Application of polyamorphism in water to spontaneous crystallization of emulsified LiCl-H2O solution

Aqueous solutions are widely explained by the hydration or the bound waterfree water notion. Amorphous polymorphism (polyamorphism) in pure water, which is presently under vigorous discussion, may provide a different view over the solutions. Here, I changed pressure, P, temperature, T, and concentration, C, of emulsified LiCl-H2O solutions and studied their freezing by detecting its heat evolution. It was experimentally indicated that the homogeneous nucleation of low-density crystalline ice I (phase Ih or Ic), in pure water and in solutions, connects to the polyamorphic transition of high-density amorphous ice (HDA) to low-density amorphous ice (LDA). Thus, the polyamorphism of water relates to the phase behavior of aqueous solution. In accordance with the recent simulation result, the nucleation was thought to occur in two stages: the appearance of the LDA-like state and the crystallization. Usefulness of the polyamorphic point of view about the solutions was seen.     

Studies directed towards total synthesis of saframycin: I. A synthesis of hexahydro-1,5-imino-3-benzazocin-7,10-dione.

A short-step synthesis of $\text{2}$, the right-hand half of antibiotic saframycin ($\text{1}$), is described. The key steps of this synthesis are the acid catalyzed intramolecular double cyclization of $\text{4}$ and the oxidative demethylation of $\text{7}$ to the quinone ($\text{2}$).     

Interfacial tension and wetting behavior of air/oil/ionic liquid systems

We measured the interfacial tension and the density of air/n-hexane, n-decane, 1-perfluorohexane/1-hexyl-3-methyl-imidazolium hexafluorophosphate systems as a function of temperature. From the air/ionic liquid surface tension values, it was suggested that Coulombic interaction between imidazolium cations and counter anions are not so much different between the surface and bulk. The density values indicated that the decrease of surface tension by saturating organics was closely correlated to the mutual solubility between ionic liquid and organics. Interfacial tension at the oil/ionic liquid interfaces suggested that ionic liquid molecules were more ordered at the oil/ionic liquid interfaces compared to the air/ionic liquid interfaces, but the decrease of the entropy due to the interfacial orientation of ionic liquid was compensated by the increase of the entropy due to the contact of different chemical species. The initial spreading coefficients and the Hamaker constants indicated that all the oil phases spread at the air/ionic liquid interfaces spontaneously, and form the complete wetting films.     

Two distinct raman profiles of glassy dilute LiCl solution

We make glass of dilute LiCl aqueous solution by cooling micrometer-sized droplets of the solution extremely quickly and measure the Raman spectra of the glass. It is found that the OH stretching vibration mode of the glass of dilute solution is composed of the OH stretching vibration mode of pure glassy water and that of the glass of solvent water in the highly concentrated solution. This is consistent with the possibility of the existence of two distinct glassy states of water in dilute LiCL solution at low temperature.     

Organofluorosilicates in organic synthesis: XV. Reaction of exo- and endo-5-norbornen-2-ylsilyl derivatives with n-bromosuccinimide. Difference in reactivity between hexacoordinate and tetracoordinate silicon compounds

The reactions of potassium 5-norbornen-2-ylpentafluorosilicate (I) and 5-norbornen-2-yltrimethylsilane (II) with NBS were examined. The former reaction gave 3-nortricyclyl bromide (IV) as the only detectable product, arising from the carbon—silicon bond cleavage. The latter reaction, however, gave 3-bromo-1-nortricyclyltrimethylsilane (V) as the major product, resulting from cleavage of the carbon—hydrogen bond α to silicon, together with IV and an unidentified product. GLC-monitoring of the reactions showed the higher reactivity of the norbornenyl derivative having the leaving group in theendo position irrespective of whether the leaving group is SiF₅ or H. Since no inhibition was observed by the addition of hydroquinone in the dark, the reactions have been regarded as homoallylic electrophilic substitutions. A concerted mechanism seems to be consistent with the experimental data. Cleavage of 1-nortricyclyltrimethylsilane by iodine monochloride to give 1-iodonortricyclene has also been studied.     

Response functions for cosmic-ray muons at various depths underground

Summary Response functions for underground muons are obtained by solving numerically the equations of hadronic cascades in the atmosphere, by assuming Feynman scaling for hadronic interactions over the whole energy region. For practical use of the response functions in cosmic-ray modulation study, calculations are made for various combinations of parameters such as zenith angle, atmospheric depth and muon threshold energy. The present response functions are consistent with cosmic-ray measurements and can be well utilized for the study on the cosmic-ray modulation.

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Riassunto Si ottengono funzioni di risposta per muoni sotterranei risolvendo numericamente le equazioni per le cascate adroniche nell'atmosfera, assumendo lo scaling di Feynman per interazioni adroniche nell'intera regione di energia. Per l'uso pratico di funzioni di risposta nello studio di modulazione dei raggi cosmici, si fanno calcoli per varie combicazioni di parametri come l'angolo di zenit, la profondità atmosferica e l'energia muonica di soglia. Le attuali funzioni di risposta sono coerenti con le misurazioni dei raggi cosmici e possono essere bene utilizzate per lo studio della modulazione dei raggi cosmici.

     

Direct imaging of the InSb001-c8 x 2 surface: evidence for large anisotropy of the reconstruction

We have observed the InSb(001)-c(8 x 2) surface by using high-resolution transmission electron microscopy in the profile-imaging geometry. All images observed at temperatures up to 420 degrees C agree well with the c(8 x 2) model reported by Kumpf et al. [Phys. Rev. Lett. 86, 3586 (2001)]]. 1/30 sec real-time observations at 420 degrees C evidence that a part of the subsurface and surface layers (called a gull-type segment) undergo switching to and from a bulk configuration. The finding is suggestive of large anisotropy in the mean square displacement of the c(8 x 2) surface.     

Evaluation analysis of prediction methods for two-phase flow pressure drop in mini-channels

Two-thousand and ninety-two data of two-phase flow pressure drop were collected from 18 published papers of which the working fluids include R123, R134a, R22, R236ea, R245fa, R404a, R407C, R410a, R507, CO₂, water and air. The hydraulic diameter ranges from 0.506 to 12 mm; Re_l from 10 to 37,000, and Re_g from 3 to 4 × 10⁵. Eleven correlations and models for calculating the two-phase frictional pressure drop were evaluated based upon these data. The results show that the accuracy of the Lockhart–Martinelli method, Mishima and Hibiki correlation, Zhang and Mishima correlation and Lee and Mudawar correlation in the laminar region is very close to each other, while the Muller-Steinhagen and Heck correlation is the best among the evaluated correlations in the turbulent region. A modified Chisholm correlation was proposed, which is better than all of the evaluated correlations in the turbulent region and its mean relative error is about 29%. For refrigerants only, the new correlation and Muller-Steinhagen and Heck correlation are very close to each other and give better agreement than the other evaluated correlations.     

High temperature effect on photo-induced electron transfer

Anharmonicity plays a very important role in the high temperature range for photo-induced electron transfer. A simple truncated oscillator model is used to investigate the effect of the disallowed states of anharmonicity on the photo-induced electron transfer. The obtained formula shows that in the high temperature limit, the electron transfer rate becomes a constant, independent of temperature, but the Marcus equation approaches zero.     

Gas‐phase acidity of bis[(perfluoroalkyl)sulfonyl]imides. Effects of the perfluoroalkyl group on the acidity

The gas‐phase acidity (GA) values were determined for a number of perfluoroalkyl‐substituted sulfonylimides by measuring proton‐transfer equilibria using a Fourier transform ion cyclotron resonance (FT‐ICR) mass spectrometer. The GA scale below 286.5 kcal mol^?1 for (CF₃SO₂)₂NH was extended and partially revised. The GA value of (C₄F₉SO₂)₂NH which is currently the strongest acid was revised from 284.1 to 278.6 kcal mol^?1. The effect of fluorine atoms on the acidity of perfluoroalkyl‐substituted sulfonylimides was described with the following model where N_(α), N_(β), N_(γ), and N_(δ) are the numbers of fluorine atoms at α, β, γ, and δ position in R_fSO₂ (R_f = perfluoroalkyl group), respectively. This correlation indicates that the electron‐withdrawing ability of the R_fSO₂ group can be described in terms of the number of fluorine atoms in the perfluoroalkyl group corrected by taking into account their positions. Copyright © 2014 John Wiley & Sons, Ltd.