Deep‐blue fluorescent compounds are particularly important in organic light‐emitting devices (OLEDs). A donor–accepotor (DA)‐type blue‐emitting compound, 1‐(10‐(4‐methoxyphenyl)anthracen‐9‐yl)‐4‐(10‐(4‐cyanophenyl)anthracen‐9‐yl)benzene (BD3), is synthesized, and for comparison, a nonDA‐type compound, 1,4‐bis(10‐phenylanthracene‐9‐yl)benzene (BD1) and a weak DA‐type compound, 1‐(10‐phenylanthracen‐9‐yl)‐4‐(10‐(4‐cyanophenyl)anthracen‐9‐yl)‐benzene (BD2), are also synthesized. The twisted conformations of the two anthracene units in the compounds, confirmed by single crystal X‐ray analysis, effectively prevent π‐conjugation, and the compound shows deep‐blue photoluminescence (PL) with a high PL quantum efficiency, almost independent of the solvent polarity, resulting from the absence of an intramolecular charge transfer state. The DA‐type molecule BD3 in a non‐doped device exhibits a maximum external quantum efficiency (EQE) of 4.2% with a slight roll‐off, indicating good charge balance due to the DA‐type molecular design. In the doped device with 4,4′‐bis(N‐carbazolyl)‐1,1′‐biphenyl (CBP) host, the BD3 exhibits higher EQE than 10% with Commission International de L'Eclairge (CIE) coordinates of (0.15, 0.06) and a narrow full‐width at half‐maximum of 45 nm, which is close to the CIE of the high definition television standard blue.
Recently, the ARID1A gene has been identified as a novel tumor suppressor in ovarian clear cell carcinoma. The prognostic significance of the loss of ARID1A expression is not known. The current study was designed to evaluate whether ARID1A was a prognostic factor for progression, survival, and chemoresistance in ovarian clear cell carcinoma. A total of 60 patients, who were surgically treated for primary ovarian clear cell adenocarcinoma, were enrolled. Surgical specimens were examined for ARID1A protein expression by immunohistochemistry. The correlations between the loss of ARID1A expression and clinicopathological characteristics, prognosis, and chemosensitivity were investigated. Loss of ARID1A expression was identified in 9 (15.0%) of 60 ovarian clear cell carcinoma samples. Loss of ARID1A staining intensity (0 þ ) was more frequently found in cells of clear cell carcinomas than in high-grade serous carcinomas (Po0.01). Loss of ARID1A expression was significantly correlated with advanced FIGO stage and high CA125 levels (P ¼ 0.02, 0.01). There were no significant correlations between loss of ARID1A expression and patient age, status of residual tumor, Ki-67 labeling index, or the status of endometriosis. Loss of ARID1A correlated with shorter progression-free survival of patients with clear cell carcinomas treated with platinum-based chemotherapy (Po0.01). Loss of ARID1A expression tended to correlate with shorter overall survival in patients with ovarian clear cell carcinomas treated with platinum-based chemotherapy. When data were stratified for the multivariate analysis, only the loss of ARID1A expression remained a significant (P ¼ 0.03) predictor of reduced progressionfree survival. Of the 60 patients with ovarian clear cell carcinomas, 14 patients had measurable residual tumor after primary cytoreductive surgery. Tumors with loss of ARID1A expression were more likely to be chemoresistant than tumors with positive ARID1A expression (100.0 vs 40.0%, P ¼ 0.04). This study demonstrates that loss of ARID1A in ovarian clear cell carcinoma is a negative prognostic factor in patients treated with platinum-based chemotherapy. Measurement of ARID1A expression may be a method to predict resistance to platinum-based chemotherapy in patients with ovarian clear cell carcinoma.
Benzene is the simplest aromatic hydrocarbon with a six-membered ring. It is one of the most basic structural units for the construction of π conjugated systems, which are widely used as fluorescent dyes and other luminescent materials for imaging applications and displays because of their enhanced spectroscopic signal. Presented herein is 2,5-bis(methylsulfonyl)-1,4-diaminobenzene as a novel architecture for green fluorophores, established based on an effective push-pull system supported by intramolecular hydrogen bonding. This compound demonstrates high fluorescence emission and photostability and is solid-state emissive, water-soluble, and solvent- and pH-independent with quantum yields of Φ=0.67 and Stokes shift of 140 nm (in water). This architecture is a significant departure from conventional extended π-conjugated systems based on a flat and rigid molecular design and provides a minimum requirement for green fluorophores comprising a single benzene ring.
Squaraine dyes are considered an important group of photoactive materials in the field of organic photovoltaic devices. In this work, we purposely tuned the side chains and number of hydroxyl (OH) groups in a series of squaraine (SQ) dyes, i.e., SQ1−4, to investigate the effect of structural variations on the material properties as well as the performance of these dyes as donor materials in bulk heterojunction (BHJ) photovoltaic cells. The material structure and properties of these SQs were systematically characterized using various tools. Solution-processed BHJ photovoltaic cells based on these SQ compounds combined with [6,6]-phenyl-C71-butyric acid methyl ester (PC 71 BM) as an acceptor gave efficient power conversion efficiencies greater than 4.0% under AM 1.5G solar illumination at 100 mW/cm 2 . Our observations show that the OH groups deepened the highest occupied molecular orbital (HOMO) of the donor and thus enhanced the open-circuit voltage, whereas the linear chain improved the charge transport properties in the BHJ films. Both the side chain and the number of OH groups play important roles in determining the aggregation behavior of these SQs in solid-state films: SQ1, which contains four OH groups and branched side chains, exhibits J-aggregation because of the steric hindrance of its side chains; SQ2, which contains four OH groups and linear side chains, exhibits both H-aggregation and J-aggregation; SQ3, which contains two OH groups and linear side chains, exhibits preferential H-aggregation; SQ4, which contains linear side chains without OH groups, exhibits J-aggregation, this is most likely because of its strong intermolecular coupling and intermolecular hydrogen-bonding interactions to form a head-totail packing mode, i.e., J-aggregation. Interestingly, the absorption of J-aggregates in BHJ cells contributes to the cells' photoresponse at long wavelengths, and thus results in higher photocurrent. Our results demonstrate a clear relationship between the molecular structures of SQ dyes and their physical properties that govern their photovoltaic performance.
We concluded that fall rates in RA patients were higher than in the general population and that balance impairment or side effects of drugs may play a role in increasing the risk of falls.
The fascination of the structure, dynamics, and recognition properties of naturally occurring helical polymers, such as the a-helix of peptides and the double helix of DNA structures have prompted chemists to design and synthesize artificial helical polymers and oligomers.[1] Although a number of synthetic polymers and oligomers that fold into single-helical conformations have been reported, only a few structural motifs are available for constructing double-helical structures. The most widely used approach is the utilization of metaldirected self-assembly, in which ligand-containing strands form double-, triple-, or quadruple-helical complexes, that is, helicates;[2] the three-dimensional structures of helicates are determined by the geometry of the template metal ions. Hydrogen-bonding-driven self-assembly is another common approach to constructing supramolecular duplexes.[3] In most cases, however, their three-dimensional structures have been characterized as ladder-or zipperlike linear conformations. It was recently disclosed that some oligoamides give rise to double-helical assemblies by making use of interstrand hydrogen-bonding and aromatic-aromatic interactions. [4] Although the hydrogen-bonding interaction is a readily available and versatile tool for constructing supramolecular assemblies, [5] it is still difficult and challenging to design double helices with predictable structures.[4c] Herein, we describe the design and synthesis of hydrogen-bonding-driven double helices by a modular strategy in which intertwined supramolecular binary complexes are employed.Our strategy is based on the crescent-shaped m-terphenyl derivatives (Figure 1). Crescent-shaped molecules, such as bipyridine and phenanthroline derivatives, have often been used to construct intertwined supramolecular complexes and
We present herein a linear expanded π-conjugation system comprising azulene units: 2,6':2',6″-terazulene. This simple hydrocarbon exhibits excellent n-type transistor performance with an electron mobility of up to 0.29 cm(2) V(-1) s(-1). The lowest unoccupied molecular orbital (LUMO) is well distributed over the entire molecule, whereas the highest occupied molecular orbital (HOMO) is localized at one end. These findings indicate a disadvantage of hole carrier transport and an advantage of n-type-specific transport behavior. This system presents an unconventional concept: polarity control of OFET by molecular orbital distribution control.
The age- and gender-specific incidence of hip fracture in the Tottori prefecture, Japan has not plateaued for either gender.
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