Asymmetric conjugate addition of α-keto esters to nitroolefins catalyzed by chiral CuII hydroxo complexes

As a part of our research project on hard anion-late transition metal complexes as mild acid–base catalysts, we describe herein that Cu^II hydroxo complexes having chiral N-substituted-diaminocyclohexanes are mild and selective catalysts, which are applicable to the catalytic asymmetric conjugate addition of α-keto esters to nitroolefins. The reaction proceeded diastereoselectively without the detectable formation of self-aldol products, affording the corresponding coupling products with anti-stereochemistry in an enantioselective manner.     

Background story of the invention of efficient blue InGaN light emitting diodes (Nobel Lecture)

Shuji Nakamura discovered p‐type doping in Gallium Nitride (GaN) and developed blue, green, and white InGaN based light emitting diodes (LEDs) and blue laser diodes (LDs). His inventions made possible energy efficient, solid‐state lighting systems and enabled the next generation of optical storage. Together with Isamu Akasaki and Hiroshi Amano, he is one of the three recipients of the 2014 Nobel Prize in Physics. In his Nobel lecture, Shuji Nakamura gives an overview of this research and the story of his inventions *** .

     

Maxwell speed distribution and analogue Hawking–Unruh temperature in an ontological model of a Harmonic oscillator ground state

Within an ontological (hidden variable) model of quantum fluctuation, one can discuss the actual   properties of a system regardless (independent) of measurement. Here we apply an ontological model proposed earlier to investigate a Harmonic oscillator in the quantum mechanical ground state. We first show that the actual speed of the oscillator fluctuates randomly following the Maxwell–Boltzmann distribution. On the other hand, the actual energy obeys a broad Gamma distribution with an average 3?ω/2$3?\omega /2$, where ω$\omega$ is the classical angular frequency, so that one may conclude that the outcome of a single energy measurement reveals the average of the actual energy. The distribution of actual speed (energy) thus formally resembles the distribution of speed (energy) of an ideal gas in thermal equilibrium of temperature T_g=?ω/2$T_g=?\omega /2$. We shall then argue that T_g$T_g$ can be written in a form analogous to the Hawking temperature for a Schwarzschild black hole in which the average distance of the oscillator from the origin plays the analogous role of the radius of the black hole event horizon. It can also be written in a form analogous to the Unruh temperature experienced by a body moving with a uniform acceleration. In the analogy, the oscillator suffers an effective acceleration which balances the attractive force of the trapping Harmonic potential, thus keeps its average position away from the origin.     

Acid/base-regulated reversible electron transfer disproportionation of N–N linked bicarbazole and biacridine derivatives

Regulation of electron transfer on organic substances by external stimuli is a fundamental issue in science and technology, which affects organic materials, chemical synthesis, and biological metabolism. Nevertheless, acid/base-responsive organic materials that exhibit reversible electron transfer have not been well studied and developed, owing to the difficulty in inventing a mechanism to associate acid/base stimuli and electron transfer. We discovered a new phenomenon in which N–N linked bicarbazole (BC) and tetramethylbiacridine (TBA) derivatives undergo electron transfer disproportionation by acid stimulus, forming their stable radical cations and reduced species. The reaction occurs through a biradical intermediate generated by the acid-triggered N–N bond cleavage reaction of BC or TBA, which acts as a two electron acceptor to undergo electron transfer reactions with two equivalents of BC or TBA. In addition, in the case of TBA the disproportionation reaction is highly reversible through neutralization with NEt₃, which recovers TBA through back electron transfer and N–N bond formation reactions. This highly reversible electron transfer reaction is possible due to the association between the acid stimulus and electron transfer via the acid-regulated N–N bond cleavage/formation reactions which provide an efficient switching mechanism, the ability of the organic molecules to act as multi-electron donors and acceptors, the extraordinary stability of the radical species, the highly selective reactivity, and the balance of the redox potentials. This discovery provides new design concepts for acid/base-regulated organic electron transfer systems, chemical reagents, or organic materials.     

Pressure-driven startup flows of liquid crystalline polymers through slit cells

A wavy texture occurs in the flows of liquid crystalline polymers through a slit cell. In the present paper the development of the wavy texture is examined in pressure-driven startup flows for four types of slit cells, using a liquid crystalline solution of 50 wt% hydroxypropylcellulose (HPC). There exists a comparatively long induction period until the wavy texture appears after the startup of the flow, and the induction time decreases with increasing apparent shear rate. However, it is found that the apparent shear strain at which the wavy texture emerges is independent of the apparent shear rate though the value of the apparent shear strain slightly varies with the type of flow cell. Furthermore, the light scattering experiments are carried out to examine the structure of wavy texture. After the startup of the flow, a homogeneous pattern of the light scattering quickly shrink in size and a spike pattern perpendicular to the flow direction is emphasized. While the wavy texture is seen, the ellipsoidal pattern of light scattering oscillates with the same frequency as the passage of the wavy texture. A structure of scattering objects in the wavy texture is proposed, based on the observation of change in the light scattering pattern with time.     

Measurement of pressure loss in the flow of polymer solutions through wavy channels

In order to examine the flow behavior of polymer solutions through porous media, the measurement of pressure loss and the experiment for flow visualization were carried out with wavy channels as one of the model channels of porous media. The test fluids used are aqueous solutions of polyacrylamide (PAA) with two different concentrations. The occurrence of the excess pressure loss, which was not due to the effect of the centrifugal force, was found for the PAA solutions. The relations between the friction factor ratio and the Deborah number were similar to that obtained for the flow through porous media. Furthermore, the results of the flow visualization suggest that the elongational property of the PAA solutions is connected with the occurrence of the excess pressure loss.