A Novel Synthesis of 4‐Pyridazineacetic Acids via Ring Expansion of N‐Cyanomethylated 3‐Pyrazoline‐4‐acetic Acids

A novel synthetic route to 4‐pyridazineacetic acids 10 – 12 has been achieved by the ring‐expansion reaction of N‐cyanomethylated 3‐pyrazoline‐4‐acetic acids 7 – 9 . 1H‐Pyrazole‐4‐acetic acids 1 – 3 were reacted with iodoacetonitrile in the presence of triethylamine in refluxing acetonitrile to give the corresponding C‐cyanomethylated 1H‐pyrazole‐4‐acetic acids 4 – 6 as major products together with N‐cyanomethylated 3‐pyrazoline‐4‐acetic acids 7 and 8 as minor products. On the other hand, reactions of 1 and 3 with chloroacetonitrile in the presence of triethylamine in refluxing chloroform afforded the corresponding N‐cyanomethylated 3‐pyrazoline‐4‐acetic acids 7 and 9 as major products. Thermal treatment of 7 – 9 with sodium hydride in N,N‐dimethylformamide caused ring expansion to yield the corresponding 4‐pyridazineacetic acids 10 – 12 .     

Phase transition in porous electrodes. II. Effect of asymmetry in the ion size

The electrochemical thermodynamics of electrolytes in porous electrodes is qualitatively different from that in the bulk with planar electrodes when the pore size is comparable to the size of the electrolyte ions. In this study, the effect of the ion size asymmetry on the thermodynamics in porous electrodes was studied by using Monte Carlo simulation. We used the electrolyte ions for which the size of the cations and that of anions is different. Due to the asymmetry in the ion size, the ionic structure and the way the surface charge is distributed on the electrode surfaces were found to be qualitatively different in the cathode and in the anode. In particular, for some ranges of applied voltage, the distribution of the surface charge induced on the electrode planes shows inhomogeneity, which is not intrinsic to the structure of the porous electrodes. The transition from the homogeneous to the inhomogeneous distribution of surface charge on changing the voltage is a second order phase transition.     

Local structures in ionic liquids probed and characterized by microscopic thermal diffusion monitored with picosecond time-resolved Raman spectroscopy

Vibrational cooling rate of the first excited singlet (S(1)) state of trans-stilbene and bulk thermal diffusivity are measured for seven room temperature ionic liquids, C(2)mimTf(2)N, C(4)mimTf(2)N, C(4)mimPF(6), C(5)mimTf(2)N, C(6)mimTf(2)N, C(8)mimTf(2)N, and bmpyTf(2)N. Vibrational cooling rate measured with picosecond time-resolved Raman spectroscopy reflects solute-solvent and solvent-solvent energy transfer in a microscopic solvent environment. Thermal diffusivity measured with the transient grating method indicates macroscopic heat conduction capability. Vibrational cooling rate of S(1) trans-stilbene is known to have a good correlation with bulk thermal diffusivity in ordinary molecular liquids. In the seven ionic liquids studied, however, vibrational cooling rate shows no correlation with thermal diffusivity; the observed rates are similar (0.082 to 0.12 ps(-1) in the seven ionic liquids and 0.08 to 0.14 ps(-1) in molecular liquids) despite large differences in thermal diffusivity (5.4-7.5 × 10(-8) m(2) s(-1) in ionic liquids and 8.0-10 × 10(-8) m(2) s(-1) in molecular liquids). This finding is consistent with our working hypothesis that there are local structures characteristically formed in ionic liquids. Vibrational cooling rate is determined by energy transfer among solvent ions in a local structure, while macroscopic thermal diffusion is controlled by heat transfer over boundaries of local structures. By using "local" thermal diffusivity, we are able to simulate the vibrational cooling kinetics observed in ionic liquids with a model assuming thermal diffusion in continuous media. The lower limit of the size of local structure is estimated with vibrational cooling process observed with and without the excess energy. A quantitative discussion with a numerical simulation shows that the diameter of local structure is larger than 10 nm. If we combine this lower limit, 10 nm, with the upper limit, 100 nm, which is estimated from the transparency (no light scattering) of ionic liquids, an order of magnitude estimate of local structure is obtained as 10 nm < L < 100 nm, where L is the length or the diameter of the domain of local structure.     

Effects of bubble size on heat transfer enhancement by sub-millimeter bubbles for laminar natural convection along a vertical plate

Injection of sub-millimeter bubbles is considered a promising technique for enhancing natural convection heat transfer for liquids. So far, we have experimentally investigated heat transfer characteristics of laminar natural convection flows with sub-millimeter bubbles. However, the effects of the bubble size on the heat transfer have not yet been understood. The purpose of this study is to clarify the effects of the bubble size on the heat transfer enhancement for the laminar natural convection of water along a vertical heated plate with uniform heat flux. Temperature and velocity measurements, in which thermocouples and a particle tracking velocimetry technique are, respectively used, are conducted to investigate heat transfer and flow characteristics for different bubble sizes. Moreover, two-dimensional numerical simulations are performed to comprehensively understand the effects of bubble injection on the flow near the heated plate. The result shows that the ratio of the heat transfer coefficient with sub-millimeter-bubble injection to that without injection ranges from 1.3 to 2.2. The result also shows that for a constant bubble flow rate, the heat transfer coefficient ratio increases with a decrease in the mean bubble diameter. It is expected from our estimation based on both experimental data and simulation results that this increase results from an increase in the advection effect due to bubbles.     

Phase behavior of mixed polyoxyethylene-type nonionic surfactants in water

Cloud temperatures, phase behavior, and the structures of liquid crystals were investigated in the aqueous systems of homogenous hexaethylene glycol dodecyl ether(C₁₂EO₆) and mixed C₁₂EO₄-C₁₂EO₈, C₁₂EO₂-EO₈, C₁₂EO₂-C₁₂EO₈, and C₁₂EO₀-C₁₂EO₈ In the mixed surfactant systems, the average polyoxyethylene- (EO-) chain lengths are kept constants, the same as C₁₂EO₆. The change in cloud temperatures is small in all the systems, whereas the phase behavior is successively changed with increasing the difference in EO-chain length in the mixture. Lamellar liquid crystal is developed in the phase diagrams and it intrudes in the two-phase region above the cloud temperature. Hence, the phase pattern of the present mixed surfactant systems resembles that of C₁₂EO₅ system, but both cloud point and W+L region appear at much higher temperature. Hence, the Hydrophile-Lipophile Balance of the surfactant is not largely changed by mixing the surfactants but the SAXS results show that the surfactant molecules are more tightly packed in the hexagonal and lamellar phases by mixing. It is considered that when surfactants of different EO-chain lengths are mixed, the considerable reduction in repulsion between the hydrophilic moieties takes place and the surfactant molecules are more tightly packed.     

Crystallization behavior and origin of c-axis orientation in sol–gel-derived ZnO:Li thin films on glass substrates

Preferentially, c-axis-oriented lithium-doped zinc oxide (ZnO:Li) thin films were prepared on Pyrex borosilicate glass substrates by a sol–gel method starting from zinc acetate dihydrate, lithium chloride, 2-methoxyethanol and monoethanolamine. Decomposition and crystallization behavior of dip-coated amorphous precursor films during post-annealing treatments were investigated by thermogravimetry–differential thermal analysis (TG–DTA), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), optical transmittance measurements, field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). It was revealed that the films contained the organic compounds at temperatures up to 300°C, which was the key to the transformation from the amorphous to the crystalline state. Thermodynamical consideration of nucleation and crystal growth was made taking account of surface energies of the film and the glass substrate and an interfacial energy between them. Mechanisms underlying the c-axis orientation were proposed based upon the initial orientation due to nucleation and final growth orientation.     

Relaxation Behavior of Laser-Polarized Xe Gas: Size Dependency and Wall Effect of the T1 Relaxation Time in Glass and Gelatin Bulbs

Size dependency of the relaxation time T₁ was measured for laser-polarized ¹²⁹Xe gas encapsulated in different sized cavities made by glass bulbs or gelatin capsules. The use of laser-polarized gas enhances the sensitivity a great deal, making it possible to measure the longer ¹²⁹Xe relaxation time in quite a short time. The size dependency is analyzed on the basis of the kinetic theory of gases and a relationship is derived in which the relaxation rate is connected with the square inverse of the diameter of the cavity. Such an analysis provides a novel parameter which denotes the wall effect on the relaxation rate when a gas molecule collides with the surface once in a second. The relaxation time of ¹²⁹Xe gas is also dependent on the material which forms the cavity. This dependency is large and the relaxation study using polarized ¹²⁹Xe gas is expected to offer important information about the state of the matter of the cavity wall.     

Novel ultra-fast luminescence from incipient ion tracks of insulator crystals: electron–hole plasma formation in the track core

Measurements of fast luminescence decay and time-resolved spectra revealed novel ultra-fast luminescence with the lifetime of several tens ps in heavy-ion-irradiated single crystals of LiF, NaF, NaCl, KCl, KBr, KI, RbI, CsCl, CsBr, CsI, -alumina, and MgO. The luminescence is furthermore characterized by a super-linear increase in the efficiency with increasing excitation density, non-tailed decay curve, and temperature-insensitive decay-rate and yield. The results mean that the luminescence neither originates from localized excited states such as self-trapped excitons, free excitons, excited defects, and excited impurity centers nor their interaction. A process which does not contradict the experimental results is the formation of the e–h plasmas and the luminescence from them.     

Measurement of fusion excitation functions of 27, 29, 31Al + 197Au

A systematic study of the sub-barrier fusion reactions with neutron-rich projectiles has been carried out for three isotopes ^27,29,31Al bombarding a ¹⁹⁷Au target. A target chamber equipped with a target stack and sets of MWPC was employed in order to enhance the efficiency of the radioactive beam experiment. Coupled-channel calculations including the quadrupole excitations do not well fit the measured fusion excitation functions, whereas flat barrier distributions to represent the coupling to the neutron transfer largely account for the observed enhancement of the sub-barrier fusion cross-sections. Received: 13 March 2001 / Accepted: 27 April 2001