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.     

Polymer‐Assisted Solution‐Phase Synthesis and Neurite‐Outgrowth‐Promoting Activity of 15‐Deoxy‐Δ12,14‐PGJ2 Derivatives

An efficient solution‐phase synthesis of rac‐15‐deoxy‐Δ^12,14‐PGJ₂ (15dPGJ₂) derivatives that contain variable α and ω chains based on a polymer‐assisted strategy and their neurite‐outgrowth‐promoting activity are described. The strategy for the synthesis of PGJ₂ derivatives involves the use of a vinyl iodide bearing cyclopentenone as a key intermediate, which undergoes Suzuki–Miyaura coupling and subsequent Lewis acid catalyzed aldol condensation for incorporation of the ω and α chains, respectively. For easy access to the PGJ₂ derivatives, a polymer‐supported catalyst and scavengers were adapted for use in these four diverse steps, in which workup and purification can be performed by simple filtration of the solid‐supported reagents. By using this methodology, we succeeded in the synthesis of 16 PGJ₂ derivatives with four alkyl boranes and four aldehydes. The neurite‐outgrowth‐promoting activity of the 16 synthetic compounds in PC12 cells revealed that the side‐chains play a major role in modulating their biological activity. The carboxylic acid on the α chain improved the biological activity, although it was not absolutely required. Furthermore, a PGJ₂ derivative with a phenyl moiety on the ω chain was found to exhibit an activity comparable to that of natural 15dPGJ₂.     

Channel-selective independent sorption and collection of hydrophilic and hydrophobic molecules by Cs2[Cr3O(OOCC2H5)6(H2O)3]2[alpha-SiW12O40] ionic crystal

An ionic crystal of Cs2[Cr3O(OOCC2H5)6(H2O)3]2[alpha-SiW12O40].4H2O 1a with hydrophilic and hydrophobic channels has been designed and successfully synthesized. The guest-free phase 1b sorbs dichloromethane and water in the hydrophobic and hydrophilic channels, respectively. The rate and equilibrium amount of the dichloromethane sorption into the hydrophobic channel and those of water into the hydrophilic channel were independent of each other. The sorption properties can be applied to the channel-selective sorption and collection of hydrophobic (dichloromethane) and hydrophilic (water) molecules from the mixture.     

Adsorption/oxidation of CO on highly dispersed Pt catalyst studied by combined electrochemical and ATR-FTIRAS methods: oxidation of CO adsorbed on carbon-supported Pt catalyst and unsupported Pt black

ATR-FTIRAS measurements combined with linear potential sweep voltammetry were conducted to investigate oxidation of CO adsorbed on a highly dispersed Pt catalyst supported on carbon black, Pt/C, and carbon-unsupported Pt black catalyst, Pt-B. Bands nu(CO) of atop- and bridge-bonded COs were resolved into those of COs adsorbed at terrace and step edge sites by curve-fitting analysis. At the high coverage near the saturation, a band around 1950-1960 cm(-1) assigned to asymmetric bridge-bonded CO, CO(B)(asym), was observed to develop on both Pt/C and Pt-B, which was the predominant type on the latter. Preferential oxidation of atop-CO adsorbed at the step edge site was commonly observed on both Pt/C and Pt-B during the potential sweep from 0.05 to 1.2 V. However, it has been found that CO(B)(asym) is the most reactive species. The high reactivity of the CO(B)(asym) on Pt/C and Pt-B is demonstrated for the first time in the present report. Adsorption of CO on the Pt/C and Pt-B resulted in growth of a sharp nu(OH) band around 3642-3645 cm(-1) which is assigned to non-hydrogen-bonded water molecules coadsorbed with CO. The nu(OH) band frequency exhibits a linear increase with potential with a Stark tuning rate of ca. 20 cm(-1)/V. Analysis of the potential dependence of this band in the CO oxidation potential region led us to conclude that this is the oxygen-containing species to oxidize adsorbed CO. Stark tuning rates of nu(CO) bands for the COs at the terrace and step edge sites on both Pt/C and Pt-B are almost independent of the adsorption sites for both atop- and bridge-bonded COs. However, CO(B)(asym) exhibits tuning rates of 41 cm-1/V and 37 cm-1/ V on Pt/C and Pt-B, respectively, which is in between the rates of atop and symmetric bridge-bonded COs.     

Iridium-catalyzed allylic alkylation of monosubstituted allylic acetates with azlactone, and separation of diastereoisomers by sequential aza-Cope rearrangement

The iridium-catalyzed allylic alkylation with azlactone and sequential aza-Cope rearrangement was demonstrated. The sequential reaction was effective in separating of diastereoisomers and afforded a diastereomerically pure azlactone derivative and oxazolinone derivative.     

Reversible photocontrol of surface wettability between hydrophilic and superhydrophobic surfaces on an asymmetric diarylethene solid surface

By alternate UV and visible light irradiation, reversible topographical changes were observed on a newly synthesized diarylethene microcrystalline surface between the rough crystalline surface of an open-ring isomer and flat eutectic surfaces. The contact angle changes of a water droplet between 80° and 150° and peak intensities changes of the open-ring isomer in XRD patterns within 2 h of repeating cycle were observed. The results indicated that reversibly photogenerated rod-shaped crystals on the surface were produced based on the lattice of the open-ring isomer crystals in the subphase.     

Templated assembly of organic-inorganic materials using the core shell structure of the P22 bacteriophage

Biomimetic chemistry offers new approaches to supramolecular materials synthesis and assembly. We have demonstrated that an assembled viral protein cage, comprising an organic core-shell structure, can be used as a template for the size constrained synthesis of Fe(2)O(3). Particle nucleation is directed by the inner scaffold protein layer, while the size constraints are determined by the outer capsid layer.     

Levels of artificial radionuclides and uranium in rain water collected from Ibaraki (Japan) following the Tomsk-7 accident in Russia

Measurements of some selected radionuclides were carried out in rain waters collected from Ibaraki Prefecture, Japan, following the nuclear accident at Tomsk-7, Russian Federation, in April 1993. The concentrations obtained for artificial radionuclides were⁹⁰Sr1.8 mBq l^–1,¹³⁷Cs0.1 Bq l^–1,¹³¹I0.1 Bq l^–1 and¹²⁹I4 Bq l^–1. Uranium (²³⁸U) concentrations in rainfalls in April 1993 were 6.3–39 ng l^–1. These data were compared to control values obtained previously and there was no appreciable influence on the radioactivity levels in Japan after the Tomsk-7 accident. Since only limited data on the concentrations of¹²⁹I and uranium in rain water are available, these new analytical results contribute to understanding the background levels for these nuclides.     

Retention and enantioselective properties of ovomucoid-bonded silica columns Influence of physical properties of base materials and spacer length

The influence of the physical properties of base silica materials and spacer length on chiral separation of enantiomers on ovomucoid (OVM)-bonded materials was investigated. With regard to the pore size of the base silica materials, the 300-Å materials gave higher enantioselectivity, than the 120-Å materials, despite the smaller amounts of bonded OVM proteins. However, higher resolution was obtained with the latter materials. With regard to the spacer length, aminopropyl (AP)-, aminobutyl-, N-(4-aminobutyl)-3-aminopropyl- and N-(6-aminohexyl)-3-aminopropyl-silica gels were activated by N,N′-di-succinimidyl carbonate (DSC) and the proteins were bound. The first two materials showed excellent chiral resolution properties for the solutes tested, and the AP materials gave higher enantioselectivity and resolution. On the other hand, only oxprenolol enantiomers were slightly resolved on the last two materials. Also, AP-silica gels activated by DSC were compared with glycerylpropyl (GP)-silica gels activated by 1,1′-carbonyldiimidazole. The former materials gave higher resolution for acidic and basic solutes despite the lower enantioselectivity, whereas for the unchanged hexobarbital the latter materials gave higher enantioselectivity and almost equal resolution. The above results reveal that the 120-Å base silica gels are more suitable than the 300- Å base silica gels for obtaining larger amounts of bonded OVM proteins and that a less hydrophobic spacer such as an AP group and a hydrophilic spacer such as a GP group are suitable.