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Small molecules and polymers with conjugated structures can be used as organic optoelectronic materials. These molecules have conventionally been synthesized by cross-coupling reactions; however, in recent years, direct functionalization of C-H bonds has been used to synthesize organic optoelectronic materials. Representative reactions include direct arylation reactions (C-H/C-X couplings, with X being halogen or pseudo-halogen) and cross-dehydrogenative coupling (C-H/C-H cross-coupling) reactions. Although these reactions are convenient for short-step synthesis, they require regioselectivity in the C-H bonds and suppression of undesired homo-coupling side reactions. This review introduces examples of the synthesis of organic optoelectronic materials using two types of direct C-H functionalization reactions. In addition, we summarize our recent activities in the development of direct C-H functionalization reactions using fluorobenzenes as substrates. This review covers the reaction mechanism and material properties of the resulting products., (© 2023 Wiley-VCH GmbH.)

Fluoroalkyl compounds are widely used, underscoring a pressing need for the development of methods for their synthesis. However, reports on perfluoroalkylation to styrenes have been sparse. In this study, both hydroxy- and hydro-perfluoroalkylation of styrene were achieved using visible light reactions, catalyzed by eosin Y, by selecting appropriate additives and controlling the eosin Y quenching cycle. These reactions are heavy-metal free, use water as the hydroxyl or hydrogen source, and employ inexpensive and readily available reagents.

Introduction: The efficacy of catheter ablation in patients with low cardiac function has been previously reported; however, only a few studies have included mid-range ejection fraction (mrEF). This study aimed to evaluate the efficacy and safety of atrial fibrillation (AF) ablation in patients with left ventricular ejection fraction (LVEF) < 50%., Methods: This study retrospectively analyzed 79 patients (reduced ejection fraction [rEF]/mrEF, 38/41; paroxysmal/persistent, 37/42; heart failure hospitalizations within one year before ablation, 36 [45.6%]) who underwent the first ablation procedure at our hospital from April 2017 to December 2021. Radiofrequency ablation and cryoablation were performed for 69 and 10 patients, respectively., Results: Complications included pacemaker implantation for postoperative sick sinus syndrome in one patient and inguinal hematoma in one patient. Regarding efficacy, there were significant postoperative improvements in echocardiographic data, blood test values, and diuretic use. After a mean follow-up of 60 months, 86.1% patients had no AF recurrence. There were 9 heart failure hospitalizations (11.4%) and 5 all-cause deaths (6.3%); no significant differences were found between the rEF and mrEF groups. No significant predictors of AF recurrence were found in preoperative patient characteristics., Conclusion: AF ablation in patients with LVEF <50% significantly improved cardiac and renal functions with few complications, resulting in a high non-recurrence rate and reduced heart failure., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Indian Heart Rhythm Society. Published by Elsevier B.V. All rights reserved.)

We fabricated a flexible and red-emissive microcrystal resonator for highly efficient optical waveguiding. The microfiber crystals of diketopyrrolopyrrole (DPP) used in this work possess a high photoluminescence (PL) quantum efficiency (Φ PL = 0.45) and exhibit a micromechanical deformation shape in the curved state. The crystals show optical fringes in their PL spectra, suggesting the existence of a naturally formed Fabry-Pérot crystal resonator owing to its flat crystal surface. The group refractive index ( n g ) and Rabi splitting energy ( ℏ Ω) indicating the coupling strength between excitons and resonator photons are large ( n g = 3.7-6.0, ℏ Ω = 1.38 eV), suggesting the strong confinement of waveguiding photons. Spatially resolved PL measurements revealed that the PL in a crystal fiber is efficiently waveguided, even in a curved crystal with a very small curvature radius of 11 μm. Strong photon confinement inside a crystal resonator is a plausible origin of efficient optical waveguiding.

Fluorine-containing polymers are one of the most useful materials among various polymers. In this study, we have developed synthesis methods for fluorine-containing polymers through sequential and chain polymerization based on the generation of perfluoroalkyl radicals by photoirradiation halogen bonding of perfluoroalkyl iodide and amines. In sequential polymerization, fluoroalkyl-alkyl-alternating polymers were synthesized by the polyaddition of diene and diiodoperfluoroalkane. In chain polymerization, polymers with perfluoroalkyl terminals were synthesized by polymerization of general-purpose monomers, with perfluoroalkyl iodide as the initiating species. Block polymers were also synthesized by successive chain polymerization to the polyaddition product., (© 2023 Wiley-VCH GmbH.)

Diphenylanthracene (DPA) and its derivatives are promising semiconducting materials for p-type organic-field-effect transistors (OFETs). In this study, to develop n-type semiconducting materials with an anthracene core, pentafluorobenzene was introduced into anthracene by C-H direct arylation, enabling the synthesis of various bis(pentafluorophenyl)anthracene (DPA-F) derivatives. The high reactivity of the pentafluorobenzene C-H bond allows direct arylation for synthesizing DPA-F derivatives in a single step. The introduction of strong electron-withdrawing pentafluorophenyl groups provides the anthracene derivatives with n-type semiconducting properties, in contrast to the p-type properties of the parent DPAs. Among the synthesized compounds, 2,6-bis(pentafluorophenyl)anthracene shows a high electron mobility of 0.12±0.02 cm 2 /Vs and an on/off ratio>10 6 in OFETs. The high crystallinity results in the smooth electron transport. This study provides a facile synthetic method for n-type semiconducting materials and insights into the molecular design of the positional effects of aromatic substituents on anthracene., (© 2023 Wiley-VCH GmbH.)

We developed a simple and sustainable method for the hydroxy-perfluoroalkylation of electron-deficient conjugated olefins and styrenes. In this protcol, in situ generated enamine forms electron-donor-accepter (EDA) complexes with perfluoroalkyl iodide, and reaction proceed with visible-light irradiation. Tertiary amine also interacts with perfluoroalkyl iodide via halogen-bonding, promoting the perfluoroalkyl radical generation. This reaction does not require any transition-metal or photoredox catalyst, and gaseous oxygen is used as the green hydroxy source. Moreover, various commercially available substrates and perfluoroalkyl iodides were tolerated, affording the desired hydroxy-perfluoroalkylated products in good to moderate yields (>50 examples, up to 90%)., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The eosin Y-catalyzed hydroperfluoroalkylation of electron-deficient alkenes is described herein. The reaction proceeded smoothly under visible light irradiation and selectively afforded a hydroperfluoroalkylated product. Various perfluoroalkyl bromides and electron-deficient olefins can be used in this reaction, and all chemicals required for this reaction are safe and readily available.

A Pd-catalysed cross-dehydrogenative coupling reaction introduced two polyfluoroarenes into simple polyaromatic hydrocarbons at sterically favourable positions. An investigation of the reaction mechanism revealed that the unique regioselectivity was determined by the reductive elimination step rather than the C-H bond cleavage step.

Purpose: The CARTOFINDER mapping system analyzes activation patterns using unipolar potentials during atrial fibrillation (AF), where isoproterenol (ISP) is conventionally used to induce non-pulmonary vein (PV) foci and confirm PV arrhythmogenicity. In 20 patients with persistent AF who underwent ablation at our hospital, arrhythmogenic foci were evaluated using both these methods., Methods: Before pulmonary vein isolation (PVI), PV and left atrium (LA) were analyzed during AF using CARTOFINDER, and the isolation line was determined based on the results. After PVI, ISP was loaded after return of sinus rhythm and confirmation of the presence of arrhythmogenic foci. The activation site in LA was ablated at the discretion of the surgeon., Results: Focal activation sites detected by CARTOFINDER correlated with the arrhythmogenic foci induced by ISP in the PVs. The results also showed that a greater number of focal activation sites in the PVs correlated to an increased response to ISP administration. In one patient, it was observed that the focal activation site identified in the PV also coincided with the site of the origin of automaticity induced by ISP after PVI., Conclusion: CARTOFINDER and ISP both reliably determined the presence of arrhythmogenic foci in PV, in patients with persistent AF. Knowledge of the nature of arrhythmogenic foci in non-PV is considered to be a topic for future studies, and further data collection is required., (© 2022. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

In the initial process of coronavirus disease 2019 (COVID-19), severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) infects respiratory epithelial cells and then transfers to other organs the blood vessels. It is believed that SARS-CoV-2 can pass the vascular wall by altering the endothelial barrier using an unknown mechanism. In this study, we investigated the effect of SARS-CoV-2 on the endothelial barrier using an airway-on-a-chip that mimics respiratory organs and found that SARS-CoV-2 produced from infected epithelial cells disrupts the barrier by decreasing Claudin-5 (CLDN5), a tight junction protein, and disrupting vascular endothelial cadherin-mediated adherens junctions. Consistently, the gene and protein expression levels of CLDN5 in the lungs of a patient with COVID-19 were decreased. CLDN5 overexpression or Fluvastatin treatment rescued the SARS-CoV-2-induced respiratory endothelial barrier disruption. We concluded that the down-regulation of CLDN5 expression is a pivotal mechanism for SARS-CoV-2-induced endothelial barrier disruption in respiratory organs and that inducing CLDN5 expression is a therapeutic strategy against COVID-19.

Purpose: Compared with conventional pulmonary vein isolation (PVI) with radiofrequency ablation, PVI with cryoballoon is an easier and shorter procedure without reconnection, particularly in the superior pulmonary vein. However, the durability of the cryoballoon may be reduced due to anatomical factors and the position of the pulmonary vein (PV). Further, inadequate isolation of the carina leads to recurrence of atrial fibrillation (AF). We aimed to determine whether using contrast-enhanced computed tomography (CT) for patient selection improves the early success rate and prevents the recurrence of AF in PVI with cryoballoon., Methods: We evaluated patients who underwent ablation for paroxysmal atrial fibrillation in our hospital between July 2019 and November 2020. After excluding patients with contraindications for cryoablation, 50 patients were selected through visual inspection of the results of preoperative contrast-enhanced CT. A treatment plan was established, and the clinical course and outcomes were followed up., Results: Of the 200 PVs of the 50 patients, only 8 PVs (4%) were incompletely isolated with a single cryoablation. Six of the eight PVs were successfully isolated with additional cryoablation. Only 2 patients (4%) underwent additional PVI with radiofrequency ablation. Four patients had AF recurrence within a mean follow-up period of 14.3 ± 5.1 months. The rate of sinus rhythm maintenance was 92%. PV reconnection was observed in 2 patients. None of the patients had postoperative atrial flutter., Conclusions: Selecting patients for cryoablation according to contrast-enhanced CT findings made the procedure easier to perform, leading to improved early success rates and clinical course., (© 2021. The Author(s).)

Polyaddition via the Co-catalyzed hydroarylation of 1-(2-pyrimidinyl)pyrrole with aromatic diynes affords poly(arylenevinylene)s under mild conditions. This reaction avoids production of stoichiometric amounts of by-products. Although structural analysis of the obtained polymers reveals the presence of 1,1-vinylidene unit, switching the counter anion of the Co catalyst and steric hindrance of the diyne monomers improves the regioselectivity of the polymers. When a catalyst with bulky counter anions is used for the reaction of less hindered diyne monomers, 1,2-vinylene linkages are formed dominantly over 1,1-vinylidene linkages (93:7). The effect of the regioselectivity of the polymer on the optical and semiconducting properties is also evaluated., (© 2021 Wiley-VCH GmbH.)

Roundabout guidance receptor 4 (Robo4) is an endothelial-specific membrane protein that suppresses pathological angiogenesis and vascular hyperpermeability by stabilizing endothelial cells. Robo4 suppresses severe systemic inflammation induced by pathogens and endotoxins and inhibits tumor growth and metastasis, therefore serving as a potential therapeutic target. Although the regulation of Robo4 expression through transcription factors and epigenetic mechanisms has been studied, the role of histone deacetylases (HDACs) has not been explored. In the present study, we investigated the involvement of HDACs in the regulation of Robo4 expression. An HDAC inhibitor, MS-275, which inhibits HDAC1, HDAC2, and HDAC3, was found to suppress Robo4 expression in endothelial cells. Small interfering RNA (siRNA)-mediated knockdown of HDAC3, but not of HDAC1 and 2, also decreased its expression level. MS-275 downregulated the expression of the transcription factor complex GABP, in addition to suppressing Robo4 promoter activity. GABP expression was also downregulated by the siRNA against HDAC3. MS-275 decreased the transendothelial electrical resistance of a monolayer of mouse endothelial cells and increased the rate of leakage of Evans blue dye in the mouse lungs. In addition, MS-275 accelerated cell migration through the endothelial cell monolayer and augmented cell extravasation in the mouse lungs. Taken together, we demonstrated that MS-275 suppresses Robo4 expression by inhibiting HDAC3 in endothelial cells and enhances endothelial and vascular permeability. Thus, we demonstrated a novel mechanism regulating Robo4 expression and vascular permeability, which is anticipated to contribute to future therapies for infectious and inflammatory diseases.

The Povarov reaction combines aromatic amines, aldehydes, and alkynes in a single step and is regarded as an annulative π-extension reaction of aromatic amines. In this study, the Povarov reaction was investigated as an efficient tool for the synthesis of aza-polycyclic aromatic hydrocarbons via multiple π-extensions. The double Povarov reaction of 1,4-diaminobenzene yielded the 4,7-phenanthroline derivative as the major product, regardless of the steric repulsion in the product. The site selectivity mainly depended on the HOMO distribution of the intermediate rather than the steric factor. Based on these insights, a 1,5,9-triazatriphenylene derivative was synthesized via a triple Povarov reaction. The structures of the synthesized compounds were unambiguously determined by single-crystal X-ray diffraction analysis. The triazatriphenylene derivative formed a smooth and stable thin film upon vacuum vapor deposition and served as a hole-blocking material in organic light-emitting diodes.

Conjugated polymers have immense potential for their use as semiconducting materials in organic optoelectronic devices. The improvement of synthetic methods for conjugated polymers is important for the practical application of conjugated polymers. For mass production, synthetic methods must be developed by considering the concerns regarding cost and environment. Reduction in the number of synthetic steps is an efficient approach to address these concerns. The utilization of direct CH functionalization is a reasonable strategy in monomer and polymer syntheses, because the prefunctionalization steps for CC bond formation can be eliminated. This review summarizes the recent developments in the efficient syntheses of conjugated polymers as well as their monomers via direct arylation (CH/CX coupling) and cross-dehydrogenative coupling (CH/CH coupling) reactions., (© 2020 Wiley-VCH GmbH.)

Cardiac involvement of malignant lymphoma is relatively common, although such a phenomenon has subclinical manifestations that are difficult to detect. We herein describe a patient with atrial fibrillation and sick sinus syndrome as the main symptoms. Computed tomography showed a mass in the right atrium extending into the superior vena cava (SVC). We implanted the patient with a leadless pacemaker. Transvenous biopsy revealed a diffuse large B-cell lymphoma. The patient was treated successfully with chemotherapy including rituximab. This case suggested that cardiac lymphoma may cause sick sinus syndrome, and leadless pacemaker implantation is a safe treatment option in patients with partial SVC obstruction.

Depositing minute light emitters into a regular array is a basic but essential technique in display technology. However, conventional lithographic methodologies involve multistep and energy-consuming processes. Here, we develop a facile method in which organic and polymeric fluorescent dyes spontaneously aggregate to form a patterned microarray. We find that a thin film of fluorescent π-conjugated polymer transforms into micrometer-sized aggregates when exposed to binary organic vapor at ambient temperature. The arrayed microaggregates can be formed over the whole substrate surface when using a quartz substrate that is prepatterned with regular hydrophilic boxes and hydrophobic grids. The resultant microarray is applicable to optical memories and displays when photoswitchable fluorophores are doped into the polymer matrix.

We have synthesised an air-stable Pd(0) catalyst bearing donor and acceptor phosphine ligands (Complex 1). This study revealed the long-term air stability and catalytic property of Complex 1 as a catalyst for cross-coupling reactions, where it was stable in air for eight months. DFT calculations revealed that the acceptor ligands in Complex 1 decreased the HOMO energy level, which provided the observed air stability. Complex 1 successfully served as a catalyst for direct C-H arylation reactions and Suzuki-Miyaura cross-coupling reactions, and catalysed the reaction of a relatively inactive substrate, 2-chrolopyridine, which could not be achieved by conventional, air-stable Pd(0) catalysts. Isolating the intermediates of the coupling reactions revealed that each intermediate possessed the donor ligand (PCy3), which was determined to be responsible for imparting the high catalytic activity exhibited by Complex 1.

Background: Catheter ablation for atrial fibrillation (AF) is an established therapy. However, postoperative recurrence is a serious issue caused by the reconduction of the isolated pulmonary veins (PV) and the onset of non-PV foci. The objectives of this study were to elucidate dormant conduction, confirm PV arrhythmia substrate, induce non-PV foci after PV isolation, and assess the acute efficacy of high dose isoproterenol (ISP) when administered in addition to adenosine., Methods: The study consisted of 100 patients with drug-refractory AF (paroxysmal and persistent) who underwent ablation therapy (either radio-frequency or cryoballoon ablation) as the first-line of therapy at our hospital. All patients first underwent PV isolation (PVI) and were administered adenosine followed by ISP (6 μg × 5 min). The effects were observed, and the therapeutic strategy was evaluated., Results: Persistent dormant conduction due to ISP administration was observed in 13 patients. In over half of the patients, arrhythmia substrates were identified in the PV. Ten patients presented with persistent PV firing. The ablation of non-PV foci was additionally performed in 23 patients., Conclusions: We found that dormant conduction, as a result of ISP administration, is persistent and ISP is useful when performing an ablation. In addition, ISP administration is useful for the identification of PV arrhythmia substrates and induction of non-PV foci. However, the effectiveness of ISP may be partially due to the complementary effect of adenosine, and, therefore, a combination of the two drugs seems preferable.

In this study, π-conjugated poly(arylenevinylene)s are synthesized via the Pd-catalyzed dehydrogenative direct alkenylation of polyfluoroarenes with diethenyl aromatic monomer. The introduction of a fluoro group promotes the cross-coupling reaction, and the formation of the undesired homocoupling byproduct is minimized by optimizing the reaction conditions. The polycondensation reactions lead to the formation of poly(arylenevinylene)s with a well-defined trans-configuration. The obtained polymers are evaluated as emitting materials for organic light-emitting diodes., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The cationic Pt complexes with amide groups have been found to show dimer emission through hydrogen bonding interactions with counter anions even at low concentration. In order to investigate further details of dimer emission, we prepared three Pt complexes, Pt·B(C 6 F 5 ) 4 , Pt·Cl, and Pt·PF 6 , whose counter anions possess different strengths of a hydrogen bonding acceptor. Hydrogen bonding interactions in the ground state and excited-state dynamics of the Pt complexes were evaluated by NMR analysis, temperature dependence, and kinetics of dimer emission. These studies revealed that the hydrogen bonding interaction in the ground state is essential for dimer emission, but too strong hydrogen bonding prevents dimer emission due to the inhibition of a stacked dimer formation in the excited state. Owing to this trade-off, the Pt complex with a moderate hydrogen bonding acceptor, PF 6 - , most effectively shows dimer emission. In general, a strong supramolecular interaction efficiently provides a desired assembled structure showing multi-molecular emission. We revealed a unique phenomenon that a moderate interaction is beneficial to effective multi-molecular emission.

Polycondensation via Pd-catalyzed cross-dehydrogenative-coupling reaction of 2,2',3,3',5,5',6,6'-octafluorobiphenyl with thiophene analogues was studied. The synthetic protocol, in which employment of prefunctionalized starting monomers was fully avoided, allowed straightforward access to an alternating π-conjugated polymer. The addition of K 2 CO 3 to the catalytic system promotes the cross-coupling reaction and suppresses the undesired homocoupling reaction, producing the corresponding donor-acceptor type π-conjugated polymers with minor homocoupling defects. The reaction also proceeded using O 2 as the terminal oxidant, resulting in lower loading of the Ag oxidant. The obtained polymer was evaluated as an emitting material for an organic light-emitting diode.

Despite the coplanar structure, a conjugated alternating copolymer forms amorphous, well-defined microspheres without π-stacked crystalline domains. Here, we gain insights into the mechanism of how the coplanar conjugated polymer forms amorphous microspheres by means of spectroscopic studies on the assembly/disassembly processes. The difference of the spectral profiles of photoabsorption and photoluminescence with varying solvent/nonsolvent composition clarifies that stepwise assembly takes place through the microsphere formation; [1] intrapolymer linear-to-folding transformation upon diffusion of polar nonsolvent and [2] interpolymer assembly of the foldamers upon further addition of the nonsolvent to form microspheres. As shown in various biopolymers such as proteins and DNA, such stepwise folding and assembly behaviors of conjugated polymers from primary to secondary and tertiary structure open a new way to create transformable functional materials.

Compounds with controllable color emissions are potentially useful as photoluminescent materials in imaging and sensing applications. Multimolecular emission can be used realizing variable-color emitters and has been demonstrated in the solid state. However, achieving multimolecular emission in solution is difficult to control. In this study, we used a combination of intermolecular interactions, namely hydrogen bonding and solvophobic effect, to modulate multimolecular emissions. A designed Pt complex demonstrated three emission colors: blue (monomer emission), yellow (emission form hydrogen-bonded dimer), and orange (aggregate emission). All of the emission modes exhibited high luminescence quantum yields, as a result of their uniform assemblies.

A 67-year-old woman complained of urinary frequency and gross hematuria. She was referred to our hospital with the diagnosis of bladder tumor. Transurethral resection of the bladder tumor (TURBT) was performed and pathological diagnosis was urothelial carcinoma (G2>G3) with muscular invasion. Because she hoped bladder preservation therapy, she received two courses of M-VAC (methotrexate, vinblastine, doxorubicin and cisplatin) therapy, one course of arterial infusion chemotherapy, and chemoradiotherapy with cisplatin. After those therapies she underwent 4 times of TURBT and two courses intravesical BCG therapy. However, solitary lung metastasis appeared 19 months after the initial TURBT. Multidisciplinary treatments including 25 courses of various multiagent chemotherapies, radiation therapy to the lung metastasis and surgical resection of a urethral recurrence were performed. Although a localized radiation pneumonitis was developed, the lung metastasis appeared to be controlled for 26 months after the radiation therapy to the lung. Bilateral ureteral and renal pelvic tumors appeared after the radiation therapy. Severe bleeding was occurred from renal pelvic tumors several times and she needed the hospital stay 2 times. Active bleeding stopped after the administration of chemotherapy each time. Although she died of occlusive jaundice due to the liver metastasis, she had been alive due to the multidisciplinary treatment for 67 months after lung metastasis appearance with relatively good performance status.

We report a case of adrenal neuroendocrine carcinoma that was treated with laparoscopic adrenalectomy. A 70-year-old man was referred to our department for investigation of a 5 cm right adrenal mass detected by abdominal CT. No increased endocrine activity attributable to the adrenals was observed clinically, and there was no obvious uptake in 123 I-MIBG scintigraphy. An adrenalectomy was performed laparoscopically. Positive immunohistochemical results for synaptophysin, chromogranin A and CD56 were compatible with neuroendocrine carcinoma.

Highly luminescent π-conjugated polymeric microspheres were fabricated through self-assembly of energy-donating and energy-accepting polymers and their blends. To avoid macroscopic phase separation, the nucleation time and growth rate of each polymer in the solution were properly adjusted. Photoluminescence (PL) studies showed that efficient donor-to-acceptor energy transfer takes place inside the microspheres, revealing that two polymers are well-blended in the microspheres. Focused laser irradiation of a single microsphere excites whispering gallery modes (WGMs), where PL generated inside the sphere is confined and resonates. The wavelengths of the PL lines are finely tuned by changing the blending ratio, accompanying the systematic yellow-to-red color change. Furthermore, when several microspheres are coupled linearly, the confined PL propagates the microspheres through the contact point, and a cascade-like process converts the PL color while maintaining the WGM characteristics. The self-assembly strategy for the formation of polymeric nano- to microstructures with highly miscible polymer blends will be advantageous for optoelectronic and photonic device applications.

The photovoltaic characteristics of an amorphous polymer containing EDOT and fluorene units were investigated. In particular, the effects of the terminal structure, residual amount of Pd, and molecular weight were systematically investigated. Direct arylation polycondensation of EDOT followed by an established purification method readily afforded polymers with different terminal structures, Pd contents, and molecular weights. Of these factors, the terminal structure of the polymer was a crucial factor affecting the photovoltaic characteristics. For example, the polymer with a Br terminal had a PCE of 2.9% in bulk-heterojunction organic photovoltaics (BHJ OPVs) with a fullerene derivative, whereas the polymer without a Br terminal had a PCE of 4.6% in the same cell configuration. The decreased Pd residues and high molecular weights of the polymers increased the long-term stability of the devices. Moreover, BHJ OPVs containing the high-molecular-weight polymer could be fabricated with an environmentally friendly nonhalogenated solvent.

We investigate the whispering gallery modes (WGMs) of self-assembled single microspheres. They consist of a recently developed highly fluorescent π-conjugated copolymer and exhibit excellent optical properties with Q-factors up to 10(4). Under continuous laser irradiation, we observe a splitting of the highly degenerate spherical WGMs into a multiplet of lines. Comparison with the calculated spectral response of a weakly distorted sphere shows that the optical excitation induces a change of the optical path length in the microcavity so that it resembles a prolate spheroid. The separation of the lines is given by the ellipticity and the azimuthal mode number. Measurements in various gaseous environments suggest that the distortion is caused by light induced oxidation of the polymer. Our findings show that photooxidation can be a beneficial mechanism for in-situ tuning of optically active polymer structures.

We report a 43-year-old TSC man with repeated hemorrhage of bilateral renal AML. He was diagnosed with TSC based on the findings of facial angiofibroma, mental retardation and epilepsy in childhood. In 2011, he experienced three times in AML-associated hemorrhage from the left kidney and received selective transarterial embolotherapy (TAE). In 2013, he also experienced AML-associated hemorrhage from the right kidney and received selective TAE. To control his AML, treatments with Everolimus was started and well tolerated. So far, his renal AML remarkably shrunk without retroperitoneal hemorrhage for 24 months, while he had some episode of side effect.

Background: The distribution of anti-factor Xa activity (AXA) values in non-valvular atrial fibrillation (NVAF) patients on edoxaban therapy has not been fully elucidated., Methods and results: The steady-state trough and peak AXA values were measured in 66 NVAF patients. The trough AXA value did not differ significantly between the 60-mg and the 30-mg OD groups (0.17±0.13 IU/ml vs. 0.12±0.11 IU/ml, respectively; P=0.17). Similarly, the peak AXA value did not differ significantly between the 2 groups (1.45±0.81 IU/ml vs. 1.25±0.48 IU/ml, respectively; P=0.26)., Conclusions: Recommended dosing should be followed for sufficient efficacy of edoxaban. (Circ J 2016; 80: 745-747).

Objective: We assessed which information from a prostate biopsy had the strongest relationship with prostate cancer detection by 3T-MRI., Materials and Methods: Sixty-one consecutive patients with biopsy-proven prostate cancer who underwent 3T-MRI before biopsy were enrolled in this retrospective study. Two radiologists independently reviewed T2-weighted and diffusion-weighted images. When the cancer lesions were revealed by biopsy and MRI depicted them at corresponding sites, we classified these lesions as MRI-detectable cancer. If the cancer lesions were revealed by biopsy, but any cancers had not been detected, we classified these lesions as MRI-undetectable cancer. We compared the Gleason score (GS), cancer ratio (CaR) and cancer length (CaL) from core biopsies between the two groups., The Results: GS, CaR and CaL differed significantly between the MRI-detectable group (N = 70), and the MRI-undetectable group (N = 73). 3T-MRI could detect cancer cores with a sensitivity of 90.5% in cores with CaR ≥ 60%, and with a sensitivity of 81.8% in those with CaL ≥ 5 mm. Receiver operating characteristic analysis showed that CaR (P = 0.006) and CaL (P = 0.010) significantly associated with the prostate cancer detection using MRI rather than GS., Conclusion: CaR and CaL from the core biopsies showed a stronger relationship to detection of the prostate cancer on 3T-MRI than the GS did.

Background and Purpose: We demonstrated previously that oxycodone has potent antinociceptive effects at supraspinal sites. In this study, we investigated changes in neuronal function and antinociceptive mechanisms of oxycodone at ventrolateral periaqueductal gray (VLPAG) neurons, which are a major site of opioid action, in a femur bone cancer (FBC) model with bone cancer-related pain., Experimental Approach: We characterized the supraspinal antinociceptive profiles of oxycodone and morphine on mechanical hypersensitivity in the FBC model. Based on the disinhibition mechanism underlying supraspinal opioid antinociception, the effects of oxycodone and morphine on GABAA receptor-mediated inhibitory postsynaptic currents (IPSCs) in VLPAG neurons were evaluated in slices from the FBC model., Key Results: The supraspinal antinociceptive effects of oxycodone, but not morphine, were abolished by blocking G protein-gated inwardly rectifying potassium1 (Kir 3.1) channels. In slices from the FBC model, GABAergic synaptic transmission at VLPAG neurons was enhanced, as indicated by a leftward shift of the input-output relationship curve of evoked IPSCs, the increased paired-pulse facilitation and the enhancement of miniature IPSC frequency. Following treatment with oxycodone and morphine, IPSCs were reduced in the FBC model, and the inhibition of presynaptic GABA release by oxycodone, but not morphine was enhanced and dependent on Kir 3.1 channels., Conclusion and Implications: Our results demonstrate that Kir 3.1 channels are important for supraspinal antinociception and presynaptic GABA release inhibition by oxycodone in the FBC model. Enhanced GABAergic synaptic transmission at VLPAG neurons in the FBC model is an important site of supraspinal antinociception by oxycodone via Kir 3.1 channel activation., (© 2014 The Authors. British Journal of Pharmacology published by John Wiley & Sons Ltd on behalf of The British Pharmacological Society.)

Background: Chromogenic anti-factor Xa activity (AXA) assay is reported to be the most appropriate method to measure the pharmacodynamics of apixaban, but the distribution of AXA in non-valvular atrial fibrillation (NVAF) patients on apixaban therapy has not been fully elucidated., Methods and results: Steady-state trough and peak AXA were measured in 124 NVAF patients taking apixaban. In 25 patients, baseline, first peak, and trough AXA were also examined, and were 0.01±0.02 IU/ml, 0.83±0.43 IU/ml, and 0.34±0.17 IU/ml, respectively. First trough AXA was significantly lower than steady-state trough AXA, although it was significantly higher than baseline (P<0.0001). Similarly, first peak AXA was significantly lower than steady-state peak AXA (P<0.0001). In 124 patients, steady-state peak AXA was significantly higher in the 5-mg b.i.d. group than in the 2.5-mg b.i.d. group (2.05±0.73 IU/ml vs. 1.51±0.65 IU/ml, respectively; P<0.001), although there was no significant difference in trough AXA. Other than dose, age and serum creatinine were significantly related to both trough and peak AXA., Conclusions: The distribution of AXA in Japanese NVAF patients on apixaban therapy in daily clinical practice both in the acute and steady-state phase was measured. In patients taking apixaban, measurement of AXA clearly showed the pharmacodynamic profile of this drug.

It has begun to be understood that μ-opioid receptor (MOR) produces ligand-biased agonism, which contributes to differential physiological functions of MOR agonists. We previously demonstrated that in oxaliplatin-induced neuropathy in rats, morphine and oxycodone exhibited antinociceptive effects while antinociception of fentanyl was partial, and such different efficacies might result from the different level of Gi/o protein activation. Based on our background, to reveal further mechanism, we focused on the role of Gi/o protein-related downstream signaling, the G-protein inwardly rectifying K(+)1 (GIRK1) channel. The GIRK1 channel blocker tertiapin-Q (30pmol) was intracerebroventricularly (i.c.v.) or intrathecally (i.t.) administered to rats with oxaliplatin-induced neuropathy. The antinociception of systemic morphine (3mg/kg, subcutaneously (s.c.)) was suppressed only by pretreatment of i.t. tertiapin-Q, while supraspinal tertiapin-Q suppressed only the antinociception of systemic oxycodone (0.56mg/kg, s.c.). Partial antinocicpetion of fentanyl (0.017mg/kg, s.c.) was neither affected by i.c.v nor i.t. tertiapin-Q. These results demonstrated that GIRK1 channels differentially contribute to antinociceptive effects of MOR agonists, and that action site of GIRK1 channels is also different between morphine and oxycodone in oxaliplatin model. This study suggests the possibility that GIRK1 channels have a crucial role for antinociception of MOR agonists in oxaliplatin-induced neuropathy., (Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.)

Confinement of light inside an active medium cavity can amplify emission. Whispering gallery mode (WGM) is one of mechanisms that amplifies light effectively by confining it inside high-refractive-index microstructures, where light propagates along the circumference of a sphere via total internal reflection. Here we show that isolated single microspheres of 2-10 μm diameter, formed from self-assembly of π-conjugated alternating copolymers, display WGM photoemission induced by laser pumping. The wavelengths of the emission peaks depend sensitively on the sphere size, position of the excitation spot and refractive index of each polymer. The Q-factor increases with increasing sphere diameter and displays a linear correlation with the reciprocal radius, indicating that the small curvature increases the efficacy of the total internal reflection. WGM photoemission from π-conjugated polymer microspheres is unprecedented and may be of high technological impact since the microspheres fulfill the role of fluorophores, high-refractive-index media and resonators simultaneously, in addition to their simple fabrication process.

Two types of heterometallic one-dimensional chains, [{Rh2(acam)4}{Pt2(piam)2(NH3)4}2]n(CF3SO3)4n·2nMeOH (2, where acam = acetamidate, piam = pivalamidate) and [{Rh2(acam)4}{Pt2(piam)2(NH3)4}]n(CF3CO2)2n·2nEtOH (3), have been synthesized and characterized by single-crystal X-ray analyses. The chain structures in 2 and 3 are composed of two kinds of dinuclear complexes, [Rh2(acam)4] (i.e., [Rh2]) and [Pt2(piam)2(NH3)4] (i.e., [Pt2]), where Rh and Pt atoms are axially linked by metal-metal bonds. In 2 and 3, each complex is one-dimensionally aligned as -{[Rh2]-[Pt2]-[Pt2]}n- or -{[Rh2]-[Pt2]}n-, respectively, in which different alignments are caused by different isomers of [Pt2] that are HH (head-head) and HT (head-tail) orientation of piam ligands and their hydrogen bonding modes. Considering the crystal structures and X-ray photoelectron spectra (XPS) measurements in 2 and 3, the oxidation states of the metal atoms are -{[Rh2(II,II)]-[Pt2(II,II)]-[Pt2(II,II)]}n- and -{[Rh2(II,II)]-[Pt2(II,II)]}n-, which are unchanged from those in the starting compounds. The diffuse reflectance spectra show that LUMOs are M-M σ-type orbitals. The gap between filled and vacant σ-type orbitals in 3 is narrower than that in 2, and is attributed to the relative higher destabilized filled σ-type orbitals caused by lower numbers of linking platinum atoms.

Although the right-ventricle to pulmonary artery( RV-PA) shunt as a source of pulmonary blood supply of Norwood procedure has improved early outcomes, disadvantages including right ventricular dysfunction or arrhythmias have been reported. So it has been still remained controversial whether BT shunt or RV-PA conduit should be selected. We examined the influence of Blalock-Taussig( BT) shunt size on regulation of the pulmonary blood flow in experimental model of a univentricular heart to determine the specific guidelines regarding suitable shunt size in the Norwood procedure. The canine univentricular heart model with the ratio of shunt size to body weight (SS/BW) of 0.8 to 1.1 showed significant negative correlation between the pulmonary/systemic blood flow ratio( Qp/Qs)and arterial PCo2, but those with SS/BW of 1.1 to 1.4 did not. Similar phenomena were shown with the grouped data on relationship between the Qp/Qs and inspired oxygen fraction. These findings imply that when SS/BW is 0.8 to 1.1, the Qp/Qs is controllable by physiologic respiratory manipulations. In the context of our clinical experiences, SS/BW of 0.9 to 1.0 is considered a useful index for suitable BT shunt in the Norwood procedure.

The aim of this in vitro study was to investigate the wear behavior of the abrader when tetragonal zirconia polycrystal (TZP), cp-titanium (CpTi) and Ti-6Al-4V alloy (TiAlV) were used as the antagonist on fixed dental prostheses (FDPs). Both hemisphere abrader and flat substrate specimens were prepared using TZP, CpTi and TiAlV. Two-body wear tests were performed in distilled water, and the wear volume of the abrader specimen was measured to evaluate the wear behavior. In addition, scanning microscopic observation and an electron probe micro-analysis were performed to elucidate the underlying mechanism of the wear. The wear volume of CpTi and TiAlV abrader specimens was approximately 20 times larger than that of TZP abrader specimen against all substrate specimens. This is due to the differences in hardness between the ultra-hardness of TZP and the comparatively low hardness of CpTi and TiAlV. The wear volume of CpTi and TiAlV abrader specimens against the TZP substrate was significantly smaller than for the CpTi and TiAlV substrates despite the hardness of TZP being much larger than those of CpTi and TiAlV. This phenomenon may be based on the adhesive wear mechanism. Elements of Ti, Al and V originating in the TiAlV substrate were detected adhering to the abrader CpTi specimen. These results suggest that FDPs of CpTi and TiAlV are susceptible to wear against not only TZP but also CpTi and TiAlV in contrast to TZP FDPs.

Background and Purpose: Oxycodone and morphine are μ-opioid receptor agonists prescribed to control moderate-to-severe pain. Previous studies suggested that these opioids exhibit different analgesic profiles. We hypothesized that distinct mechanisms mediate the differential effects of these two opioids and investigated the role of G protein-gated inwardly rectifying potassium (K(IR)3 also known as GIRK) channels in their antinociceptive effects., Experimental Approach: Opioid-induced antinociceptive effects were assessed in mice, using the tail-flick test, by i.c.v. and intrathecal (i.t.) administration of morphine and oxycodone, alone and following inhibition of K(IR)3.1 channels with tertiapin-Q (30 pmol per mouse, i.c.v. and i.t.) and K(IR)3.1-specific siRNA. The antinociceptive effects of oxycodone and morphine were also examined after tertiapin-Q administration in the mouse femur bone cancer and neuropathic pain models., Key Results: The antinociceptive effects of oxycodone, after both i.c.v. and i.t. administrations, were markedly attenuated by K(IR)3.1 channel inhibition. In contrast, the antinociceptive effects of i.c.v. morphine were unaffected, whereas those induced by i.t. morphine were attenuated, by K(IR)3.1 channel inhibition. In the two chronic pain models, the antinociceptive effects of s.c. oxycodone, but not morphine, were inhibited by supraspinal administration of tertiapin-Q., Conclusion and Implications: These results demonstrate that K(IR)3.1 channels play a primary role in the antinociceptive effects of oxycodone, but not those of morphine, at supraspinal sites and suggest that supraspinal K(IR)3.1 channels are responsible for the unique analgesic profile of oxycodone., (© 2013 The British Pharmacological Society.)

It may be difficult to access a route to deliver a stent-graft for abdominal aortic aneurysm in high-risk patients with bilateral iliofemoral occlusive disease. These two patients underwent both endovascular aortic aneurysm repair by a modified iliac access conduit technique and sequential ipsilateral iliofemoral artery bypass using the conduit, which provided excellent results. The iliac access conduit facilitates endovascular aortic aneurysm repair and ipsilateral iliofemoral bypass of high-risk patients with abdominal aortic aneurysm and bilateral iliofemoral occlusive disease.

The rewarding effects of μ-receptor agonists can be suppressed under several pain conditions. We recently showed that clinically used μ-receptor agonists possess efficacies for relieving the neuropathic pain induced by chemotherapeutic drug in rats; however, it is possible that the use of μ-receptor agonists may trigger the rewarding effects even under chemotherapeutic drug-induced neuropathic pain. Nevertheless, no information is available regarding whether μ-receptor agonists produce psychological dependence under chemotherapeutic drug-induced neuropathic pain. Therefore, we examined the effects of neuropathy induced by chemotherapeutic drugs on the rewarding effects of morphine, oxycodone, and fentanyl in rats. Repeated treatment with oxaliplatin or paclitaxel produced neuropathy as measured by the von Frey test. Rewarding effects produced by antinociceptive doses of μ-receptor agonists were not suppressed under oxaliplatin- or paclitaxel-induced neuropathy. Furthermore, the morphine-induced increase in the release of dopamine from the nucleus accumbens, which is a critical step in the rewarding effects of μ-receptor agonists, was not altered in paclitaxel-treated rats. These results suggest that the rewarding effects of μ-receptor agonists can still be established under oxaliplatin- or paclitaxel-induced neuropathic pain. Therefore, patients should be carefully monitored for psychological dependence on μ-receptor agonists when they are used to control chemotherapeutic drug-induced neuropathic pain.

Oxaliplatin is a chemotherapeutic agent that induces chronic refractory neuropathy. To determine whether opioids effectively relieve this chronic neuropathy, we investigated the efficacies of morphine, oxycodone, and fentanyl, and the mechanisms underlying opioid antinociception, in oxaliplatin-induced neuropathy in rats. Rats exhibited significant mechanical allodynia following 2 weeks of chronic oxaliplatin administration. Within the range of doses that did not induce sedation and/or muscle rigidity, morphine (3 mg/kg, subcutaneously, s.c.) and oxycodone (0.3-0.56 mg/kg, s.c.) completely reversed oxaliplatin-induced mechanical allodynia, whereas fentanyl (0.017-0.03 mg/kg, s.c.) showed partial antinociception. The antinociception of the optimal doses of morphine and oxycodone were completely inhibited by pertussis toxin (PTX; 0.5 μg/rat, i.c.v.), a Gi/o protein inhibitor, while the partial effect of fentanyl was not affected in the oxaliplatin model. In the [(35)S]-GTPγS binding assay, activation of μ-opioid receptor by fentanyl, but not by morphine or oxycodone, in the mediodorsal thalamus was significantly reduced in oxaliplatin-treated rats. These results indicate that the lower antinociceptive potency of fentanyl in the oxaliplatin model might in part result from the loss of PTX-sensitive Gi/o protein activation, and the degree of Gi/o protein activation might be related to the potency of antinociception by opioids in this model.

Although norepinephrine transporter (NET) inhibition has an additional effect on μ-opioid receptor (MOR)-mediated anti-nociception in inflammatory and neuropathic pain, its effect on cancer pain is not well characterized. We investigated the additional effect of NET inhibition on MOR activation using a mouse femur bone cancer (FBC) pain model by comparing the anti-nociceptive effect of the dual-acting opioids tramadol and tapentadol and the clinically used MOR-targeted opioids oxycodone and morphine. The anti-nociceptive effects of subcutaneously administered opioids were assessed using the von-Frey filament test. Oxycodone (1 - 10 mg/kg) and morphine (5 - 50 mg/kg) dose-dependently exhibited potent anti-nociceptive effects, whereas tramadol (10 - 56 mg/kg) and tapentadol (10 - 30 mg/kg) exhibited partial effects. Rota-rod analyses of tapentadol at a higher dose (> 30 mg/kg) showed a significant decrease in motor coordination, which was partially recovered by pretreatment with MOR or α(1)-adrenoceptor antagonists. The partial anti-nociceptive effect of tapentadol (30 mg/kg) was completely suppressed by a MOR antagonist, but not by α(1)- or α(2)-adrenoceptor antagonists, suggesting that neither α(1)-adrenoceptor- nor α(2)-adrenoceptor-mediated pathways are involved in anti-nociception in the FBC model. We conclude that addition of NET inhibition does not contribute to MOR-mediated anti-nociception in bone cancer pain.

Polycondensation of 1-(2-pyrimidinyl)pyrrole with 2,7-dibromo-9,9-dioctylfluorene via Ru-catalyzed direct arylation gives the corresponding conjugated polymer with a molecular weight of 19 800 in 86% yield. The introduction of directing group, 2-pyrimidinyl substituent, into the pyrrole monomer induces ortho-metalation and provides the site-selective direct arylation polycondensation at the α-position of pyrrole unit without the protection of β-position. The removal of 2-pyrimidinyl substituent on the pyrrole unit proceeds efficiently and results in the enhancement of coplanarity along the main chain of the polymer., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)