Intraoperative Transbronchial Metallic Coil Marking for Small Peripheral Pulmonary Lesions in a Hybrid Operation Room.

: Computed tomography (CT)-guided transbronchial metallic coil marking is useful for identifying the locations of small peripheral pulmonary lesions. Even deeply located lesions may be accurately identified and resected with adequate margins. This method is also applicable to multiple lesions.

Electron Transfer Enhanced by a Minimal Energetic Driving Force at the Organic-Semiconductor Interface.

The energetic driving force for electron transfer must be minimized to realize efficient optoelectronic devices including organic light-emitting diodes (OLEDs) and organic photovoltaics (OPVs). Exploring the dynamics of a charge-transfer (CT) state at an interface leads to a comprehension of the relationship between energetics, electron-transfer efficiency, and device performance. Here, we investigate the electron transfer from the CT state to the triplet excited state (T) in upconversion OLEDs with 45 material combinations.

Wavily Curved Perylene Diimides: Synthesis, Characterization, and Photovoltaic Properties.

Solubility enhancement is a key issue for developing the perylene diimide-based functional materials. Introduction of curved structure proved an effective solubilizing method without employing steric repulsion. In this work, wavily curved perylene diimides were developed as a new family of highly soluble curved perylene diimides.

Blue organic light-emitting diode with a turn-on voltage of 1.47 V.

Among the three primary colors, blue emission in organic light-emitting diodes (OLEDs) are highly important but very difficult to develop. OLEDs have already been commercialized; however, blue OLEDs have the problem of requiring a high applied voltage due to the high-energy of blue emission. Herein, an ultralow voltage turn-on at 1.

Visible-Light-Induced Reductive Coupling of Arylacetylenes with Benzothiazole Sulfones.

In this study, we propose heavy-metal-free reductive coupling of arylacetylenes with benzothiazole sulfones. The reactions of alkyl or benzylic benzothiazole sulfones with arylacetylenes are successfully performed in the presence of Hantzsch esters and KCO under visible-light irradiation to afford 1,2-disubstituted alkenes in moderate to good yields, with -isomer as the major product. The utility of this protocol is expanded to α-deuterative coupling using a deuterated Hantzsch ester, furnishing the corresponding alkenes with high deuterium incorporation.

Clinical significance of completion of radium-223 treatment and acute adverse events in patients with metastatic castration-resistant prostate cancer.

Objectives: In the treatment of castration-resistant prostate cancer (CRPC) with bone metastases, radium-223 dichloride (Ra-223) is the only bone-targeted drug that shows survival benefits. Completing six courses of Ra-223 treatment is thought to be associated with better patient survival, but this treatment has a relatively high rate of acute adverse events.

Methods: This retrospective study included 85 patients from 12 institutions in Japan to investigate the clinical significance of the completion of Ra-223 treatment and acute adverse events in CRPC patients.

Influence of N-Substituents on Photovoltaic Properties of Singly Bay-Linked Dimeric Perylene Diimides.

The influence of N-substituents on the photovoltaic properties of singly bay-linked perylene diimides (diPDIs) was systematically investigated to understand the aromatic-aliphatic balance, which is beneficial for achieving high device performance in organic photovoltaic (OPV) systems. The synthesis of various N-substituted diPDIs was successfully achieved using a newly developed one-step procedure, resulting in sufficiently high yields. Detailed investigations of seven variants of diPDIs demonstrated that the primary alkyl substituents, particularly the 2-ethylhexyl group, induce the self-organized growth of thin films with high crystallinity.

5,11-Diazadibenzo[hi,qr]tetracene: Synthesis, Properties, and Reactivity toward Nucleophilic Reagents.

5,11-Diazadibenzo[hi,qr]tetracene was synthesized as a new nitrogen-substituted polycyclic heteroaromatic compound by Pd-catalyzed cycloisomerization of an alkyne precursor followed by oxidative cyclization with bis(trifluoroacetoxy)iodobenzene. The substitution of imine-type nitrogen atoms significantly enhanced its electron-accepting character and facilitated the direct nucleophilic addition of arylamines under strongly basic conditions to afford the desired amino-substituted products. The introduction of amino groups induced a remarkable red-shift in their absorption spectra; the tetrasubstituted product exhibited intense near-infrared absorbing property.

Randomized phase II trial of uracil/tegafur and cisplatin versus pemetrexed and cisplatin with concurrent thoracic radiotherapy for locally advanced unresectable stage III non-squamous non-small cell lung cancer: NJLCG1001.

Background: The optimal regimen for concurrent chemoradiotherapy (CCRT) of locally advanced non-squamous non-small cell lung cancer (NSCLC) was not definitive. We conducted randomized phase II study, NJLCG0601, and chemoradiotherapy with uracil/tegafur (UFT) and cisplatin achieved promising efficacy without severe toxicities. Here, we evaluated between this regimen and pemetrexed plus cisplatin in chemoradiotherapy for stage III non-squamous NSCLC.

Curved Perylene Diimides Fused with Seven-Membered Rings.

Curved perylene diimides fused with seven-membered rings have been synthesized using a regioselective bay-functionalization method and Pd-catalyzed intramolecular C-H/C-Br coupling reaction. X-Ray analysis and temperature-dependent NMR spectroscopy revealed the curved molecular structure with a certain degree of conformational flexibility. The curved and expanded π-conjugation altered the electronic properties while retaining the intrinsic properties of the parent perylene diimide.

Safe central venous catheters for esophageal cancer treatment.

 Introduction : Central venous catheter (CVC) use is essential for treating esophageal cancer. Peripherally inserted central catheters (PICC) are commonly used recently for improved patient comfort and safety. We compared centrally inserted central catheters (CICC) and PICC insertions and examined their safety.

[Resection of Anterior Mediastinal Tumor Followed by Left Brachiocephalic Vein Reconstruction;Report of a Case].

A 65-year-old man was referred to our hospital because of an abnormal shadow on a chest radiogram. Swelling of the face and upper limbs were noted. Enhanced computed tomography showed a 62×101 mm mass in the anterior mediastinum with invasion to the superior vena cava (SVC) and the right upper lobe of the lung.

Development of Perylene-Based Non-Fullerene Acceptors through Bay-Functionalization Strategy.

Perylene has had a tremendous impact in the history of material research for the molecular semiconductors. Among numerous derivatives of this polyaromatic hydrocarbon, perylene diimide (PDI) represents a promising class of organic materials envisioned as non-fullerene acceptors (NFAs) for the practical organic photovoltaic (OPV) applications due to their enhanced photo- and thermal stability and remarkably high electron affinity, some of which realize band-like transport properties. The present review guides some of the representative achievements in the development of rationally designed PDI systems, highlighting synthetic methodologies based on bay-functionalization strategies for creating well-designed molecular nanostructures and structure-performance relationship of perylene-based small molecular acceptors (SMAs) for the photovoltaic outcomes.

Regioselective Bay-Functionalization of Perylenes Toward Tailor-Made Synthesis of Acceptor Materials for Organic Photovoltaics.

The development of an efficient synthetic protocol for multiply bay-functionalized perylenes and application of these products to photovoltaics are reported. Tetrabenzyl 1-(4-tert-butylphenoxy)perylene-3,4,9,10-tetracarboxylate underwent a regioselective bromination at the 7-position followed by a further bromination at the 12-position to provide a 7,12-dibromide in high 84% yield. This compound was transformed into a tetrasubstituted C -symmetric dibromide by a controlled monoetherification and a final bromination.

Unresectable Advanced Gastric Cancer with Skin Invasion followed by Total Gastrectomy after Second-Line Chemotherapy.

Conversion surgery has been reported but few cases have undergone surgical R0 resection after second-line chemotherapy. We report a case of an unresectable locally advanced gastric cancer in a patient who finally underwent the operation (R0) after second-line chemotherapy. The 77-year-old male was diagnosed with gastric cancer (cT4 [SI; Skin, Liver] N0M0 c Stage IIIA) with invasion to the skin of the abdominal wall, and chemotherapy was initially performed because of his poor performance status and due to the large defect in the abdominal wall that might occur if an operation was performed.

Triplet-Triplet Annihilation-Based Upconversion Sensitized by a Reverse Micellar Assembly of Amphiphilic Ruthenium Complexes.

We have developed a new photon upconversion (UC) system utilizing a new amphiphilic sensitizer that comprises a hydrophilic ruthenium complex and a lipophilic bisanthracene appendage. At concentrations higher than 5 μM in toluene, the sensitizer formed a reverse micellar assembly which facilitated the triplet sensitization of 9,10-diphenylanthracene (DPA) more efficiently than homogeneously dispersed solutions to enhance the UC efficiency up to 38.2%.

Selective Formation of Helical Tetrapyrrin-Fused Porphyrins by Oxidation of β-to-β Linked meso-Aminoporphyrin Dimers.

Oxidation of β-to-β directly linked and sulfur-bridged meso-amino Ni -porphyrin dimers with PbO gave helical tetrapyrrin (biliverdin analogue)-fused Ni -porphyrins. These ring cleaving reactions differ markedly from the previously reported oxidation of a β-β linked Ni -porphyrin dimer carrying one amino group, which gave an azepine-fused porphyrin dimer. The tetrapyrrin-fused Ni -porphyrins display intense NIR absorption bands at 1200-1400 nm and reversible redox processes because of the highly π-conjugated networks and rigid structures.

Porphyrin-Stabilized Nitrenium Dication.

An azepine-fused Ni -porphyrin dimer was synthesized by oxidative amination of β-β linked Ni -porphyrin dimer, and its N-aryl congener was synthesized by twofold Buchwald-Hartwig amination of β-to-β linked and dichlorinated Ni -porphyrin dimer. Oxidation of the NH congener gave neutral aminyl radical and nitrenium ion successively in a similar manner to the previously reported NH-bridged Ni -porphyrin dimer. Oxidation of the N-aryl congener afforded formal nitrenium dication in a single-step two-electron oxidation.

meso-Functionalization of Boron(III) Subporphyrin with Boron(III) meso-Lithiosubporphyrin.

Boron(III) meso-lithiosubporphyrin was prepared by bromine-lithium exchange of B-tolyl B meso-bromosubporphyrin with n-butyllithium at -98 °C. The resulting subporphyrinyllithium was treated with various electrophiles such as benzophenone, N,N-dimethylformamide, CO , chlorotrimethylsilane, N-fluorobenzenesulfonimide, and dimesitylboryl fluoride to give the corresponding meso-functionalized B subporphyrins. The nucleophile was also used to construct B subporphyrin dimers such as bis(B subporphyrinyl)ketone, bis(B subporphyrinyl)carbinol, and disilane-bridged B subporphyrin dimer.

Stable Diporphyrinylaminyl Radical and Nitrenium Ion.

Nitrenium ions, isoelectronic nitrogen counterparts of carbenes, are important intermediates in various biological and chemical processes. Herein we describe the first synthesis and characterization of a stable nitrenium ion without resonance stabilization by adjoining amino groups. Namely, a stable salt of a diporphyrinylnitrenium ion was synthesized by stepwise oxidation of the corresponding diporphyrinylamine through a stable aminyl radical.

Effective stabilization of a planar phosphorus(iii) center embedded in a porphyrin-based fused aromatic skeleton.

Organophosphorus(iii) compounds usually take on stable pyramidal structures with a large inversion barrier of 30-35 kcal mol. In contrast, diphenylphosphine-fused Ni(ii) porphyrin, where the phosphorus atom is directly attached at the meso-position and embedded in a rigid skeleton, exhibits a considerably planarized phosphorus center. Here we report the synthesis of a mesityl-substituted Ni(ii) porphyrin analogue, , which allowed an evaluation of the inversion barrier (Δ‡203) by variable temperature H NMR spectroscopy which showed it to be exceptionally small, at 14.

A 1,5-Naphthyridine-Fused Porphyrin Dimer: Intense NIR Absorption and Facile Redox Interconversion with Its Reduced Congener.

Pt -catalyzed cyclization of β-to-β ethynylene-bridged meso-amino Ni porphyrin dimer 4 followed by oxidation with PbO afforded 1,5-naphthyridine-fused porphyrin dimer 5 in good yield. This dimer possesses a redox-active 1,4-diazabutadiene linkage that is interconvertible with its reduced 1,2-diaminoethene linkage upon treatments with NaBH or PbO . The dimer 5 exhibits an intense NIR absorption and a narrow HOMO-LUMO gap with a remarkably low reduction potential mainly due to effective bonding interactions in the LUMO through the 1,4-diazabutadiene linkage.

Embedding heteroatoms: an effective approach to create porphyrin-based functional materials.

Incorporation of planarized heteroatom(s) onto the porphyrin periphery is an effective approach to create porphyrin-based functional materials. In the last three decades, such an "embedding heteroatom" strategy has been actively explored in order to realize attractive electronic, optical, and electrochemical properties. This review aims to cover a variety of synthetic methodologies that have been developed for the construction of heteroatom-embedded porphyrins.