluated. Applying the technique of alkaline elution to study DNA integrity, it was found that CAPC could produce single-strand breaks in the DNA of Chinese hamster cells after exposure to white fluorescent light. At equicytotoxic doses, the number of DNA strand breaks produced by CAPC photosensitization was about three times lower than that induced by X-irradiation. During incubation in growth medium after exposure to CAPC-plus-fluorescent light, cells rejoined DNA strand breaks at a rate similar to that observed after X-irradiation. Resistance to 6-thioguanine (6-TG') or to ouabain (OUA') were used as end points of mutagenic potential. Following a treatment that caused -90% cell killing, there was a slight mutagenic effect, i.e. the frequencies were increased by -40% above the background or spontaneous mutations. However, this enhancement was not statistically significant. Taken together, the foregoing, plus an earlier observation that there is no variation in the sensitivity of cells to CAPC + light through the cell cycle, lead to the inferences that DNA damage does not play a major role in cell killing and that the mutagenic potential of this treatment is small.     

Evaluation of the Hydrophilic Property of Sodium Ion-pair Complexes with 3m-Crown-m Ethers (m = 5, 6) and Their Benzo-derivatives by Solvent Extraction

The ion-pair formation constants {K(j)(0): j = MA (metal salt), MLA} of NaO(2)CCF(3) (Na(+)tfa(-)) and its ion-pair complexes (MLA) in water (w) were determined potentiometrically at 25 degrees C and an ionic strength (I) of zero. 15-Crown-5 (15C5), 18-crown-6 ethers (18C6), and their mono-benzo derivatives were used as crown ethers (L). The extraction of Natfa by these four L from w into 1,2-dichloroethane was done at 25 degrees C, and then the extraction constants (K(ex)) for NaLtfa were calculated by using the K(j) values, which were estimated from the corresponding K(j)(0) ones at I of the w-phases, and other equilibrium constants. Also, the distribution constants (K(D,MLA)) of NaLtfa between the two phases were obtained from a thermodynamic cycle expressing K(ex). An interaction of w-molecules with NaLA was considered using a relation of log K(D,MLA) with log K(D,L), derived from the Scatchard-Hildebrand equation, where K(D,L) denotes the distribution constant of L between the two phases. The interaction increased in the order of NaL (picrate) < free L 相似文献   

Analysis and computation of probability density functions for a 1-D impulsively controlled diffusion process

This paper proposes appropriate boundary conditions to be equipped with Kolmogorov's Forward Equation that governs a stationary probability density function for a 1-D impulsively controlled diffusion process and derives an exact probability density function. The boundary conditions are verified numerically with a Monte Carlo approach. A finite-volume method for solving the equation is also presented and its accuracy is investigated through numerical experiments.     

Field determination of trace iron in fresh water samples by visual and spectrophotometric methods.

Sensitive visual and micro spectrophotometric methods have been developed for field determination of trace iron in fresh water samples. For the visual method, a water sample (0.45-microm filtrate acidified to 0.1 M HCl) was placed in a glass vial and mixed with a reagent solution containing 1,10-phenanthroline, sodium thiocyanate and 0.1 M HCl. Iron was extracted as pink ferroin thiocyanate with 1 ml of 4-methy-2-pentanone. The sample up to 20 ml was added step-by-step, until the color of the extract was detected visually. Without any special instrument or color standard, iron down to 0.001 mg 1(-1) (0.025 microg) in a sample can be determined with an error of 20% in the field. For the micro spectrophotometric method, the extract for 20 ml of sample was separated by capillary suction in a column (micro pipette chip) with acrylic fibers. A part of the extract was pushed out into a micro cell for the absorbance measurement at 525 nm. The column was re-usable after washing with ethanol. This method had a detection limit of 0.001 mg 1(-1) and allowed determinations within an error of 5%. The proposed methods were applied to deionized-, tap-, river-, lake- and reservoir-water samples.