Effect of atmospheric pressure on the phase transitions of α,α-trehalose dihydrate DTA study of the dehydration behavior in open systems

The phase transitions of α,α-trehalose dihydrate (T _h) were investigated by either differential thermal analysis (DTA) with an in-house apparatus of variable-pressure type equipped with an open sample holder or commercially available TG (thermal gravimetry)-DTA apparatus for comparison under the same experimental conditions as to the heating rate (2°C min⁻¹), the type of pan (open), and the particle size of T _h (63 μm). The former DTA measurements were carried out under five different total pressures, 101, 75, 61, 48 and 35 kPa, which provided quite helpful information necessary for confirmative assignments of the endothermic peaks due to either melting or dehydration of T _h. The usage of largely different amount of T _h, 126 and 14 mg for the DTA and TG-DTA measurements respectively, led to their different DTA traces, showing that there were largely different extents of the influence by the measured sample surface exposed to the surrounding atmosphere on its dehydration behavior. In addition the high thermal sensitivity achieved with such mass of T _h gave rise to an interesting discovery of an unidentified thermal event at 92°C prior to either melting or dehydration of T _h.     

Orientational ordering of crystal domains in ionic liquid based mixtures

By in situ observations using simultaneous X-ray diffraction and the DSC (differential scanning calorimetry) method, the effect of water, methanol, ethanol, and benzene on the crystallization has been observed in an ionic liquid (IL)-rich phase. The IL is a hydrophilic ionic liquid, N, N-diethyl-N-methyl-N-2-methoxyethyl ammonium tetrafluoroborate, [DEME][BF4]. At a small amount of the above additional molecules in the IL, the conventional preferred orientation on the Debye rings was seen by the X-ray diffraction. At 0.9 mol % H2O, twinlike crystal domains develop extraordinary on the microdomains. By the "crystal-growth enhancement effect" at a slight amount of water, a composite domain structure, which consists of the large domain and the weakly orientated microdomains, is formed without internal strains. Above 2.9 mol % H2O, the domain structure, however, disappears completely. It is remarkable that, in a thermal cycling experiment using pure [DEME][BF4], the similar composite domain structure appeared. This is also caused by an uptake of a slight amount of water.     

Control of photobleaching in photodynamic therapy using the photodecarbonylation reaction of ruthenium phthalocyanine complexes via stepwise two-photon excitation

In this study, we have investigated the photochemical properties and photodynamic effects of ruthenium phthalocyanine (RuPc(CO)(Py)) and naphthalocyanine (RuNc(CO)(Py)) complexes. When a nanosecond-pulsed laser is used, the photodecarbonylation of our Ru complexes efficiently proceeds via stepwise two-photon excitation, while the reaction yields are negligibly small when a continuous-wave (CW) laser is employed. The pulsed laser selective photodecarbonylation decreases the Q-band absorbance, which satisfies what the photodynamic therapy (PDT) requires of the photobleaching. For RuPc(CO)(Py), the photochemical reactions including both the photodecarbonylation and just photobleaching occur in HeLa cells in vitro. Toxicity and phototoxicity tests indicate that our RuPc(CO)(Py) and RuNc(CO)(Py) complexes in concentrations of 0.3-1 microM and 1-2 microM, respectively, are applicable as PDT agents. The phototoxicity is consistent with the photochemical properties of these complexes, namely, excited triplet lifetimes (10 and 4.8 micros for the Pc and Nc complexes, respectively) and singlet oxygen yields (0.48 and 0.35 for the Pc and Nc complexes, respectively). On the basis of these results, we propose a novel concept for achieving a greater depth of necrosis in PDT as follows: (1) PDT of upper cellular layers using CW-laser irradiation; (2) efficient photobleaching in upper cellular layers using pulsed dye-laser irradiation, which results in an increase in the therapeutic depth of red light; (3) PDT directed toward deeper tumor tissues using CW laser irradiation. In addition, these Ru complexes are promising as CO release agents for investigative biochemistry.     

Preparation of polyurea capsules using electrocapillary emulsification

Polyurea capsules have been prepared using the electrocapillary emulsification method in order to control the particle size within the submicron range. The polyurea capsules have been synthesized via the interfacial polycondensation between tetraethylenepentamine (TEP) dissolved in an aqueous phase and toluenediisocyanate (TDI) dissolved in a mixture of cyclohexane and chloroform. The oil phase contains a lipophilic nonionic surfactant (sorbitan sesquioleate, SO-15) as an emulsion stabilizer. Scanning electron microscope (SEM) observations reveal that the capsule size is decreased as (i) the amount of the aqueous phase injected into the oil phase is decreased and (ii) the dropping rate of the aqueous phase is decreased. Indeed, the mole ratio of the two monomers makes a significant impact on the capsule size. Under the best experimental condition examined in this study, we obtained polyurea capsules with a diameter of approximately 200 nm, which should be useful in developing bioreactors or carriers.     

Weight loss and isotopic shifts for water drops frozen on a liquid nitrogen surface

A liquid nitrogen freezing method was used to collect raindrops for the determination of isotope-size distribution. Water drops that fall onto a surface of liquid nitrogen stay suspended for 10 to 20 s, until their temperature reaches the Leidenfrost point (126 K). As their temperature falls to the freezing point, they release their heat by thermal conduction. At the freezing point, latent heat of fusion is released, along with a significant loss of water. After freezing completely, the ice droplets stay suspended, cooling by thermal conduction until they reach the Leidenfrost point. They then lose buoyancy and start sinking. Consistent isotopic changes of 1.5 +/- 0.4 and 0.33 +/- 0.05 per thousand for hydrogen and oxygen, respectively, were found for droplets with radii between 1.0 and 1.5 mm. Isotope fractionation appeared to occur at the same time as water loss, as the droplets were freezing, in what was probably a kinetic effect.     

Generation of nitrene by the photolysis of N-substituted iminodibenzothiophene

To evaluate the ability of dibenzothiophene N-substituted sulfilimines as photochemical nitrene sources, their photolyses in the presence of several trapping reagents, such as sulfides, olefins, and phosphorus compounds, were performed. In the reactions, the corresponding imino-transfer compounds, namely sulfilimines, aziridines, and iminophosphoranes, were formed in good yields, indicating dibenzothiophene N-tosyl and N-acylsulfilimines have a potent nature as nitrogen sources.     

Spectral evidence and DFT calculations on the formation of Bis(2,2'-bipyridine)platinum(II)-N-base adducts

The formation of 1:1 adducts of Pt(bpy)2(2+) (bpy = 2,2'-bipyridine) with various N bases (B) has been ascertained in water at ambient temperature by spectrophotometric titration and electrospray ionization mass spectroscopy. A pseudo-five-coordinated complex, [Pt(bpy)2(B)](2+) with a monodentating bpy, is proposed based on density functional theory calculation. The formation constants (Kc) increase with the nucleophilicity of B except for sterically hindered N-bases, indicating an associative ligand-substitution mechanism.     

A rigid C3v-symmetrical host for saccharide recognition: 1,3,5-tris(2-hydroxyaryl)-2,4,6-trimethylbenzenes

A rigid C(3v)-symmetrical host molecule, syn-1,3,5-tris(2-hydroxy-5-pentylphenyl)-2,4,6-trimethylbenzene, was readily obtained via Suzuki coupling and thermal atropisomerization. The host molecule effectively associated with various saccharides by multipoint hydrogen bonds, whereas its anti-atropisomer and analogue lacking in methyl groups showed much weaker association with saccharides. Thermodynamic analyses suggested that the difference of the association strength was caused by entropic factors.     

Notes on subtlety and ineffability in P κ λ

A type of subtlety for P_κλ called “strongly subtle” is introduced to show almost ineffability is consistencywise stronger than Shelah property. The following are also shown: is strongly subtle” has rather strong consequences. (ii) The ideal is not strongly subtle} is not λ-saturated , and completely ineffable ideal is not precipitous. (iii) In case that λ^<κ=2^λ, almost λ-ineffability coincides with λ-ineffability. (iv) It is not provable that κ is λ^<κ-ineffable whenever κ is λ-ineffable.Research partially supported by “Grant-in-Aid for Scientific research (C), The Ministry of Education, Science, Sports and Culture of Japan 09640299”, and “Japan Society for the Promotion of Science 14540142”.The author is very grateful to the referee for his correcting many errors and helpful suggestions.     

Observation of B+ --> plambdagamma

We report the first observation of the radiative hyperonic B decay B+ --> plambdagamma, using a 140 fb(-1) data sample recorded on upsilom(4S) resonance with the Belle detector at the KEKB asymmetric energy e+e- collider. The measured branching fraction is [symbol: see text](B+ --> plambdagamma) = (2.16(+0.58)(-0.53) +/- 0.20) x 10(-6). We examine its M(plambda) distribution and observe a peak near threshold. This feature is expected by the short-distance b --> sgamma transition. A search for B+ --> pepsilon0gamma yields no significant signal, and we set a 90% confidence-level upper limit on the branching fraction of [symbol: see textB+ --> pepsilon0gamma <4.6 x 10(-6).