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Septic shock is characterized by dysregulated vascular permeability. We hypothesized that the vascular permeability of endothelial cells (ECs) would be regulated by serotonin via serotonin-Rho-associated kinase (ROCK) signaling. We aimed to determine the impact of 5-hydroxyindoleacetic acid (5-HIAA) on septic shock as a novel biomarker. Plasma 5-HIAA levels and disease severity indices were obtained from 47 patients with sepsis. The association between 5-HIAA levels and severity indices was analyzed. Permeability upon serotonin stimulation was determined using human pulmonary microvascular ECs. 5-HIAA were significantly higher in septic shock patients than in patients without shock or healthy controls (p = 0.004). These elevated levels were correlated with severity indexes (SOFA score [p, Scientific Reports, 11, art. no. 14146; 2021

In this work, tetraphenyldiphenoquinone (DPQ) was synthesized and characterized by single crystal structure analysis, ultraviolet–visible spectroscopy (UV–Vis) and cyclic voltammetry (CV). DPQ–based organic field-effect transistors (OFET) were fabricated with bottom contact configuration using bare SiO2/Si substrate and hexamethyldisilazane (HMDS) treated substrate, respectively. The HMDS-treated device showed hole mobility of 8.7 × 10−7 cm2 V−1 s−1, current on/off ratio of 1.2 × 102 and threshold voltage of −39 V. Devices with bare substrate showed no FET behaviors. Finally, film morphology was investigated by X-ray diffraction (XRD) analyses and the results showed that the HMDS treatment exhibits better crystallinity of DPQ on the film thus obtaining FET performance.

In this work, 3’-flouro-2,2',6,6'-tetraphenyl-4,4'-dipyranylidene (3FDP) was originally synthesized and investigated with density functional theory (DFT) calculations, ultraviolet–visible spectroscopy (UV–Vis) and cyclic voltammetry (CV) in comparison with 2,2',6,6'-tetraphenyl-4,4'-dipyranylidene (DP) and 4’-flouro-2,2',6,6'-tetraphenyl-4,4'-dipyranylidene (4FDP). 3FDP-based organic field-effect transistors (OFETs) were fabricated with bottom contact configuration on bare SiO2/Si substrate, 1,1,1,3,3,3-hexamethyldisilazane (HMDS) and octadecyltrichlorosilane (OTS) treated substrate, respectively. The HMDS-treated device showed highest mobility of 4 × 10−4 cm2 V−1 s−1, on/off ratio of 4 × 103 and threshold voltage of −10 V. Finally, vacuum deposited 3FDP films morphology was investigated by X-ray diffraction (XRD) analyses and the results showed higher crystallinity of HMDS-treated 3FDP film compared to the OTS-treated film, leading to a better FET performance.

Lung abscess is usually treated with long-term antibiotic therapy. Due to the lack of a safe and easy drainage technique, drainage is only applied in refractory cases. We herein describe three cases in which drainage was successfully performed by endobronchial ultrasonography using a modified guide sheath. This procedure may have advantages in the detection of causative pathogens and early infection source control, and may therefore lead to the appropriate selection of antibiotics and reduce the duration of antibiotic therapy., Internal Medicine, 58(1), pp.97-100; 2019

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Corynebacterium ulcerans infection was recently recognized as a zoonosis. We present 2 cases of severe pneumonia complicated by diffuse pseudomembrane formation on the bronchus caused by C. ulcerans?producing diphtheria toxin. Our purpose is to alert medical professionals to the virulence of Corynebacterium species other than C. diphtheriae., Emerging Infectious Diseases, 24(3), pp.588-591; 2018

Mycobacterium tuberculosis (M. tuberculosis) produces a diverse range of antigenic proteins in its dormant phase. The cytokine profiles of CD4+ T cell responses, especially subsets other than Th1 type (non-Th1 type), against these latency-associated M. tuberculosis antigens such as α-crystallin (Acr), heparin-binding hemagglutinin (HBHA), and mycobacterial DNA-binding protein 1 (MDP-1) remain elusive in relation to the clinical stage of M. tuberculosis infection. In the present study, peripheral blood mononuclear cells (PBMCs) collected from different stages of M. tuberculosis-infected cases and control PBMCs were stimulated with these antigens and ESAT-6/CFP-10. Cytokine profiles of CD4+ T cells were evaluated by intracellular cytokine staining using multicolor flow cytometry. Our results demonstrate that Th1 cytokine responses were predominant after TB onset independent of the type of antigen stimulation. On the contrary, non-Th1 cytokine responses were preferentially induced by latency-associated M. tuberculosis antigens, specifically IL-10 response against Acr in latent M. tuberculosis infection. From these results, we surmise a shift in the CD4+ T cell response from mixed non-Th1 to Th1 dominant type during TB progression.

Trifluoromethylphenyl-substituted phthalimide derivatives favorably form triboluminescence (TL) active noncentrosymmetric crystals. Oligothienyl-, oligophenyl-, and naphthyl-substituted phthalimide derivatives were successfully developed as a series of metal free TL compounds. X-ray crystal structure analyses of bithienyl and naphthyl derivatives revealed noncentrosymmetric layer structures in the same direction. Introduction of suitable electron rich π-units such as thienyl groups enhances their photoluminescence and TL characteristics, and the colors can be also controlled in the visible region. A rigid naphthyl-substituted imide derivative exhibits extremely high TL performance.

Background: A pneumatocele is a transient thin-walled lesion and rare complication in adult pneumonia. A variety of infectious pathogens have been reported in children with pneumatoceles. We report the first case of adult pneumonia with pneumatocele formation that is likely caused by Streptococcus pyogenes and coinfection with influenza A virus. Case presentation: A 64-year-old Japanese man presented with a one-week history of fever, sore throat, and arthralgia. He was referred to our university hospital for respiratory distress. He required mechanical ventilation in the intensive care unit (ICU). Bacterial culture detected S. pyogenes in the bronchoscopic aspirates, which was not detected in blood. Although a rapid influenza antigen test was negative, an influenza A polymerase chain reaction (PCR) test was positive. Therefore, he was diagnosed with coinfection of influenza A and group A streptococcus (GAS) pneumonia complicated by probable streptococcal toxic shock syndrome. A chest radiograph on admission showed diffuse patchy opacification and consolidation in the bilateral lung fields. Multiple thin-walled cysts appeared in both middle lung fields on computed tomography (CT). On the following day, the bilateral cysts had turned into a mass-like opacity. The patient died despite intensive care. An autopsy was performed. The pathology investigation revealed multiple hematomas formed by bleeding in pneumatoceles. Conclusions: There have been no previous reports of a pneumatocele complicated by S. pyogenes in an adult patient coinfected with influenza A. Further molecular investigation revealed that the S. pyogenes isolate had the sequence type of emm3., BMC Infectious Diseases, 20(1), art.no.892; 2020

Impaired efferocytosis is a key mechanism of inflammatory lung diseases, including chronic obstructive pulmonary disease and cystic fibrosis.Cigarette smoking activates RhoA and impairs efferocytosis in alveolar macrophages, but the mechanism has not been fully elucidated. We investigated the role of endoplasmic reticulum (ER) stress induced by cigarette smoking in the disruption of efferocytosis.Both tunicamycin (10 μg/ml) and thapsigargin (0.1 and 1 μM), which are ER stress inducers, suppressed efferocytosis in J774 cells,and a Rho-associated coiled-coil-forming kinase (ROCK) inhibitor (Y27632) reversed this effect.We validated the effect of tunicamycin on efferocytosis in experiments using RAW264.7 cells. Then, we investigated the role of the unfolded protein response (UPR) in efferocytosis impaired by ER stress. A PERK inhibitor (GSK2606414) restored the efferocytosis that had been impaired by TM, and an eIF2α dephosphorylation inhibitor (salubrinal) suppressed efferocytosis. Cigarette smoke extract (CSE) induced ER stress in J774 macrophages and RhoA activation in J774 cells, and the CSE-induced ROCK activity was successfully reversed by GSK2606414 and tauroursodeoxycholic acid. Finally, we confirmed that ER stress suppresses efferocytosis in murine alveolar macrophages and that GSK2606414 could rescue this process. These data suggest that cigarette smoke-induced ER stress and the UPR play crucial roles in RhoA activation and suppression of efferocytosis in the lung., Scientific Reports, 10(1), art.no.12620; 2020

A Pd-catalyzed single-step C-H arylation of dioxythiophene derivatives bearing unprotected reactive functional groups (-OH, -COOH, -N3) in a phosphine-free manner has been developed. Various dioxythiopene-based oligoarenes with extended π-conjugation are obtained with good yields (up to 90%). These oligoarenes display suitable optical properties (absorption and emission maxima, quantum yields) and contain reactive functional groups suitable for further conjugations with bioactive molecules. This new methodology is step economical (fewer synthetic steps) and environmentally friendly (no toxic metal-containing by-products) and the oligoarenes synthesized are potentially applicable for bio-labeling, bioimaging, and biosensing.

We have developed methods for installing aryl substituents directly on the phosphino groups of the 1,3-diphosphacyclobutane-2,4-diyl system. The aryl substituents tuned the electronic and structural characteristics of the biradical unit both in solution and in the solid state. 1-tert-butyl-2,4-bis(2,4,6-tri-tert-butylphenyl)-1,3-diphosphacyclobuten-4-yl anion, prepared from phosphaalkyne (Mes*C≡P; Mes* = 2,4,6-tBu3C6H2) and t-butyllithium, was allowed to react with an electron-deficient N-heterocyclic reagent. The corresponding N-heteroaryl-substituted P-heterocyclic biradicals were produced via SNAr reactions. Biradicals bearing perfluorinated pyridyl substituents exhibited photoabsorption properties comparable to those of previously reported derivatives because the highest occupied and lowest unoccupied molecular orbit levels were reduced by a similar amount. In contrast, the triazine substituent reduced the band gap of the biradical unit, and the large red shift in the visible absorption and high oxidation potential were further tuned via subsequent SNAr and Negishi coupling reactions. The amino-substituted triazine structure provided a strongly electron-donating biradical chromophore, which produced unique p-type semiconducting behavior even though there was no obvious π-overlap in the crystalline state. The single-electron transfer reaction involving Mes*C≡P, phenyllithium, and iodine afforded 1,3-diphenyl-2,4-bis(2,4,6-tri-tert-butylphenyl)-1,3-diphosphacyclobutane-2,4-diyl via the intermediate P-heterocyclic monoradical. The tetraaryl-substituted symmetric biradical product was used to determine the electron density distribution from the X-ray diffraction data. The data show highly localized radicalic electrons around the skeletal carbon atoms, moderately polarized skeletal P-C bonds in the four-membered ring, and no covalent transannular interaction.

Although IFN-γ release assays (IγRAs) provide increased specificity over tuberculin skin tests, the early and sensitive detection of reactivation of latently infected Mycobacterium tuberculosis is required to control tuberculosis (TB). Recently, a multicolor flow cytometry has been developed to study CD4+ T cell cytokine responses (IFN-γ/IL-2/TNF-a) to purified protein derivatives (PPD) and M. tuberculosis-specific antigens (ESAT-6/CFP-10) and provided useful information regarding anti-TB immunity. However, the diagnostic relevancy remains uncertain. Here, we analyzed three additional CD4+ T cell cytokine responses (IL-10/IL-13/IL-17) to latent mycobacterial antigens (a-crystallin, methylated heparin-binding hemagglutinin [HBHA], and mycobacterial DNA-binding protein 1 [MDP-1]) as well as PPD and ESAT-6/CFP-10 in 12 IGRA+ TB cases and 8 healthy controls. No significant difference in IFN-γ response was observed between TB cases and controls, which was likely due to the high variation among the individuals. However, we found a significant increase over healthy controls in (i) the IL-2 response to HBHA in recovery stage TB cases, (ii) the number of M. tuberculosisspecific polyfunctional CD4+ T cells in on-treatment and recovery stage cases, and (iii) the IL-17 response to HBHA and MDP-1 in on-treatment and recovery stage cases. These results suggest that a combination of these T cell cytokine parameters could aid in accurate diagnosis of latent TB infection., Japanese Journal of Infectious Diseases, 66(3), pp.207-215; 2013

This study investigated the Ca2+-activated K+ currents (KCa) of Merkel cells, which were freshly dissociated from rat glabrous skin, using whole-cell and excised patch configurations of the patch clamp technique. With the whole-cell voltage clamp, the application of slow (50 mV/s) voltage ramps from -100 to +100 mV produced an N-shaped current-voltage (I-V) relationship. Maximum current activation occurred at +38.0 ± 10.6 mV (N = 14). Replacement of extracellular Ca2+ by Mg2+ and the addition of 2 mM EGTA abolished the N-shaped I-V relationship, and 1 mM TEA reduced it to < 40%. Using inside-out patches with symmetrical 150 mM KCl solutions, channels were observed with a slope conductance of 280 pS and a reversal potential of 0 mV. Reducing the [K+]o to 5 mM shifted the reversal potential, which was expected for a K+ selective channel. The channel open-state probability (Po) was increased by increasing cytosolic [Ca2+]i. Po also increased with depolarization. These data indicate the presence of large-conductance Ca2+-activated K+ (BKCa) channels in Merkel cells.

Nanostructures of poly(3,4-ethylenedioxythiophene) (PEDOT) are assembled by using an anodic aluminum oxide template directly fabricated on gold-coated silicon wafers. Inside these templates, PEDOT and hydroxy functionalized PEDOT form tubes. On the other hand, alkyl- and perfluoro-functionalized PEDOTs assembled as nanorods. This approach allows a platform to understand the molecular and nanostructural effect on the surface wettability of these materials. In the water/air interface, the contact angle of water droplet (CAwater) for the smooth alkyl-functionalized PEDOT films increases when alkyl chain gets longer. In contrast, the contact angle reachs saturation at 130° with alkyl chain longer than ethyl in assembled nanorod arrays. It remains the same even in the case of perfluoro-functionalized PEDOT. Moreover, ethyl-functionalized PEDOT (PEDOT-C2) nanorods displays superoleophilicity and the oil deoplet cannot stay on the film in water. Based on the wettability studies, it is concluded that the nanostructures contribute predominantly for the surface wettability of these nanomaterials when the length of alkyl chain crosses certain threshold.

Light absorption from visible to NIR region is required to increase the photocurrent and to enhance the photo-energy conversion efficiencies in dye-sensitized solar cells (DSSCs). We have now developed novel thienopyrazine dye TP1 which has absorption up to 700 nm. Quinoxaline dye QX2 with absorption at shorter wavelengths than TP1 has been synthesized for comparisons. The power conversion efficiencies of DSSCs with TP1 and QX2 showed 4.4% and 3.2%, respectively. The absorption edge in IPCE of TP1 reached 800 nm and the open circuit voltage (Voc) of QX2 was high (0.77 V). To improve the device performances, QX2 was used as a co-adsorbent dye with TP1. In the mixed sensitizer based DSSC, a high power conversion efficiency of 6.2% was achieved due to the effective light harvesting and steric effect of QX2.

Photoinduced electron-transfer reaction of α-bromomethyl-substituted benzocyclic β-keto esters with tertiary amines was investigated. Debrominated β-keto esters and ring-expanded γ-keto esters were obtained as major products. On the basis of mechanistic experiments it was concluded that these products are formed via a reaction sequence of selective carbon–bromine bond cleavage and subsequent competitive hydrogen abstraction and Dowd–Beckwith ring-expansion of the resulting primary alkyl radicals. The characteristic product distribution observed for the type of amine used is rationalized on the basis of selective reaction pathways of generated radical intermediates that depend on the nature of the amine radical cations.

Organic field-effect transistors with hydrogen-bonded diketopyrrolopyrrole-thiophene co-oligomers were fabricated by a solution-process method with annealing at 200 °C, showing ambipolar charge-carrier transfer with field-effect mobilities up to μ(h) = 6.7 × 10(-3) cm(2) V(-1)s(-1) and μ(e) = 5.6 × 10(-3) cm(2) V(-1) s(-1).

Fused polycyclic indeno[1,2-b]fluorene derivatives with aryl substituents at the 6,12-positions have been prepared as a potential antiaromatic 20π electronic system. They showed strong absorptions in the visible region and amphoteric redox properties. The quinoid-type molecular structures were revealed by X-ray crystal-structure analysis, which indicated that the bond lengths of the quinoid unit depend on the aryl substituents. Whereas nucleus-independent chemical shift NICS(1) calculations indicate the antiaromatic nature of the s-indacene core, they have higher stability than substituted acene derivatives. The derivatives with difluorophenyl or anthryl groups were stable in solution. Vapor-deposited thin films showed ambipolar carrier transportation in the field-effect transistor devices.

Novel 2,6-diphenyl-4 H -pyranylidene derivatives were designed and synthesized as dyes for dye-sensitized solar cells (DSSC). Dyes 2a , b with a phenyl substituent showed high DSSC energy conversion efficiencies of 5.3% ( J sc = 10.3 mA/cm 2 , V oc = 0.72 V, FF = 0.72) and 4.7% ( J sc = 8.9 mA/cm 2 , V oc = 0.73 V, FF = 0.72) at 100 mW/cm 2 under simulated AM 1.5 G solar light conditions. These values are twice better than that of dye 1 without the phenyl substituent under the same conditions. Both the photocurrent density ( J sc ) and open circuit voltage ( V oc ) of DSSCs based on dyes 2a , b are increased compared with 1 . It can be attributed to their twisted structures, absorption abilities and proper energy levels. This result shows that the tetraphenylpyranylidene is a promising electron-donor unit for high-efficiency DSSCs.

A series of asymmetric N-phenyl imides with trifluoromethyl and pentafluorosulfanyl substituents at the terminal phenyl position have been prepared. They are colorless both in solution and the solid state, and they show blue emission in the solid state. X-ray crystal structure analysis of trifluoromethyl and pentafluorosulfanyl substituted derivatives revealed highly ordered noncentrosymmetric molecular arrangements with large net-dipole moments related to the piezoelectric behavior. XRD measurements of the powders afforded intense sharp reflection peaks, indicating formation of the lamellar ordering. By grinding with a spatula, their solids showed vivid blue triboluminescence.

Ladder-type heteroacenes based on indolodibenzothiophene have been synthesized. The route involved a regioselective twofold intramolecular acid-induced cyclization of the central bis(butylsulfinyl)...

We present a working example of phase recognition by lattice phonon Raman spectroscopy, a technique which has proved to be a powerful tool for identifying new polymorphs. The spectra show that a newly resolved triclinic structure of the organic semiconductor dibenzo-tetrathiafulvalene (DB-TTF) is one of its four polymorphic modifications, labeled the δ-phase, which was previously identified only from spectroscopic data. The now available XRD data allow for the computation of the minimum potential energy structure. Calculated density and energy of the triclinic polymorph are found to be very close to the previously identified β polymorph. These similarities account for the often encountered co-existence of the β and δ crystal phases.

A series of halogen and alkyl substituted diindenopyrazinediones and bis(dicyanomethylene) derivatives have been synthesized as new n-type organic semiconductors based on nitrogen-containing heterocycles. Halogen groups were introduced to improve the electron injection. Their crystal structures and solid physical properties are discussed. Alkyl groups were introduced to increase the solubility in organic solvents. Furthermore, hexanoyl groups were introduced by oxidation of alkyl groups to increase the solubility and electron affinity. Dicyanomethylene groups were also introduced to further enhance the electron-accepting properties. Drop-cast as well as vapour deposited thin films showed n-type FET properties.

Four novel 1,3-dithiol-2-ylidene dyes BDY-1, BDY-2, BDY-3, and BDY-4 were developed for dye-sensitized solar cells. Among these dyes, BDY-4 containing a 9,9-dibutyl-9H-fluorene spacer and a phenyl ...

Three new quinoxalinoTTF derivatives with methyl, trifluoromethyl and fluoro groups were synthesized and characterized by UV–vis absorption spectroscopy, differential scanning calorimetry, X-ray single crystal analysis, X-ray diffraction, and field-effect transistor (FET) characteristics. All of them have π-stacking structures in the single crystals. The quinoxalinoTTF derivative with trifluoromethyl groups exhibited an n-type FET, which is a rare example of n-channel FETs based on TTF derivatives. The highest electron mobility is 0.01 cm 2 V −1 s. The FET polarity was converted to p-channel from n-channel by replacing the trifluoromethyl groups with methyl groups. The hole mobility is as high as 0.2 cm 2 V −1 s. In contrast, the fluoro substituted derivative did not show FET properties due to the poorly ordered molecular arrangement.

A triphenylamine (TPA) dye with two hexyl groups at the opposable 3,3′-positions of a bithiophene linker (1a) was prepared and compared to a dye with a regio regular 4,3′-dihexylbithiophene unit (1b). The absorption spectrum of 1a showed a blue shift in comparison to 1b, suggesting the structure of 1a was twisted in comparison to 1b. The twisted structure agreed with the structure optimized by DFT calculations. By replacing one thiophene unit of 1a and 1b with a pyridine ring (2a and 2b, respectively), a further blue shift was observed. Dye-sensitized solar cells (DSSCs) were prepared from these dyes and a conventional Ru dye (N719). Under one sun conditions, DSSCs/2a showed comparable or higher open-circuit voltage (Voc) than did DSSCs/N719. The high Voc was attributed solely to long electron lifetime in the DSSCs/2a. A previous study has suggested that TPA dyes with long π-conjugation unit suffer from larger dispersion forces between the dyes and acceptors, I3− and/or I2, causing short electron lifetime...

A couple of naphthalenediimide 4 and 5 and series of perylenediimide derivatives 6–9 carrying TEMPO radical were prepared and their redox, FET, and magnetic properties were investigated. The radica...

2,2′-(1,4-Phenylene)bis(2,3-dihydro-1H-naphtho[1,8-de]-1,3,2-diazaboroine) [PND] and 2,2′-(4,4′-biphenylene)bis(2,3-dihydro-1H-naphtho[1,8-de]-1,3,2-diazaboroine) [BND] were synthesized and characterized by using differential scanning calorimetry (DSC) measurements, single crystal X-ray structure analysis, UV–vis absorption and electrochemical measurements, thin-film X-ray diffraction (XRD) and AFM studies. Organic field-effect transistors (OFETs) were fabricated by vacuum deposition with a bottom contact geometry using Au electrodes. Annealing treatment optimizes the organic active layer and increases the charge carrier mobility. Field-effect mobilities of 7.2 × 10 −3 for PND and 4.1 × 10 −4 cm 2 V −1 s −1 for BND were found.

Dibenzotetrathiafulvalene (DBTTF) analogs containing fused thiophene spacers were synthesized and characterized by cyclic voltammetry, UV―vis absorption spectroscopy, quantum chemical calculations, single-crystal X-ray analysis, overlap integral calculations, field-effect transistor (FET) characteristics, X-ray diffraction, and atomic force microscopy (AFM). The single-crystal X-ray analysis revealed that the DBTTF with a thieno[3,2-b]thiophene spacer has a molecular geometry with short intramolecular S···S contacts and a herringbone packing structure with short intermolecular S···S contacts leading to large two-dimensional overlap integrals. The molecule afforded a crystalline thin film with well-ordered molecular orientation corresponding to the single-crystal structure. The FET device based on this molecule exhibited good mobility of 0.29 cm 2 V ―1 s ―1 and low threshold voltage of ―0.3 V The effects of the thiophene spacer on the properties, structure, and FET performances were investigated here.

The crystal structure of the 2:1 co-crystal of 1,2,5-thiadiazole-3,4-dicarboxylic acid and 4,4′-bipyridine, (C4H2N2O4S)2·C10H8N2, has been determined by X-ray diffraction at the monoclinic space group C2/c with cell parameters of a = 21.388(7) A, b = 6.735(2) A, c = 14.877(5) A, β = 110.431(3)°, and Z = 4. There are one molecule of thiadiazole and a half molecule of bipyridine in the asymmetric unit. The dihedral angle between the pyridine ring planes is 40.5(3)°. Two intramolecular O–H···N [2.730(7) A] and O–H···O [2.433(6) A] hydrogen bonds are observed in the thiadiazole molecule. In the crystal structure, the molecules form a unique two-dimensional ladder-type network linked by intermolecular O–H···N [2.704(4) A] hydrogen bonds and S···O [3.100(5) A] heteroatom interactions. In the crystal structure of the title co-crystal, the molecules form a unique two-dimensional ladder-type network linked by intermolecular O–H···N hydrogen bonds and S···O heteroatom interactions.

Nitrogen heterocycles containing C=N double bonds have electron-accepting properties and can be used as n-type semiconductors for organic field-effect transistors. Thiazole, benzothiadiazole, pyraz...