Reproducing Kernels for Iterated Parabolic Operators on the Upper Half Space with Application to Polyharmonic Bergman Spaces

We consider parabolic operators of fractional order and their iterates on the upper half space of the euclidean space. We deal with Hilbert spaces of solutions of those parabolic equations. We shall show, in this note, the existence of reproducing kernels and give a formula by using their fundamental solutions. As an application, we also discuss the polyharmonic Bergman spaces and give their reproducing kernels by using the Poisson kernel on the upper half space.     

Reconstitution of Biosynthetic Machinery for the Synthesis of the Highly Elaborated Indole Diterpene Penitrem

Penitrem A is one of the most elaborated members of the fungal indole diterpenes. Two separate penitrem gene clusters were identified using genomic and RNA sequencing data, and 13 out of 17 transformations in the penitrem biosynthesis were elucidated by heterologous reconstitution of the relevant genes. These reactions involve 1) a prenylation‐initiated cationic cyclization to install the bicyclo[3.2.0]heptane skeleton (PtmE), 2) a two‐step P450‐catalyzed oxidative processes forming the unique tricyclic penitrem skeleton (PtmK and PtmU), and 3) five sequential oxidative transformations (PtmKULNJ). Importantly, without conventional gene disruption, reconstitution of the biosynthetic machinery provided sufficient data to determine the pathway. It was thus demonstrated that the Aspergillus oryzae reconstitution system is a powerful method for studying the biosynthesis of complex natural products.     

Mechanochromic Delayed Fluorescence Switching in Propeller-Shaped Carbazole–Isophthalonitrile Luminogens with Stimuli-Responsive Intramolecular Charge-Transfer Excited States

Herein, the universal design of high-efficiency stimuli-responsive luminous materials endowed with mechanochromic luminescence (MCL) and thermally activated delayed fluorescence (TADF) functions is reported. The origin of the unique stimuli-triggered TADF switching for a series of carbazole–isophthalonitrile-based donor–acceptor (D–A) luminogens is demonstrated based on systematic photophysical and X-ray analysis, coupled with theoretical calculations. It was revealed that a tiny alteration of the intramolecular D–A twisting in the excited-state structures governed by the solid morphologies is responsible for this dynamic TADF switching behavior. This concept is applicable to the fabrication of bicolor emissive organic light-emitting diodes using a single TADF emitter.     

Optical simulation of reduced retinal illuminance caused by senile miosis

In order to simulate elderly vision for young observers, we developed an optical goggle using filters whose transmittance optically simulates the senile miosis: reduction in retinal illuminance as a function of ambient illuminance. First, we measured the pupil size of young and elderly subjects (mean age were 21.8 and 67.1 years, respectively) under six illuminance conditions (from 0.03 to 4850 lx), and formulated the relationship between illuminance and pupillary area functions in both age groups. Next, the transmittance formulae for the filter simulating the senile miosis were derived based on the properties of the pupillary area and visual functions of the elderly and the young subjects including the effect of mydriasis induced by the reduction of light due to the filter in young observers. Finally, we developed a goggle-type simulator using active optical devices which enables young people to experience senile miosis in any environment in real time.     

Improvement of water vapor adsorption ability of natural mesoporous material by impregnating with chloride salts for development of a new desiccant filter

The aim of this study is the development of a new adsorbent for the desiccant material which can be regenerated by the domestic exhaust heat by using natural mesoporous material, Wakkanai siliceous shale. To improve this shale’s performance to adsorb/desorb the water vapor, lithium chloride, calcium chloride or sodium chloride was supported into the mesopores by impregnating with each chloride solution. Especially sodium chloride was effective to increase the water vapor adsorption amount 5–7 times of that of natural shale in the relative humidity range from 50 to 70%. Moreover, the appropriate impregnating concentrations were determined as 5wt% from the relationship between the maximum water vapor adsorption amount and the mesopore volume. Based on these results, a new desiccant filter has been developed by impregnated original paper with lithium chloride and sodium chloride. This paper contained shale powder in the synthetic fibers. The dehumidification performance of this filter was evaluated under the simulated summer condition in Tokyo. From the cyclic adsorption/regeneration test, this shale and chlorides filter could adsorb and desorb 60 g/h water vapor repeatedly at the regeneration temperature of 40°C. On the other hand, a silica gel filter and a zeolite filter adsorbed and desorbed only 10 g/h and 25 g/h, respectively. These results suggested that the shale impregnated with the chlorides has the best dehumidification ability as a new desiccant material. Further, the desiccant filter made from the shale will achieve the effective use of the low temperature exhaust heat.     

High Diastereoselection of a Dissymmetric Capsule by Chiral Guest Complexation

Encapsulation of chiral guests in the dissymmetric capsule 1?4 BF₄ formed diastereomeric supramolecular complexes G ? 1?4 BF₄ ( G : guest). When chiral guests 2 a – q were encapsulated within the dissymmetric space of the self‐assembled capsule 1?4 BF₄, circular dichroism (CD) was observed at the absorption bands that are characteristic of the π–π* transition of the bipyridine moiety of the capsule, which suggests that the P and M helicities of the capsule are biased by the chiral guest complexation. The P helicity of diastereomeric complex (S)‐ 2 l ? 1?4 BF₄ was determined to be predominant, based on CD exciton coupling theory and DFT calculations. The diastereoselectivity was highly influenced by the ester substituents, such that benzyl ester moieties were good for improving the diastereoselectivity. A diastereomeric excess of 98 % was achieved upon the complexation of 2 j . The relative enthalpic and entropic components for the distereoselectivity were obtained from a van’t Hoff plot. The enthalpic components were linearly correlated with the substituent Hammett parameters (σ_p⁺). The electron‐rich benzyl ester moieties generated donor–acceptor π–π stacking interactions with the bipyridine moiety, which resulted in a significant difference in energy between the predominant and subordinate diastereomeric complexes.     

Mechanochromic Delayed Fluorescence Switching in Propeller‐Shaped Carbazole–Isophthalonitrile Luminogens with Stimuli‐Responsive Intramolecular Charge‐Transfer Excited States

Herein, the universal design of high‐efficiency stimuli‐responsive luminous materials endowed with mechanochromic luminescence (MCL) and thermally activated delayed fluorescence (TADF) functions is reported. The origin of the unique stimuli‐triggered TADF switching for a series of carbazole–isophthalonitrile‐based donor–acceptor (D–A) luminogens is demonstrated based on systematic photophysical and X‐ray analysis, coupled with theoretical calculations. It was revealed that a tiny alteration of the intramolecular D–A twisting in the excited‐state structures governed by the solid morphologies is responsible for this dynamic TADF switching behavior. This concept is applicable to the fabrication of bicolor emissive organic light‐emitting diodes using a single TADF emitter.