A Defect‐Free Ring Polymer: Size‐Controlled Cyclic Poly(tetrahydrofuran) Consisting Exclusively of the Monomer Unit

A series of size‐controlled, cyclic poly(tetrahydrofuran)s ( of 4 400–8 600) that consist exclusively of the monomer, i.e., oxytetramethylene, unit ( I ) have been prepared in high yield through the metathesis polymer cyclization of a telechelic precursor having allyl groups, 1 , in the presence of a Grubbs catalyst, and the subsequent hydrogenation of the linking, i.e., 2‐butenoxy, unit in the presence of an Adams' catalyst (PtO₂). A remarkable topology effect has subsequently been observed upon the isothermal crystallization of these two model polymers, showing distinctive spherulite growth rates and spherulite morphologies in comparison with the relevant linear poly(tetrahydrofuran) counterpart that has ethoxy end groups ( II ).

     

Modulating the ground state,stability and charge transport in OFETs of biradicaloid hexahydro-diindenopyrene derivatives and a proposed method to estimate the biradical character

Biradicaloid compounds with an open-shell ground state have been the subject of intense research in the past decade. Although diindenoacenes are one of the most developed families, only a few examples have been reported as active layers in organic field-effect transistors (OFETs) with a charge mobility of around 10⁻³ cm² V⁻¹ s⁻¹ due to a steric disadvantage of the mesityl group to kinetically stabilize compounds. Herein, we disclose our efforts to improve the charge transport of the diindenoacene family based on hexahydro-diindenopyrene (HDIP) derivatives with different annelation modes for which the most reactive position has been functionalized with (triisopropylsilyl)ethynyl (TIPS) groups. All the HDIP derivatives show remarkably higher stability than that of TIPS-pentacene, enduring for 2 days to more than 30 days, which depends on the oxidation potential, the contribution of the singlet biradical form in the ground state and the annelation mode. The annelation mode affects not only the band gap and the biradical character (y₀) but also the value of the singlet–triplet energy gap (ΔE_S–T) that does not follow the reverse trend of y₀. A method based on comparison between experimental and theoretical bond lengths has been disclosed to estimate y₀ and shows that y₀ computed at the projected unrestricted Hartree–Fock (PUHF) level is the most relevant among those reported by all other methods. Thanks to their high stability, thin-film OFETs were successfully fabricated. Well balanced ambipolar transport was obtained in the order of 10⁻³ cm² V⁻¹ s⁻¹ in the bottom-gate/top-contact configuration, and unipolar transport in the top-gate/bottom-contact configuration was obtained in the order of 10⁻¹ cm² V⁻¹ s⁻¹ which is the highest value obtained for biradical compounds with a diindenoacene skeleton.

Biradicaloid HDIP derivatives show that the ΔE_S–T gap does not follow the reverse trend of the biradical character but depends more on the delocalization of the radical centres at the outer rings.     

Biosynthesis of Indole Diterpene Lolitrems: Radical-Induced Cyclization of an Epoxyalcohol Affording a Characteristic Lolitremane Skeleton

Lolitrems are tremorgenic indole diterpenes that exhibit a unique 5/6 bicyclic system of the indole moiety. Although genetic analysis has indicated that the prenyltransferase LtmE and the cytochrome P450 LtmJ are involved in the construction of this unique structure, the detailed mechanism remains to be elucidated. Herein, we report the reconstitution of the biosynthetic pathway for lolitrems employing a recently established genome-editing technique for the expression host Aspergillus oryzae. Heterologous expression and bioconversion of the various intermediates revealed that LtmJ catalyzes multistep oxidation to furnish the lolitrem core. We also isolated the key reaction intermediate with an epoxyalcohol moiety. This observation allowed us to establish the mechanism of radical-induced cyclization, which was firmly supported by density functional theory calculations and a model experiment with a synthetic analogue.     

Enhanced Operational Durability of Thermally Activated Delayed Fluorescence-Based Organic Light-Emitting Diodes with a Triazine Electron Transporter

In organic light-emitting diodes (OLEDs) based on materials that show thermally activated delayed fluorescence (TADF), the internal quantum efficiency of 100 % can be obtained without using phosphorescence-based organometallics that contain rare metals. Therefore, with TADF-based emitters, it is possible to fabricate high-performing OLEDs at a lower cost. However, compared with fluorescence- and phosphorescence-based OLEDs, an understanding of degradation mechanisms in TADF-based OLEDs is still insufficient for future commercialization. In particular, it is widely recognized that the development of electron transport materials is crucial for improving OLED characteristics, especially driving voltages and operational durability. In this study, it was demonstrated that the operational durability of TADF-based OLEDs was greatly improved by introducing a triazine-based material of 2,4,6-tris(1,1′-biphenyl-4-yl)-[1,3,5]triazine (pT2T) as a hole-blocking layer (HBL) compared with a conventional HBL material of 2,4,6-tris(biphenyl-3-yl)-[1,3,5]triazine (T2T). Several experiments were carried out to make the reasons of the improved durability clearer, and attributed the improved durability to the shift of a carrier recombination zone from the emitting layer/HBL interface and the suppressed formation of excited-state quenchers in the pT2T HBL, because of the higher electron mobility of pT2T and the better stability of its radical anion state.     

Synthesis of C12-Keto Saxitoxin Derivatives with Unusual Inhibitory Activity Against Voltage-Gated Sodium Channels

A novel series of C12-keto-type saxitoxin (STX) derivatives bearing an unusual nonhydrated form of the ketone at C12 has been synthesized, and their Na_V-inhibitory activity has been evaluated in a cell-based assay as well as whole-cell patch-clamp recording. Among these compounds, 11-benzylidene STX ( 3 a ) showed potent inhibitory activity against neuroblastoma Neuro 2A in both cell-based and electrophysiological analyses, with EC₅₀ and IC₅₀ values of 8.5 and 30.7 nm , respectively. Interestingly, the compound showed potent inhibitory activity against tetrodotoxin-resistant subtype of Na_V1.5, with an IC₅₀ value of 94.1 nm . Derivatives 3 a – d and 3 f showed low recovery rates from Na_V1.2 subtype (ca 45–79 %) compared to natural dcSTX ( 2 ), strongly suggesting an irreversible mode of interaction. We propose an interaction model for the C12-keto derivatives with Na_V in which the enone moiety in the STX derivatives 3 works as Michael acceptor for the carboxylate of Asp¹⁷¹⁷.     

Photophysical Properties and Efficient,Stable, Electrogenerated Chemiluminescence of Donor–Acceptor Molecules Exhibiting Thermal Spin Upconversion

The photophysical properties and electrogenerated chemiluminescence (ECL) of three donor–acceptor molecules composed of dicyanobenzene and methyl‐, tert‐butyl‐, and phenyl‐substituted carbazolyl groups, 1,2,3,5‐tetrakis(3,6‐disubstituted‐carbazol‐9‐yl)‐4,6‐dicyanobenzene (4CzIPN‐Me, 4CzIPN‐tBu, and 4CzIPN‐Ph, respectively) are described. These molecules show delayed fluorescence as a result of thermal spin upconversion from the lowest triplet state to the lowest singlet state at room temperature. The three molecules showed yellow to yellowish–red ECL. Remarkably, the ECL efficiencies of 4CzIPN‐tBu in dichloromethane reached almost 40 %. Moreover, stable ECL was emitted from 4CzIPN‐tBu and 4CzIPN‐Ph. In case of 4CzIPN‐Me, the ECL intensity decreased during voltage cycles because of polymerization. Quantum chemical calculations revealed that polymerization was inhibited by the steric hindrance of the bulky tert‐butyl and phenyl groups on the carbazolyl moieties and lowered the spin density on the carbazolyl groups through electron conjugation for 4CzIPN‐Ph.     

The Importance of Excited‐State Energy Alignment for Efficient Exciplex Systems Based on a Study of Phenylpyridinato Boron Derivatives

Understanding excited‐state dynamics is critical for improving the photoluminescence (PL) efficiency of exciplexes. A series of exciplexes based on conventional hole‐transporting materials as donor and newly developed phenylpyridinato boron derivatives as acceptor were investigated. High PL efficiencies were achieved in only some combinations, and a large difference in performance among combinations provided insight into nonradiative processes in exciplex systems. Furthermore, the triplet local excited states (³LE) of each donor and acceptor were found play an important role in triplet exciplex harvesting. Significant contributions from triplets were clearly observed when the charge‐transfer excited states (¹CT and ³CT) and ³LE were ideally aligned. We also demonstrated fine control of relative energy alignment via the concentration to improve the PL efficiency.     

Transmission electron microscopy observation of GaAs/Al0.3Ga0.7As T-shaped quantum well structure fabricated by glancing angle molecular beam epitaxy on GaAs(100) reverse-mesa etched substrates

GaAs/Al_0.3Ga_0.7As multi-layer structures were grown on GaAs (100) reverse-mesa etched substrates by glancing angle molecular beam epitaxy (GA-MBE). A(111)B facet was formed as a side-facet. Surface migration of Ga and Al atoms from the (100) flat region to the (111)B side-facet region has been investigated to fabricate T-shaped GaAs/AlGaAs quantum wells (QWs) under the condition that Ga and Al atoms impinge only an the (100) flat region and do not impinge on the (111)B side-facet. Observation of T-shaped GaAs/AlGaAs quantum wires (QWRs) by cross-sectional transmission electron microscopy (TEM) revealed that there is no migration of Al atoms from the (100) to the (111)B facet region at a substrate temperature (T_s) as high as 630°C, under a V/III ratio of 28 (in pressure ratio). On the other hand, very thin GaAs epitaxial layers grown on the (111)B side-facet region owing to the Ga migration were observed for substrate temperatures of 600 and 630°C. It was found that the mass flow of Ga atoms from the (100) region to the (111)B side-facet region increases, with the thermal activation energy of 2.0 eV, as the substrate temperature increases from 570 to 630°C. The GA-MBE growth on a reverse-mesa etched GaAs substrate at a low temperature 570°C or lower is desirable to fabricate a nm-scale GaAs/AlGaAs QWR structure with nm-scale precision.     

Preferential migration of indium atoms on the (411)A plane in InGaAs grown on GaAs channeled substrates by molecular beam epitaxy

Lateral profiles of In content in a 1.5 μm thick In_xGa_1−xAs (x 0.2) layer grown on GaAs channeled substrates (CSs) with (411)A side-slopes by molecular beam epitaxy (MBE) have been investigated with the use of energy dispersive X-ray spectroscopy (EDX). The observed profiles of the In content suggested that In atoms migrate preferentially in the [1 ] direction on the (411)A plane during MBE growth. This preferential migration of In atoms along [1 ] on the (411)A plane was confirmed by comparing observed lateral profiles of In content in InGaAs layers grown on GaAs CSs and simulated In profiles which are calculated by taking into account of an additional one-way flow of In atoms along [1 ].     

A novel mediator-polymer-modified anode for microbial fuel cells

A high-performance anode system based on a combination of mediator-polymer-modified graphite felt and bacteria capable of reducing extracellular materials shows significant potential for practical use in microbial fuel cells (MFCs).