Cytochrome P450 (CYP) arachidonic acid epoxygenase 2J2 converts arachidonic acid to four regioisomeric epoxyeicosatrienoic acids, which exert diverse biological activities in cardiovascular system and endothelial cells. However, it is unknown whether this enzyme highly expresses and plays any role in cancer. In this study, we found that very strong and selective CYP2J2 expression was detected in human carcinoma tissues in 101 of 130 patients (77%) as well as eight human carcinoma cell lines but undetectable in adjacent normal tissues and nontumoric human cell lines by Western, reverse transcription-PCR, and immunohistochemical staining. In addition, forced overexpression of CYP2J2, and CYP BM3F87V or addition of epoxyeicosatrienoic acids (EET) in cultured carcinoma cell lines in vitro markedly accelerated proliferation by analyses of 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide, cell accounts, and cell cycle analysis, and protected carcinoma cells from apoptosis induced by tumor necrosis factor A (TNF-A) in cultures. In contrast, antisense 2J2 transfection or addition of epoxygenase inhibitors 17-ODYA inhibited proliferation and accelerated cell apoptosis induced by TNF-A. Examination of signaling pathways on the effects of CYP2J2 and EETs revealed activation of mitogenactivated protein kinases and PI3 kinase-AKT systems and elevation of epithelial growth factor receptor phosphorylation level. These results strongly suggest that CYP epoxygenase 2J2 plays a previously unknown role in promotion of the neoplastic cellular phenotype and in the pathogenesis of a variety of human cancers. (Cancer Res 2005; 65(11): 4707-15)
PBDTBO, a conjugated polymer comprising benzo[1,2-b:4,5-b']dithiophene (BDT) and 5,6-bis(octyloxy)benzo[c][1,2,5]oxadiazole (BO) units, exhibits a deep HOMO energy level of -5.27 eV and excellent solubility. A device incorporating PBDTBO and [6,6]-phenyl-C(61)-butyric acid methyl ester (1:1, w/w) exhibited a power conversion efficiency of 5.7%.
A cluster of cases of pulmonary hemosiderosis among infants was reported in Cleveland, Ohio, during 1993 and 1994. These unusual cases appeared only in infants ranging in age from 1 to 8 months and were characterized by pulmonary hemorrhage, which caused the babies to cough up blood. A case-control study identified major home water damage (from plumbing leaks, roof leaks, or flooding) as a risk factor for development of pulmonary hemorrhage in these infants. Because of an interest in the possibility that trichothecene mycotoxins might be involved in this illness, a number of isolates ofStachybotrys chartarum were grown in the laboratory on rice, and extracts were prepared and analyzed both for cytotoxicity and for specific toxins. Two isolates of Memnoniella echinata, a fungus closely related to S. chartarum, were also included in these studies. S. chartarum isolates collected from the homes were shown to produce a number of highly toxic compounds, and the profiles of toxic compounds from M. echinata were similar; the most notable difference was the fact that the principal metabolites produced by M. echinatawere griseofulvins.
This study shows that carotid intima-media thickening, but not carotid atherosclerotic plaque, is positively associated with ARD. Further studies to explore the underlying mechanism are awaited.
We synthesized and characterized a series of novel twodimensional Se-atom-substituted donor (D)−π-acceptor (A) conjugated polymersPBDTTTBO, PBDTTTBS, PBDTTSBO, PBDTSTBO, PBDTTSBS, PBDTSTBS, PBDTSSBO, and PBDTSSBSfeaturing benzodithiophene (BDT) as the donor, thiophene (T) as the π-bridge, and 2,1,3benzooxadiazole (BO) as the acceptor with different number of Se atoms at different π-conjugated locations, including the π-bridge, side chain, and electron-withdrawing units. We then systematically investigated the effect of different locations and the number of Se atoms in these two-dimensional conjugated polymers on the structural, optical, and electronics such as bandgap energies of the resulting polymers, as determined through quantumchemical calculations, UV−vis absorption spectra, and grazing-incidence Xray diffraction. We found that through the rational structural modification of the 2-D conjugated Se-substituted polymers the resulting PCEs could vary over 3-fold (from 2.4 to 7.6%), highlighting the importance of careful selection of appropriate chemical structures such as the location of Se atoms when designing efficient D−π-A polymers for use in solar cells. Among these tested BO-containing polymers, PBDTSTBO that has moderate band gaps and good open-circuit voltages (up to 0.86 V) when mixed with PC 71 BM (1:2, w/w) provided the highest power conversion efficiency (7.6%) in a single-junction polymer solar cell, suggesting that these polymers have potential applicability as donor materials in the bulk heterojunction polymer solar cells.
We have used Stille coupling polymerization to synthesize a series of new crystalline low–band gap conjugated polymersPTHBO, PBTTBO, and PTTTBOconstituting mainly electron-rich thiophene (TH), 2,2′-bithiophene (BT), and thieno[3,2-b]thiophene (TT) units in conjugation with electron-deficient 2,1,3-benzooxadiazole (BO) moieties. All of these polymers exhibited (i) sufficient energy offsets with respect to those of fullerenes to allow efficient charge transfer and (ii) low-lying highest occupied molecular orbital (HOMO, −5.47 eV). These polymers exhibited excellent thermal stability, high crystallinity, and broad spectral absorptions. As a result, bulk heterojunction photovoltaic devices derived from these polymers and fullerenes provided open-circuit voltages (V oc) as high as 1.02 V. In particular, the photovoltaic device comprising the PTTTBO/PC61BM (1:1) blend system and 1,8-diiodooctane (DIO, 0.5 vol %) as an additive exhibited excellent performance, under AM 1.5 G irradiation (100 mW cm–2), with a value of V oc of 0.85 V, a short-circuit current density (J sc) of 11.6 mA cm–2, a fill factor (FF) of 0.54, and a promising power conversion efficiency (PCE) of 5.3%.
Molecular engineering of conjugated polymers for tuning their energy bands is an important process in the quest for highly efficient bulk heterojunction (BHJ) polymer photovoltaic devices. One effective approach is to construct a conjugated polymer by conjugating two chemical units possessing different electron donating (donor) and accepting (acceptor) capabilities. Conjugated copolymers featuring donoracceptor (D/A) subunits are promising materials for solar cell applications because of their tunable energy bands and solubility that can be tailored to the performances of the photovoltaic devices. Under proper processing conditions, the conjugated polymers with rigid and planar D/A segments can undergo self-assembly to form crystalline structures that improve charge carrier mobility and provide better resistance to the permeation of water and oxygen compared to amorphous polymers. Conjugated polymers withD/A structure have been investigated thoroughly over the last few years. In this highlight, we present an overview of recent developments in BHJ organic photovoltaics employing D/A crystalline copolymers as active layer materials for photon-to-electron conversion, with particular emphasis on crystalline D/A polymers featuring newly developed acceptor structures, including thieno [3,4-c]pyrrole-4,6-dione, diketo-pyrrole-pyrrole, bithiazole, thiazolothiazole and thieno[3,2-b]thiophene moieties, and conclude with future perspectives.
We used Stille coupling of electron-rich benzo[1,2b:4,5-b′]dithiophene (BDT) presenting conjugated alkylthiophene (T), alkylphenyl (P), or alkylfuran (F) side chains with electrondeficient alkoxy-modified 2,1,3-benzooxadiazole (BO) moieties to obtain a series of two-dimensional, conjugated, D−π−A polymers (PBDTTBO, PBDTPBO, and PBDTFBO). The side chains of the BDT units altered the solubility, conformations, and electronic properties of the synthesized conjugated polymers, allowing tuning of their photovoltaic properties when blended with fullerenes. Density functional theory calculations revealed that the presence of these side chain groups on the BDT donor units affected the torsion angles between the side chain groups and the conjugated main chains but resulted in only slightly different energy levels for the highest occupied molecular orbitals for these polymers, consistent with results obtained experimentally using cyclic voltammetry. These polymers displayed excellent thermal stabilities (5 wt % degradation temperatures: >330°C) and broad spectral absorptions (from 450 to 700 nm). Transmission electron microscopy images revealed that the morphologies of active layers comprising these two-dimensional conjugated polymers and the fullerene derivative PC 71 BM did, however, vary substantially depending on the structure of the side chains that affects the solubility of the polymers. As a result, the efficiencies of photovoltaic devices incorporating PBDTFBO, PBDTPBO, or PBDTTBO polymers and PC 71 BM varied greatly, from 3.6 to 5.9%. When using 1-chloronaphthalene (1 vol %) or 1,8-diiodooctane (1 vol %) as an additive for processing the active layer, the power conversion efficiencies (PCEs) of photovoltaic devices incorporating blends of PBDTFBO, PBDTPBO, or PBDTTBO and PC 71 BM (1:2) improved to 5.4, 6.4, and 7.4%, respectively, due to their optimized morphologies, with the PCE of 7.4% being among the highest values reported for conjugated polymers involving BO moieties. Thus, the photovoltaic properties of these conjugated polymers were highly tunable through slight modifications of their side chain structures.
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