Encapsulation of saline solution by tetrahydrofuran clathrate hydrates and inclusion migration by recrystallization

Encapsulation of saline solution as an impurity in tetrahydrofuran clathrate hydrates grown in a stoichiometric solution with 3 wt % NaCl and the release of a saline solution during melting along with inclusion migration by hydrate recrystallization during annealing are studied using a directional growth apparatus in combination with a Mach-Zender interferometer. Interferometric observation revealed that the salt concentration increased locally in the solution near the growth interface. The time evolution of salt concentration in the solution was in accordance with the numerical results obtained from the diffusion equation for salt, assuming perfect rejection of salt by the hydrate. However, after the interfacial pattern developed into a serrated pattern (periodical array of trough and crest), the salt concentration in the solution ceased to increase, deviating from the theoretical value. This indicates that the saline solution was encapsulated by the growth hydrate. On the other hand, upon melting of the slowly grown hydrate, the salt concentration near the interface was observed to be locally high at the location of the trough during growth, whereas it was dilute at the location of the growth crest. Furthermore, when the hydrate was annealed under an applied temperature gradient, the inclusions (encapsulated saline solution) in the hydrate migrated toward the bulk solution and were finally expelled by hydrate recrystallization. The migration speed of the inclusions increased with a larger temperature gradient. By melting the sample over a sufficiently long anneal time, the melt was determined to be completely desalinated.     

An electric cyclophane: cavity control based on the rotation of a paraphenylene by redox switching

Although a free rotation around a single bond gives no mechanical output, it has let us imagine a molecular motor. A para-substituted aromatic ring can be regarded as a rotator with the para-rotation axis. When it is incorporated in a wider pi-conjugated system, a quinoidal structure is generated accompanied by oxidation on the substituted groups at the 1,4-position, and the axis is fixed. A paraphenylenediamine was selected as the nanomechanical molecular module capable of locking and releasing the free rotation using an electrode in solution. We inserted the module into a simple molecular system, cyclophane. It was clarified that the cyclophane was able to open and close its cavity in a reversible redox process repeatedly.     

Superbunch hadron colliders

A novel concept of a high luminosity hadron collider is proposed. This would be a typical application of an induction synchrotron being newly developed. Extremely long bunches, referred to as superbunches, are generated by a multibunch stacking method employing barrier buckets at the injection into the collider and are accelerated with a step voltage induced in the induction gaps. Superbunches intersect with each other, yielding a luminosity of more than 10(35) cm(-2) sec(-1). A combination of vertical crossing and horizontal crossing must be employed in order to avoid any significant beam-beam tune shift.     

Reconstruction of morphology of micron-sized,monodisperse composite polymer particles by the solvent-absorbing/releasing method

Micron-sized, monodisperse polystyrene (PS)/poly(n-butyl methacrylate) (PBMA) (2/1 w/w) composite particles having different morphologies were prepared by the solvent-absorbing/releasing method (SARM). There was an obvious influence of the releasing rate of toluene from the toluene-swollen composite particles on the reconstructed morphology by the SARM. In the case of fast release, the reconstructed morphology was a bicontinuous structure that is similar to that formed by spinodal decomposition. On the other hand, in the case of slow release, a hemispherical structure was formed that consisted of PS and PBMA phases.Part CCLIV of the series Studies on Suspension and Emulsion     

Effect of charge ordering and disordering on terahertz radiation characteristics of magnetoresistive Pr0.7Ca0.3MnO3 thin films

Terahertz (THz) radiation from voltage-biased photoswitching devices made on magnetoresistive manganite Pr0.7Ca0.3MnO3 have been investigated for thin films grown under different conditions. We find that the temperature dependence of THz radiation near the charge-ordering temperature strongly depends on the growth condition of Pr0.7Ca0.3MnO3, whereas THz radiation shows no such temperature dependence near the spin-ordering temperature.     

First total synthesis of cucurbitaxanthin A applying regioselective ring opening of tetrasubstituted epoxides

The synthesis of cucurbitaxanthin A 1 was accomplished via the C(15)-3,6-epoxides 7e and 7f prepared by regioselective ring opening of the 3-hydroxy-5,6-epoxides 6e and 6f.     

On Modular Standard Modules of Association Schemes

We will determine the structure of the modular standard modules of association schemes of class two. In the process, we will give the theoretical interpretation for the p-rank theory for strongly regular graphs, and understand the p-rank as the dimension of a submodule of the modular standard module. Considering the modular standard module, we can obtain the detailed classification more than the p-rank and the parameters.     

Stereoselective synthesis of alkynyl C-2-deoxy-beta-d-ribofuranosides via intramolecular nicholas reaction: A versatile building block for nonnatural C-nucleosides

The reaction of 3,5-di-O-benzyl-2-deoxy-d-ribofuranose with various alkynyllithium reagents afforded diastereomeric mixtures of the corresponding ring-opened alkynyldiols. The resulting diastereomeric mixtures were successively treated with Co(2)(CO)(8), a catalytic amount of TfOH, Et(3)N, and iodine in one pot to give alkynyl C-3,5-di-O-benzyl-2-deoxy-beta-d-ribofuranosides with high beta-selectivities. The cobalt-mediated cyclization (intramolecular Nicholas reaction) is reversible; thus, thermodynamically more stable beta-anomers were obtained preferentially. The alkynyl C-deoxyribofuranosides were converted to a variety of C-deoxyribofuranoside derivatives.     

New ferroelectric liquid crystals with a trifluoromethyl group

New chiral dopants, possessing a trifluoromethyl group, have been synthesized. These dopants have different polar groups, located between the chiral centre and the diphenylacetylene core. The polar part is chosen from ester, methylene ether and ether linkages. Each new chiral dopant was mixed with a non-chiral liquid crystal mixture or a ferroelectric liquid crystal mixture, and their transition temperatures and electrooptic properties measured. The largest spontaneous polarization, 4·1 nC cm^-2, was obtained at 25°C for the ferroelectric liquid crystal mixture in which the dopant, with a methylene ether linkage, was incorporated. Molecular orbital calculations (MNDO method) for the dopants show that the calculated dipole moments are correlated with the measured spontaneous polarization, and the calculated results explain the experimental results quite well. In addition, it has been found that the conformation of the chiral part is an important factor which affects the magnitude of spontaneous polarization.