A New Design Strategy for Efficient Thermally Activated Delayed Fluorescence Organic Emitters: From Twisted to Planar Structures

In the traditional molecular design of thermally activated delayed fluorescence (TADF) emitters composed of electron‐donor and electron‐acceptor moieties, achieving a small singlet–triplet energy gap (ΔE_ST) in strongly twisted structures usually translates into a small fluorescence oscillator strength, which can significantly decrease the emission quantum yield and limit efficiency in organic light‐emitting diode devices. Here, based on the results of quantum‐chemical calculations on TADF emitters composed of carbazole donor and 2,4,6‐triphenyl‐1,3,5‐triazine acceptor moieties, a new strategy is proposed for the molecular design of efficient TADF emitters that combine a small ΔE_ST with a large fluorescence oscillator strength. Since this strategy goes beyond the traditional framework of structurally twisted, charge‐transfer type emitters, importantly, it opens the way for coplanar molecules to be efficient TADF emitters. Here, a new emitter, composed of azatriangulene and diphenyltriazine moieties, is theoretically designed, which is coplanar due to intramolecular H‐bonding interactions. The synthesis of this hexamethylazatriangulene‐triazine (HMAT‐TRZ) emitter and its preliminary photophysical characterizations point to HMAT‐TRZ as a potential efficient TADF emitter.     

Differential Effect of Azetidine Substitution in Firefly Luciferin Analogues

Replacing an N,N-dimethylamino group in a classical fluorophore with a four membered azetidine ring provides an improved luminescence quantum yield. Herein, we extended this strategy to bioluminescent firefly luciferin analogues and evaluated its general validity. For this purpose, four types of luciferin cores were employed, and a total of eight analogues were evaluated. Among these analogues, unexpectedly, only the benzothiazole core analogue benefited from an azetidine substitution and showed enhanced bioluminescence. In addition, fluorescence measurements revealed that an azetidine substitution improved the fluorescence quantum yield by 2.3-times compared to a N,N-dimethylamino group. These findings clarify the differential effects of azetidine substituents in luciferins and present one possible strategy for enhancing photon output in benzothiazole type luciferins through a synthetic approach.     

A hydrogen‐storing quinaldine polymer: nickel‐electrodeposition‐assisted hydrogenation and subsequent hydrogen evolution

Quinaldine‐substituted poly(acrylic acid) (PQD) and its hydrogenated 1,2,3,4‐tetrahydroquinaldine derivative (PHQD) were prepared, and a cycle of hydrogen fixing and hydrogen evolution in and from the polymer, respectively, is described. A PQD layer coated on a carbon substrate was electrochemically reduced or hydrogenated using water as a hydrogen source, accompanied by the electrodeposition of nickel microparticles in the polymer layer, to convert PQD to PHQD. The conversion efficiency was enhanced by coating PQD on the substrate as a scaffold of nickel electrodeposition, in comparison with that of quinaldine and PQD dissolved in the electrolyte. The formed PHQD evolved hydrogen by simply warming it in water containing an iridium complex catalyst. Hydrogen fixing and evolution under mild conditions could suggest a new system of hydrogen carriers. © 2017 Society of Chemical Industry     

Near-Infrared Bioluminescence Imaging with a through-Bond Energy Transfer Cassette

A coelenterazine (CTZ) analogue emitting near-infrared (NIR) bioluminescence was synthesized for through-bond energy transfer (TBET)-based imaging modalities. The analogue, named Cy5-CTZ, was prepared by conjugating cyanine-5 (Cy5) dye to CTZ through an acetylene linker. This novel derivative is intrinsically fluorescent and emits NIR-shifted luminescence upon reacting with an appropriate luciferase, the Renilla luciferase. This Cy5-CTZ substrate is optically stable in physiological samples and rapidly permeabilize through the plasma membrane into the cytosolic compartment of live cells.     

Drying behavior of sludge with drying accelerator

Abstract

For fuelization of high moisture content sludge, efficient sludge drying technique using a drying accelerator was investigated. In the experiment, drying accelerator types and drying conditions were changed and the effect of accelerator type and/or drying condition on sludge drying behavior was evaluated by analyzing drying characteristic curve. Depending on drying accelerator type, the addition of drying accelerator did not always exert superiority in drying rate, but sludge with added acrylic resin having low glass transition temperature (DA10) demonstrated significantly enhanced drying rate. Addition of surface activating agent (SAA) instead of resin type drying accelerator also enhanced the sludge drying rate. The highest drying rate was obtained by addition of DA10 and SAA together, and the sludge drying rate has significantly been augmented at the high drying temperature condition.     

Identification of a Putative β-Arrestin Superagonist of the Growth Hormone Secretagogue Receptor (GHSR)

Ghrelin is a pleiotropic feeding hormone which also has a pivotal role in the central nervous system. Upon the activation of its receptor, growth hormone secretagogue receptor (GHSR), the Gα_q/11-mediated and the β-arrestin-mediated signaling pathways are activated. As the β-arrestin pathway is a potential drug target, there is a strong need for β-arrestin-biased GHSR modulators. Activation of the β-arrestin pathway should inhibit the Gα_q/11-mediated calcium flux through internalization of the receptor. Hence, we used the antagonistic activity in the calcium assay as the first screening for the β-arrestin activation. By conducting the second screening assay for the β-arrestin activation based on extracellular signal regulated kinase (ERK) 1/2 phosphorylation, we discovered a putative β-arrestin-biased superagonist. The activity of the compound was not completely blocked with the competitive antagonist, which implies that the effect is mediated, at least partly, by allosteric binding of the compound.     

Development of a contrast‐enhanced micro computed tomography protocol for the oval squid (Sepioteuthis lessoniana) brain

Coleoid cephalopods (squid, cuttlefish, and octopus) have a well‐developed and complex central nervous system. Its absolute size is the largest among invertebrates, and the brain‐to‐body mass ratio is larger than that of fish and reptiles and equivalent to that of birds and mammals. Although a number of histological studies have been conducted on the brains of cephalopods, most of them used a light microscope or an electron microscope, which show the microstructure of the brain, but often cannot image the whole brain instantaneously. Of late, micro computed tomography (CT) has gained popularity for imaging animal brains because it allows for noninvasive three‐dimensional (3D) reconstruction and preprocessing that are not cumbersome. To perform micro‐CT on cephalopod brains, we first tested conditions suitable for preprocessing, paying special attention to staining conditions that would provide high contrast images. Four agents, iodine in 99.5% ethanol, iodine potassium iodide in water (IKI), phosphotungstic acid in 70% ethanol, and nonionic iodinated contrast agent in water, were tested at various concentrations and durations on brain of juvenile oval squid. To evaluate the quality of staining, we calculated the contrast ratio of the two‐dimensional (2D) images and compared 3D segmentation of the best and worst 2D images. We concluded that 3% IKI staining for 7 days was the best combination to enhance the images contrast of the oval squid brain, in which each brain lobe was clearly detected and 3D segmentation of the whole brain was possible. The wider applicability of this preprocessing method for micro‐CT of the brains of other cephalopods is discussed.     

FPGA-based system for effective IQ imbalance mitigation of RF power amplifiers

To provide an adequate signal integrity to a power amplifier (PA), we propose a digital system for the degradation at the transmitter path, and it is implemented on a field-programmable gate array (FPGA) board. The proposed system offers the following features: A -ary quadrature amplitude modulation (QAM) digital signal generation and in-phase/quadrature (IQ) imbalance mitigation, and by default, it performs as a predistortion model extraction from PA-measured data. The simulations and tests provided are performed to effectively verify the PA linearity by using 256-QAM signals. The nonlinearities are predicted as a reliable solution for linearizing the PA from measurements of AM/AM and AM/PM conversion curves. The performance is evaluated in terms of linearity, computation complexity, and FPGA hardware synthesis according to a dependability compliance of digital signal processing. Finally, the model is validated with input/output data observations to linearize the model with a fitting normalized mean squared error (NMSE) of around  dB, a spurious free dynamic range of 40 dBm, and an adjacent channel power ratio reduction by  dBm, for a class-AB broadband radio frequency PA GaN HEMT of 10 W working at 2.34 GHz.     

Mechanism‐Based Inhibitor of DNA Cytosine‐5 Methyltransferase by a SNAr Reaction with an Oligodeoxyribonucleotide Containing a 2‐Amino‐4‐Halopyridine‐C‐Nucleoside

In chromatin, 5‐methylcytosine (mC), which represents the fifth nucleobase in genomic DNA, plays a role as an inducer of epigenetic changes. Tumor cells exhibit aberrant DNA methylation patterns, and inhibition of human DNA cytosine‐5 methyltransferase (DNMT), which is responsible for generating mC in CpG sequences, is an effective strategy to treat various cancers. Here, we describe the design, synthesis, and evaluation of the properties of 2‐amino‐4‐halopyridine‐C‐nucleosides (d^XP) and oligodeoxyribonucleotides (ODNs) containing d^XP as a novel mechanism‐based inhibitor of DNMTs. The designed ODN containing ^XPpG forms a complex with DNMTs by covalent bonding through a nucleophilic aromatic substitution (S_NAr) reaction, and its cell proliferation activity is investigated. This study suggests that d^XP in a CpG sequence of DNA could serve as a potential nucleic acid drug lead in cancer chemotherapy and a useful chemical probe for studies of epigenetics. Our molecular design using a S_NAr reaction would be useful for DNMTs and other protein–DNA interactions.