Creation of Circularly Polarized Luminescence from an Achiral Polyfluorene Derivative through Complexation with Helix‐Forming Polysaccharides: Importance of the meta‐Linkage Chain for Helix Formation

A circularly polarized luminescence (CPL) material has been created by polymer–polymer complexation between a helix‐forming polysaccharide, schizophyllan (SPG), and a meta‐phenylene‐linked polyfluorene derivative (mPFS). Computational modeling revealed that mPFS can adopt a helical structure although a conventional polyfluorene derivative with a para‐phenylene linkage tends to enjoy a rigid rodlike conformation. Our detailed experimental examination showed that mPFS forms a chiral nanowire complex through cohelix formation with SPG. We have found, as expected, that this cohelical complex emits highly efficient CPL even in an aqueous solution. The appearance of the high CPL property is due to 1) a high quantum yield of the fluorene unit and 2) immobilization of the helically twisted conformation of mPFS in an isolated manner through cohelix formation with SPG. One can propose, therefore, that the SPG/mPFS complex acts as a new high‐performance CPL material with a solvent‐dispersible nanowire structure.     

Effect of fuel ratio of coal on the turbulent flame speed of ammonia/coal particle cloud co-combustion at atmospheric pressure

This study aims to clarify the effect of fuel ratio of coal on the turbulent flame speed of ammonia/coal particle cloud co-combustion at atmospheric pressure under various turbulence intensities. High-fuel-ratio coals are not usually used in coal-fired thermal power plants because of their low flame stability. The expectation is that ammonia as a hydrogen-energy carrier would improve the ignition capability of coal particles in co-combustion. Experiments on spherical turbulent flame propagation of co-combustion were conducted for various coal types under various turbulence intensities, using the unique experimental apparatus developed for the co-combustion. Experimental results show that the flame speed of co-combustion with a low equivalence ratio of ammonia/oxidizer mixture for bituminous coal case was found to be three times faster than that of pure coal combustion and two times faster than that of pure ammonia combustion. On the other hand, the flame speed of co-combustion for the highest-fuel-ratio coal case is lower than that of the pure ammonia combustion case, although the flame propagation can be sustained due to the ammonia mixing. To explain the difference of tendencies depending on the fuel ratio of coal, a flame propagation mechanism of ammonia/coal particle cloud co-combustion was proposed. Two positive effects are the increases of local equivalence ratio and the increases of radiation heat flux, which increases the flame speed. In opposite, a negative effect is the heat sink effect that decreases the flame speed. The two positive effects on the flame speed of co-combustion overwhelm a negative effect for bituminous coal case, while the negative effect overcomes both positive effects for the highest-fuel-ratio coal case. The findings of the study can contribute to the reduction of solid fuel costs when the ammonia is introduced as CO₂ free energy carrier and can improve the energy security through the utilization of high-fuel-ratio coals.     

Effect of ammonia/oxygen/nitrogen equivalence ratio on spherical turbulent flame propagation of pulverized coal/ammonia co-combustion

Because ammonia is one of the most promising candidates for energy carrier in the future, various applications of ammonia as a fuel are currently considered. One medium for utilizing ammonia is by introducing it to coal-fired boilers. To the best of our knowledge, this paper is the first to report the fundamental mechanism of the flame propagation phenomenon for pulverized coal/ammonia co-combustion. The effects of the equivalence ratio of the ammonia-oxidizer mixture on the flame propagation velocity of pulverized coal/ammonia co-combustion in turbulent fields were clarified by the experiments employing a unique fan-stirred constant volume chamber. The flame propagation velocities of pulverized coal/ammonia co-combustion, pure ammonia combustion, and pure pulverized coal combustion were compared. As expected, the flame propagation velocity of pulverized coal/ammonia was higher than that of the pure pulverized coal combustion for all conditions. However, the comparison of the flame propagation velocities of pulverized coal/ammonia co-combustion and that of the pure ammonia combustion, revealed that whether the flame propagation of the pulverized coal/ammonia was higher than that of the pure ammonia combustion was dependent on the equivalence ratio of the ammonia-oxidizer. This unique feature was explained by a mechanism including three competing effects proposed by the authors. In the ammonia lean condition, the positive effects, which are the strong radiation from the luminous flame and the increment of local equivalence ratio by the addition of volatile matter, are larger than the negative effect, which is the heat absorption by coal particles in preheat zone. In the ammonia rich condition, the effect of an increment of the local equivalence ratio by the addition of volatile matter turns into a negative effect. Consequently, the negative effects overcome the positive effect in the ammonia rich condition resulting in a lower flame propagation velocity of pulverized coal/ammonia co-combustion.     

Optically Active Conjugated Polymer from Solvent Chirality Transfer Polymerization in Monoterpenes

Disubstituted acetylene monomers [1,2‐diphenylacetylenes (DPAs: DPA‐pC1, DPA‐mC1, DPA‐pC8); 1‐phenyl‐2‐hexylacetylene (PHA‐pC1)] are tested for asymmetric polymerization in chiral monoterpenes used as solvents and compared with the corresponding monosubstituted acetylene monomer [1‐phenylacetylene (PA‐pC1)]. DPA‐pC1 containing a trimethylsilyl group in the para‐position of the phenyl ring produces an optically active polymer with a large Cotton effect, despite the absence of a stereogenic center. The polymer sample obtained by polymerization in 87% ee (–)‐α‐pinene shows the strongest CD signal (g_CD value at 385 nm: ∼3.2 × 10⁻³). The Cotton bands of the polymers obtained in (–)‐ and (+)‐α‐pinenes show the opposite sign in the CD signals. Theoretical calculations show that only the cis‐cisoid model adopts a helical conformation. A time‐correlated single photon counting experiment shows that the emission of the chiral polymer originates from a virtually single excited species with a 98% component fraction. This polymer solution does not show any significant decrease in g_CD value over a wide temperature range of 20 to 80 °C. No noticeable decrease in the g_CD value is detected when the polymer solution is kept at relatively low temperatures for a prolonged period (35 d). In contrast, the other polymers show no CD signal.

     

Enzymatic resolution and evaluation of enantiomers of cis-5'-hydroxythalidomide

The straightforward synthesis of both enantiomers of cis-5'-hydroxythalidomide, a major metabolite of thalidomide, has been accomplished by enzymatic kinetic resolution of a racemic substrate catalyzed by Pseudomonas stutzeri lipase TL. cis-5'-Hydroxythalidomide shows resistance to racemization (and epimerization) at physiological pH. A tube formation assay to assess the ability to inhibit angiogenesis revealed that cis-5'-hydroxythalidomides are inactive.     

Isotope Effect on Physical Properties of BEDT-TTF Based Organic Superconductors

Abstract

The isotope shifts of the superconducting transition temperature for K-(BEDT-TTF)₂Cu[N(CN)₂]Br were evaluated from the resistivity and dc magnetization measurements. The deuteration of the terminal ethylene groups of the donor molecule lowered T_c by 0.4 to 0.5K, whereas the ¹³C substitution on the same fragments gave no isotope shifts within the experimental accuracy.     

Optically active, lyotropic liquid crystalline poly(diphenylacetylene) derivative: hierarchical chiral ordering from isotropic solution to anisotropic solid films

The side chain chirality of a poly(diphenylacetylene) derivative was transferred and amplified spontaneously from solution to a bulk film due to lyotropic liquid crystallinity.     

Existence of an Almost Periodic Solution in a Difference Equation with Infinite Delay

In order to obtain the existence of an almost periodic functional difference equation x(n + 1) = ?(n,x_n ),n ∈ Z ⁺ and where x_n is defined by x_n (s) = x(n + s) for s ∈ Z ^?, on an axiomatic phase space B, we consider a certain stability property, which is referred to as BS-stable under disturbances from Ω(?) with respect to K, this stability implies ρ-stable under disturbances from Ω(?) with respect to compact set K.