Tailormade bottom-up synthesis of covalent organic frameworks (COFs) from various functional building blocks offer not only tunable topology and pore size but also multidimensional properties. High crystallinity is one of the prerequisites for their structures and associated physicochemical properties. Among different π-conjugated motifs for constructing COFs, pyrene-based tetragonal structures are effective in achieving highly ordered and crystalline states.
View Article and Find Full Text PDFThe torsion angle between donor and acceptor segments of a thermally activated delayed fluorescence (TADF) molecule is one of the most critical factors in determining the performance of TADF-based organic light-emitting diodes (OLEDs) because the torsion angle affects not only the energy gap between the singlet and triplet but also the oscillator strength and spin-orbit coupling. However, the torsion angle is difficult to analyze, because organic molecules are in an amorphous state in OLEDs. Here, we determined the torsion angle of a highly efficient TADF emitter, DACT-II, in an amorphous state by dynamic nuclear polarization enhanced solid-state NMR measurements.
View Article and Find Full Text PDFOrganic light-emitting diodes (OLEDs) using thermally activated delayed fluorescence (TADF) materials have advantages over OLEDs using conventional fluorescent materials or high-cost phosphorescent materials, including higher efficiency and lower cost. To attain further high device performance, clarifying internal charge states in OLEDs at a microscopic viewpoint is crucial; however, only a few such studies have been performed. Here, we report a microscopic investigation into internal charge states in OLEDs with a TADF material by electron spin resonance (ESR) at a molecular level.
View Article and Find Full Text PDFHere, we explored the possibility of using cycloparaphenylenes (CPP) within a donor-acceptor TADF emitter design. contains four electron-donating moieties connected to a . In the 15 wt % doped in CzSi film, showed sky-blue emission with λ = 475 nm, Φ = 29%, and triexponential emission decays with τ of 4.
View Article and Find Full Text PDFThe members of the imidazole family have been widely used for electron transporting, host, conventional fluorescent, and phosphorescent materials. Although the imidazole core also has great potential as an acceptor segment of deep-blue thermally activated delayed fluorescence (TADF) owing to its high triplet energy, the emission color of imidazole-based TADF organic light-emitting diodes (OLEDs) has so far been limited to blue to green. In this work, four acridan-imidazole systems are theoretically designed aiming for deep- or pure-blue emitters.
View Article and Find Full Text PDFThermally activated delayed fluorophores (TADF) with donor-acceptor (D-A) structures always face strong conjugation between donor and acceptor segments, rendering delocalized new molecular orbitals that go against blue emission. Developing TADF emitters with blue colors, high efficiencies, and long lifetimes simultaneously is therefore challenging. Here, a D-void-A structure with D and A moieties connected at the void-position where the frontier orbital from donor and acceptor cannot be distributed, resulting in nonoverlap of the orbitals is proposed.
View Article and Find Full Text PDFIn this work we showcase the emitter in which we employed a twin-emitter design of our previously reported material, . This new system presented a red-shifted emission at 488 nm compared to that of at 475 nm and showed a comparable photoluminescence quantum yield of 57.1% in a 20 wt % CzSi film versus 63.
View Article and Find Full Text PDFThe conversion of a high-energy photon into two excitons using singlet fission (SF) has stimulated a variety of studies in fields from fundamental physics to device applications. However, efficient SF has only been achieved in limited systems, such as solid crystals and covalent dimers. Here, we established a novel system by assembling 4-(6,13-bis(2-(triisopropylsilyl)ethynyl)pentacen-2-yl)benzoic acid (Pc) chromophores on nanosized CdTe quantum dots (QDs).
View Article and Find Full Text PDFThree multichromophore thermally activated delayed fluorescence (TADF) molecules, , , and , were synthesized and characterized. These molecules were designed by connecting the TADF moiety 4,5-di(9-carbazol-9-yl)phthalonitrile () to different positions of a central benzene ring scaffold. Three highly soluble emitters all exhibited near-quantitative photoluminescence quantum yields (Φ) in toluene.
View Article and Find Full Text PDFWe utilized nanoporous mayenite (12CaO·7AlO), a cost-effective material, in the hydride state (H) to explore the possibility of its use for hydrogen storage and transportation. Hydrogen desorption occurs by a simple reaction of mayenite with water, and the nanocage structure transforms into a calcium aluminate hydrate. This reaction enables easy desorption of H ions trapped in the structure, which could allow the use of this material in future portable applications.
View Article and Find Full Text PDFPrevious research has suggested that emotion regulation strategies (ERSs) are associated with abnormal eating behaviors and attitudes (AEBs). Available data have demonstrated that frequent rumination, a major maladaptive ERS, is associated with elevated AEBs, whereas adaptive ERSs, such as problem-solving and cognitive reappraisal, showed negative associations with AEBs. Most previous studies examined the association of a single ERS with AEBs.
View Article and Find Full Text PDFAlterations in the cortical dopamine system and microglial activation have been implicated in the pathophysiology of attention-deficit/hyperactivity disorder (ADHD), one of neurodevelopmental disorders that can be conventionally treated with a dopamine enhancer (methylphenidate) albeit unsatisfactorily. Here, we investigated the contributions of the dopamine D1 receptor (D1R) and activated microglia and their interactions to the clinical severities in ADHD individuals using positron emission tomography (PET). Twenty-four psychotropic-naïve ADHD individuals and 24 age- and sex-matched typically developing (TD) subjects underwent PET measurements with [C]SCH23390 for the D1R and [C](R)PK11195 for activated microglia as well as assessments of clinical symptoms and cognitive functions.
View Article and Find Full Text PDFVisible-light-driven hydrogen (H) production from water is a promising strategy to convert and store solar energy as chemical energy. Covalent organic frameworks (COFs) are front runners among different classes of organic photocatalysts. The photocatalytic activity of COFs depends on numerous factors such as the electronic band gap, crystallinity, surface area, exciton migration, stability of transient species, charge separation and transport, etc.
View Article and Find Full Text PDFA growing body of evidence has indicated that individuals with autism spectrum disorder (ASD) exhibit abnormal reactions to sensory stimuli and impaired face processing. Although behavioral studies have reported that individual differences in sensory processing patterns are correlated with performance in face processing tasks, the neural substrates underlying the association between sensory processing patterns and face processing remain unknown. Using functional magnetic resonance imaging, the present study examined the relationships between sensory processing patterns assessed with the Adolescent/Adult Sensory Profile (AASP) and brain activity during a one-back task with two types of stimuli (face or house pictures).
View Article and Find Full Text PDFThe serotonin system has been implicated in the pathophysiology of anorexia nervosa (AN). A recent report proposed that body image distortion (BID), a core symptom of AN, may relate to abnormalities of the serotonin system, especially the serotonin transporter (5HTT). Positron emission tomography (PET) studies of underweight patients with active AN reported alterations in serotonin receptors, but not 5HTT.
View Article and Find Full Text PDFACS Appl Mater Interfaces
February 2019
A novel thermally activated delayed fluorescent (TADF) compound, 9-(3-((4,6-diphenyl-1,3,5-triazin-2-yl)oxy)phenyl)-3,6-diphenyl-9 H-carbazole (PhCz- o-Trz), with a donor-σ-acceptor (D-σ-A) motif is developed. A flexible small space σ-junction is adopted to partly suppress the intramolecular charge transfer (intra-CT) while inversely enhancing the intermolecular charge transfer (inter-CT) between D/A moieties, realizing the coexistence of both intra-CT and inter-CT in an amorphous aggregate. The coexistence of dual CTs increases the complexity of the singlet and triplet state mixing, enhancing the triplet-to-singlet spin-flip transition and thereby the TADF emission.
View Article and Find Full Text PDFA unique superparamagnetic-like behavior and a large "positive magneto-LC effect" were observed in the solid phases and the hexagonal columnar (Col ) liquid crystalline (LC) phase, respectively, of novel achiral non-π-delocalized nitroxide diradical compounds (R,S)-1, which showed polymorphism in the solid phases (solids I and II). The SQUID magnetization measurement revealed that (1) (R,S)-1 containing a small amount of racemic diastereomers (R*,R*)-1 possessed an unusual and large temperature-independent magnetic susceptibility (χ >0) component in the original nanocrystalline solid I that was responsible for the observed superparamagnetic-like behavior under low magnetic fields and did not arise from the contamination by extrinsic magnetic metal or metal ion impurities, besides ordinary temperature-dependent paramagnetic susceptibility (χ >0) and temperature-independent diamagnetic susceptibility (χ <0) components, (2) a large increase in molar magnetic susceptibility (χ ) (positive magneto-LC effect) that occurred at the solid I-to-liquid crystal transition upon heating was preserved as an additional χ increase in the resulting polymorphic nanocrystalline solid II by cooling, and (3) such unique magnetic phenomena were induced by thermal processing for (R,S)-1 or by adding a small amount of (R*,R*)-1 to (R,S)-1 as the impurity.
View Article and Find Full Text PDFThis paper examines the reform experience of the 10th Annual Meeting of the Japanese Society for Pharmaceutical Palliative Care and Sciences from Instructional Systems perspectives, to check whether it was effective, efficient, and appealing for participants. "Instructional Systems" has been a research area in educational technology for the past 50 years, and has also been applied to training and human resource development in healthcare domains. If an annual meeting is to be designed for participants' learning, then perspectives of Instructional Systems can be applied to interpret the effort of the reform.
View Article and Find Full Text PDFBackground: The α7 subtype of the nicotinic acetylcholine receptor (nAChR) is considered important in higher cognitive functions, and cholinergic loss underpins the pathophysiology of Alzheimer's disease (AD). However, the relationships between α7 nAChR function and clinical functions or amyloid-β (Aβ) deposition remain to be explored in the living AD brain.
Objective: We aimed to elucidate the relationship between α7 nAChR availability in the specific cholinergic region and cognitive decline in the Aβ-confirmed AD brain.
Schizophrenia and schizophrenia-like symptoms induced by the dopamine agonists and N-methyl-D aspartate type glutamate receptor antagonists occur only after the adolescent period. Similarly, animal models of schizophrenia by these drugs are also induced after the critical period around postnatal week three. Based upon the development-dependent onsets of these psychotomimetic effects, by using a DNA microarray technique, we identified the WD repeat domain 3 (WDR3) and chitobiosyldiphosphodolichol beta-mannosyltransferase (ALG1) genes as novel candidates for schizophrenia-related molecules, whose mRNAs were up-regulated in the adult (postnatal week seven), but not in the infant (postnatal week one) rats by an indirect dopamine agonist, and phencyclidine, an antagonist of the NMDA receptor.
View Article and Find Full Text PDFThe efficiency of organic light emitting diodes (OLEDs) can be improved by controlling the orientation of the transition dipole moment of the emitters. Currently, no effective methods exist for orienting the transition dipole moments in solution processed active layers for OLEDs. We investigate the orientation of the transition dipole moment of small molecular emitters in a host matrix of poly(9,9-dioctylfluorene) (PFO) by means of angle dependent luminescence intensity measurements.
View Article and Find Full Text PDF[10]Cycloparaphenylene ([10]CPP) and its tetraalkoxy derivatives were synthesized on the gram scale in 7 steps starting from 1,4-benzoquinone or 2,5-dialkoxy-1,4-benzoquinone. The key steps involve the highly cis-selective bis-addition of 4-bromo-4'-lithiobiphenyl to the quinones to produce a five-ring unit containing cyclohexa-1,4-diene-3,6-diol moiety, the platinum-mediated dimerization of the five-ring unit, and the HSnCl-mediated reductive aromatization of cyclohexadienediol. The tetraalkoxy substituents increased the solubility of [10]CPP in common organic solvents.
View Article and Find Full Text PDFMolecular orientation in amorphous organic semiconducting thin-film devices is an important issue affecting device performance. However, to date it has not been possible to analyze the "distribution" of the orientations. Although solid-state NMR (ssNMR) spectroscopy can provide information on the "distribution" of molecular orientations, the technique is limited because of the small amount of sample in the device and the low sensitivity of ssNMR.
View Article and Find Full Text PDFThe synapse-associated protein 97/discs, large homolog 1 of Drosophila (DLG1) gene encodes synaptic scaffold PDZ proteins interacting with ionotropic glutamate receptors including the N-methyl-D-aspartate type glutamate receptor (NMDAR) that is presumed to be hypoactive in brains of patients with schizophrenia. The DLG1 gene resides in the chromosomal position 3q29, the microdeletion of which confers a 40-fold increase in the risk for schizophrenia. In the present study, we performed genetic association analyses for DLG1 gene using a Japanese cohort with 1808 schizophrenia patients and 2170 controls.
View Article and Find Full Text PDFInter- and intramolecular charge-transfer processes are combined using an exciplex-forming host and a thermally activated delayed fluorescent dopant, for fabricating efficient fluorescent organic light-emitting diodes along with the reduced efficiency roll-off at high current densities. Extra conversion on the host from triplet exciplexes to singlet exciplexes followed by energy transfer to the dopant reduces population of triplet excitons on dopant molecules, thereby reducing the triplet exciton annihilations at high current densities.
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