Photo-induced Morphological Changes of Lipid Bilayer Vesicles Enabled by a Visible-Light-Responsive Azo Compound.

Living cells and organelles are separated by a lipid membrane bilayer. It is possible to induce morphological changes in this membrane by disturbing the order of the membrane using external stimuli and understanding the details of this mechanism is expected to be applicable to intracellular transport. DBA (DBAB-BODIPY-aminopropyl), which contains (1) a DBAB (4-[di(biphenyl-4-yl)amino]azobenzene) moiety that undergoes photo-isomerization under visible light irradiation, and (2) a BODIPY (borondipyrromethene) fluorophore was synthesized. The π-π* transition absorptions of both the azo moiety and that of BODIPY moiety in DBA were observed, independently. The photo-isomerization rate constant of the DMSO solution of DBA at 299K is 5.5 ×10-3/s. The structure of the fluorescent group in DBA did not readily influence the isomerization. Upon introducing DBA into the lipid bilayer membranes of a vesicle suspension and irradiating the vesicles with visible light to isomerize the azo group, a morphological change in of the vesicles was observed due to the disturbance of the membrane order. Thus, DBA is a useful molecule for artificial modulation of the lipid membrane morphology.

Irreducible inferior shoulder dislocation requiring open reduction: A case report.

In inferior shoulder dislocation (ISD) cases, closed reduction usually achieves reduction and irreducible ISD is extremely rare. To date, only two cases requiring open reduction have been reported. Herein, we describe a case of an irreducible ISD that required open reduction. A 90-year-old woman fell at home and presented to our hospital. Plain radiography revealed a right ISD and greater tuberosity avulsion fracture. Because reduction under general anesthesia was difficult, we performed open reduction. The humeral head was entrapped by the inferior shoulder capsule. Since inferior instability remained after reduction, we reduced and fixed the greater tuberosity fracture and repaired the rotator cuff tear (RCT). This case suggested that humeral head entrapment by the inferior capsule and decreased force couple toward the humeral head by the greater tuberosity fracture and RCT cause irreducibility. Moreover, since instability can remain after reduction for ISD accompanying greater tuberosity fracture or RCT, preparing for implantations to repair these lesions is recommended.

Acid-fast bacilli smear test of a blood culture sample for the diagnosis of disseminated Mycobacterium genavense infection: A case report.

Mycobacterium genavense, a nontuberculous Mycobacterium, is found in immunosuppressed patients, particularly in those with HIV. Mycobacterium genavense incubation under standard culture conditions is difficult, and its identification is challenging using routine culture methods. Herein, we report the case of a 40-year-old Japanese man with HIV presenting with disseminated M. genavense infection. An analysis using an automated blood culture system did not show positive signals during 6 weeks of incubation. However, an acid-fast bacilli smear of his blood sample was positive for the bacterium. Mycobacterium genavense was identified using sequencing analysis, targeting the heat shock protein 65 gene. The patient recovered from the infection, following antibiotic therapy for 18 months. Under suspicion of disseminated M. genavense infection and the absence of bacterial growth in blood culture samples, an acid-fast bacilli smear test of the sample may be useful for timely diagnosis.

Thiopyrylium Scaffolds from the Lewis/Brønsted-Acid-Promoted Cyclization of Thioethers.

A series of acene- or heteroacene-fused thiopyrylium salts was synthesized from diarylthioethers that contain formyl groups via an intramolecular Friedel-Crafts cyclization. The reaction, promoted by a Lewis or Brønsted acid, afforded the new thiopyrylium salts in good yield. Kinetic investigations and density functional theory calculations were used to explore the mechanism of the reaction. The electronic structures of the thiopyrylium salts were examined by UV-vis absorption spectroscopy, which afforded insight into the electronic transitions within these molecules.

Reaction of ketone hydrazones with TeCl4: isolation and reactions of novel divinyl telluride.

The reaction of acetophenone hydrazones with TeCl4 in the presence of DBU gave a mixture of divinyl ditellurides and divinyl tellurides, which easily reacted with Cu powder in refluxing toluene to afford divinyl tellurides in good yields. The reaction of divinyl tellurides with bromine (1.2 eq.) gave the corresponding tellurium dibromide rather than the addition of the double bond whereas 3 molar amount of bromine gave excess brominated and oxidized products. The reaction of divinyl tellurides with 2-(trimethylsilyl)phenyl triflate in the presence of CsF gave (E)-2-alkenyldiaryl tellurides in good yields.

Synthesis and Properties of Thiophene-Fused Thiopyrylium Salts.

A new family of thiophene-fused thiopyrylium salts has been synthesized via Lewis-acid-induced Rieche formylation, followed by an intramolecular Friedel-Crafts cyclization of a series of diarylthioethers. Moreover, in the case of diarylthioethers that bear formyl groups, Lewis-acid-promoted intramolecular cyclizations afforded novel thiophene-fused bisthiopyrylium salts in good yield. The electronic structures of the new compounds were determined experimentally by NMR and UV-vis absorption spectroscopy and theoretically investigated by density functional theory calculations. The results of our examinations revealed effective conjugation of the π-electrons over the entire linearly fused heteroacene framework.

Acute progressive bilateral carpal tunnel syndrome associated with remitting seronegative symmetrical synovitis with pitting edema syndrome: A case report.

The association between carpal tunnel syndrome (CTS) and remitting seronegative symmetrical synovitis with pitting edema (RS3PE) syndrome, an elderly onset rheumatic disease, is not fully understood. Here, we describe a case of acute CTS caused by RS3PE syndrome. An 84-year-old man visited the hospital with sudden onset of severe neuralgia in the median nerve and pitting edema in both hands. Computed tomography showed low-density areas around the flexor tendons and median nerve compression in the carpal tunnel. Rapidly progressing intolerable neuralgia and paralysis required urgent carpal tunnel release in the left hand. After surgery, we considered the possibility of RS3PE syndrome and started the administration of prednisolone. The pitting edema and neuralgia improved. In this case, imaging and intraoperative findings suggest that the effusion generated from flexor tenosynovitis associated with RS3PE syndrome increased the internal pressure in the carpal tunnel rapidly, which led to acute CTS and urgent surgery.

Buchwald-Hartwig Amination of Phosphinines and the Effect of Amine Substituents on Optoelectronic Properties of the Resulting Coupling Products.

The Buchwald-Hartwig amination of a phosphinine bearing a bromophenyl moiety was carried out using a dinuclear Ni catalyst. A variety of monoarylamines, diarylamines, and alkylamine, as well as heterocycles, were successfully converted into novel phosphinines bearing amine units. The photophysical properties of these novel phosphinines were examined, including the substituent-dependent absorption/emission features and intramolecular charge-transfer interactions.

2,5-Diaryltellurophenes: Effect of Electron-Donating and Electron-Withdrawing Groups on their Optoelectronic Properties.

The transformation of 1,2-bis(1-arylvinyl)ditellurides into 2,5-diaryltellurophenes by sequential ditelluride exchange and thermal intramolecular cyclization reactions is presented, and the optoelectronic properties of a series of 2,5-diaryltellurophenes with both electron-donating and electron-withdrawing aryl substituents are disclosed. Furthermore, the multicolored emissive tellurophenes in solution at room temperature have been demonstrated.

Small fluorescent molecules for monitoring autophagic flux.

We have developed two types of fluorescent probes, DALGreen and DAPGreen, for monitoring autophagy, that exhibit fluorescence upon being incorporated into autophagosomes. DALGreen enhances its fluorescence at acidic pH, which is favorable for monitoring late-phase autophagy, whereas DAPGreen remains fluorescent with almost constant brightness during the autophagic process. With these probes that stain autophagosomes as they are being formed, the real-time change of autophagic phenomena of live cells may be traced, which is an advantage over conventional approaches with small molecules that stain mature autophagosomes. The use of both dyes allows monitoring of the membrane dynamics of autophagy in any type of cell without the need for genetic engineering, and therefore, will be useful as a tool to study autophagic phenomena.

Live Cell Imaging of Mitochondrial Autophagy with a Novel Fluorescent Small Molecule.

There has been a growing interest in mitophagy, mitochondria-selective autophagy, which plays an essential role in maintaining intracellular homeostasis. We have developed a small-molecule fluorescent probe, Mtphagy Dye, for visualizing mitophagy, which was readily synthesized from a known perylene derivative, perylene-3,4-dicarboxylic anhydride. Mtphagy Dye has suitable fluorescent properties for detecting mitochondrial acidification during mitophagy in the long-wavelength region that does not damage mitochondria. Using Mtphagy Dye, we were able to visualize mitophagy with both cases of Parkin-dependent and -independent HeLa cells.

Stable 1H-Benzo[c]thio- and 1H-Benzo[c]selenophen-2-ium Tetrafluoroborates: Insight into Electronic Structures, Electrochemical Behavior, and Reactivity.

The synthesis of 1H-benzo[c]thio- and 1H-benzo[c]selenophen-2-ium tetrafluoroborates by the reaction of triphenylcarbenium tetrafluoroborate with 1-ethylidene-1,3-dihydrobenzo[c]thiophene or 1-ethylidene-1,3-dihydrobenzo[c]selenophene, respectively, is reported. The electronic structure of these novel 1H-benzo[c]chalcogenophenium salts was examined on the basis of their electronic spectra, whereby transitions were assigned in agreement with theoretical calculations. Electrochemical measurements revealed irreversible one-electron reduction waves for these 1H-benzo[c]chalcogenophenium salts.

First Isolation of Bicyclic Ditellurides from the Reaction of Camphor Hydrazone with Tellurium Tetrachloride.

Reaction of camphor hydrazone with TeCI4 under basic conditions gave an isomeric mixture of vinyl ditelluride and Wagner-Meerwein rearranged ditelluride. Initially formed tellurocamphor enolized and oxidized to give vinyl telluride, whereas tellurocamphor complexed with TeC4 to afford carbocation, which rearranged in a Wagner-Meerwein manner to afford the rearranged ditelluride. Photolysis of ditelluride in methyl methacrylate solution gave the radical polymerization product, PMMA, in which ditelluride acted as a radical initiator.

One-pot synthesis of dibenzo[b,h][1,6]naphthyridines from 2-acetylaminobenzaldehyde: application to a fluorescent DNA-binding compound.

Dibenzo[b,h][1,6]naphthyridines were synthesized in one pot by reacting 2-acetylaminobenzaldehyde with methyl ketones under basic conditions via four sequential condensation reactions. This method was also applied to the synthesis of 1,2-dihydroquinolines. 6-Methyl-1,6-dibenzonaphthyridinium triflates showed strong fluorescence, and the fluorescence intensities were changed upon intercalation into double-stranded DNA.

Tandem carbon-carbon bond insertion and intramolecular aldol reaction of benzyne with aroylacetones: novel formation of 4,4'-disubstituted 1,1'-binaphthols.

An efficient route to 4-aryl-2-naphthols from arynes and aroylacetones was developed by carbon-carbon bond insertion followed by an intramolecular aldol reaction and dehydration. Benzyne derived from 2-(trimethylsilyl)phenyl triflate reacted with benzoylacetones in refluxing acetonitrile to give 4-aryl-2-naphthols and 3-aryl-1-naphthols.

Reaction of arynes with amino acid esters.

An efficient route to a variety of 2-phenylindolin-3-ones from amino acid methyl esters has been developed. The reaction of amino acid methyl esters with benzyne prepared from 2-(trimethylsilyl)phenyl triflate and CsF gave 2-phenylindolin-3-ones in moderate to good yields.

Synthesis and properties of fluorescence probe for detection of peroxides in mitochondria.

In this study, a new type of fluorescence probe, diphenylpyrenylphosphine-conjugated alkyltriphenylphosphonium iodide which was accumulated in mitochondria, has been synthesized. This probe was detected peroxide in living cell. Comparison of the reactivity toward several peroxide indicated that the probe was existed in mitochondrial membrane. Using this probe, generation of peroxide in mitochondria of living cell was successfully visualized.

Reaction of benzyne with salicylaldehydes: general synthesis of xanthenes, xanthones, and xanthols.

The reaction of salicylaldehydes with benzyne prepared from o-trimethylsilyphenyl triflate and CsF gave xanthenes and xanthones. When the reaction was carried out under basic conditions, 9-hydroxyxanthenes (xanthols) were obtained in good yields.

Synthesis and reaction of alpha-dithiolactone.

Treatment of di-tert-butylthioketene S-oxide (5 a) with Lawesson reagent at room temperature resulted in the formation of 3,3-di-tert-butylthiirane-2-thione (4 a) in high yield. The oxidation of 4 a with mCPBA (mCPBA=m-chloroperbenzioc acid) gave 3,3-di-tert-butylthiirane-2-thione S-oxide (6) almost quantitatively. The reactions of 4 a with dimethyl acetylenedicarboxylate (DMAD) and benzyne afforded dimethyl 2-(2,2,4,4-tetramethylpentan-3-ylidene)-1,3-dithiole-4,5-dicarboxylate (13) and 2-(2,2,4,4-tetramethylpentan-3-ylidene)benzo[d][1,3]dithiole (15), respectively, in high yields, suggesting that 4 a is an excellent 1,3-dipole. The reaction of 4 a with ethylenebis(triphenylphosphine)platinum (16) gave dithiolato-platinum complex (22) in high yield. The structure of 22 was determined by X-ray crystallographic analysis.

Reaction of thioketones with propiolic acids.

The reaction of adamantane-2-thione with propiolic acid afforded a novel type of cycloadduct, spiro[adamantane-2,2'-6'H-[1,3]-oxathiin]-6'-one (3a), in quantitative yield. The reaction of thiobenzophenone with propiolic acid gave 2,2-diphenyl-6'H-[1,3]-oxathiin]-6'-one and 4-phenyl-3-thia-3,4-dihydronaphthoic acid in 34% and 35% yields, respectively. The reaction might proceed through a concerted process, as confirmed by kinetics. The reaction of adamantane-2-thione with 2-butynoic acid or phenylpropiolic acid gave the corresponding adducts regioselectively. Interestingly, only one isomer was obtained by the reaction of thiofenchone with propiolic acid, suggesting that the reaction proceeded diastereospecifically. Oxidation of adducts by dimethyldioxirane or m-chloroperoxybenzoic acid gave the corresponding sulfoxides and sulfones. The sulfoxides were thermally decomposed to give disulfide or another type of 1,3-oxathiin-6-one.