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1.
Xenopus laevis melanophores express two melanopsins, Opn4x and Opn4m. We identified Opn4x immunoreactivity throughout the melanophore cytoplasm and in the cell membrane. The strongest immunopositivity for Opn4m was observed in the nuclear region, and no labeling was seen in the cell membrane. This immunodistribution suggests Opn4x as the functional photopigment. In X. laevis melanophores, light triggers pigment dispersion and clock gene induction at blue wavelength, which maximally activates melanopsins. Although light stimulation activates phospholipase C and increases intracellular calcium and cGMP, this nucleotide does not participate in photo‐induced melanin dispersion. Nevertheless, the guanylyl cyclase activator YC‐1 stimulates Per1 expression, similar to blue light pulse, and the use of pharmacological inhibitors indicates the participation of the phosphoinositide cascade. Since cAMP levels does not change after blue light stimulation, the cAMP/PKA pathway most probably is not involved in blue light induction of Per in X. laevis melanophores. Given the localization of melanopsins and our pharmacological data, the light‐induced clock gene expression seems to be mediated by Opn4x through phosphoinositide cascade and rise in cGMP, thus leading to the reset of the biological clock in our model.  相似文献   

2.
Melanopsin is a G protein‐coupled receptor with a peak sensitivity in the blue part of the spectrum, which plays a key role in nonvisual light‐mediated signaling. Recently, its importance in forming visual pathway as well as its role in blood vessels photorelaxation was also revealed. Melanopsin was discovered in 1998 in Xenopus leavis. Since then, the melanopsin presence was demonstrated across the species. The existence of two melanopsin genes (opn4m and opn4x) as well as melanopsin isoforms resulting from alternative splicing contributes to the variety in melanopsin‐regulated processes. In this review, the diversity in melanopsin‐induced signaling, regulation of melanopsin activity by phosphorylation and regulation of melanopsin mRNA are discussed.  相似文献   

3.
We established a cell line (HEK‐hMel) expressing melanopsin in a tetracycline dependent manner to elucidate new aspects of melanopsin's light response. Different light stimuli were evaluated using FOS expression as response parameter. Immunoblotting was used to evaluate expression of melanopsin and FOS and qPCR to quantify FOS mRNA responses. The magnitude of the FOS response was found to correlate with the amount of melanopsin expressed by the cells, and a transient FOS mRNA induction followed by FOS protein still elevated after 24 h of illumination was revealed. Exposing the cells to darkness after light resulted in reduction of the response compared to exposure to light solely showing dependency on continuous light. Increasing irradiances of blue light (480 nm) up to 1011 quanta cm?2 s?1 elicited steep increases in FOS mRNA, while increases between 1012 and 5 × 1013 quanta  cm?2 s?1 resulted in equally high FOS expression. The HEK‐hMel cells were used to characterize facets of melanopsin's light‐induced FOS response not approachable in vivo. Novel information such as dependency of the FOS response on both melanopsin amount and light intensity in addition to a detailed time‐course of both FOS mRNA and protein were revealed.  相似文献   

4.
There is growing awareness that circadian clocks are closely related to the intracellular redox state across a range of species. As the redox state is determined by the exchange of the redox species, electrochemically controlled extracellular electron transfer (EC‐EET), a process in which intracellular electrons are exchanged with extracellular electrodes, is a promising approach for the external regulation of circadian clocks. Herein, we discuss whether the circadian clock can be regulated by EC‐EET using the cyanobacterium Synechococcus elongatus PCC7942 as a model system. In vivo monitoring of chlorophyll fluorescence revealed that the redox state of the plastoquionone pool could be controlled with EC‐EET by simply changing the electrode potential. As a result, the endogenous circadian clock of S. elongatus cells was successfully entrained through periodically modulated EC‐EET by emulating the natural light/dark cycle, even under constant illumination conditions. This is the first example of regulating the biological clock by electrochemistry.  相似文献   

5.
Abstract— In addition to the direct inhibitory effects of visible light (cool-white fluorescent, < 3500 lux) on growth and amino acid transport previously reported for cultures of the yeast Saccharomyces cereui-siae (strain Y185 rho+) grown at 12°C in medium containing glucose, yeast carbon base, KH2PO4, ammonium ion and proline, we have found evidence for endogenous, light-entrainable, self-sustaining circadian and ultradian oscillators underlying both cell division and transport activity. Diurnal light (? 3000 lux) cycles (LD), imposed on cultures previously grown in the dark, phased or synchronized cell number increase to a 24-h period with bud release being confined primarily to the dark intervals (although not necessarily every cell divided during any given division ‘burst’). The observed division or budding rhythm freeran with a circadian period (?26h) only approximating 24 h for a number of days in constant darkness (DD) following prior entrainment by LD, thereby implicating an endogenous circadian clock. Further, a similar light-entrainable circadian rhythm in the uptake of “C-histidine or 14C-lysine occurred in nondividing (or very slowly dividing) cultures during the “stationary” (infradian) phase of growth synchronized by a 24-h LD cycle and then released into DD for as long as 10 days. Some experiments revealed a bimodal (ultradian) periodicity in both LD and DD with secondary peaks or shoulders occurring at intervals of ?12h, corresponding approximately to subjective ‘dawn’ and ‘dusk’. Transport in cultures of the Y185 rho- petite mutant, which lacks cytochromes a/a3, b and cl, could not be synchronized by LD cycles, a finding that is consistent with the hypothesis that these chromophores may be primary photoreceptors for synchronization of rhythms in this microorganism.  相似文献   

6.
Visible‐light‐driven Ag/AgBr/TiO2/activated carbon (AC) composite was prepared by solgel method coupled with photoreduction method. For comparison, TiO2, TiO2/AC, and Ag/AgBr/TiO2 were also synthesized. Their characteristics were analyzed by XRD, SEM‐EDS, TG‐DSC and UV–vis techniques. Photocatalytic activity and antibacterial performance under visible‐light irradiation were investigated by ICP‐AES, ATR‐FT‐IR and spectrophotometry methods using methylene blue and Escherichia coli as target systems, respectively. The results showed that Ag/AgBr was successfully deposited on anatase TiO2/AC surface, and exhibited a distinct light absorption in the visible region. Ag/AgBr/TiO2/AC displayed excellent antibacterial performance both in dark and under visible‐light illumination. The growth of E. coli cell was inhibited in the presence of Ag/AgBr/TiO2/AC in dark. Moreover, upon visible‐light illumination, a significant damage of cell membrane was noticed. Ag/AgBr/TiO2/AC was also shown higher photocatalytic efficiency for methylene blue degradation than those of TiO2, TiO2/AC, and Ag/AgBr/TiO2. This is attributed to the synergetic effect between AC and Ag/AgBr/TiO2, of which AC acts as the role of increasing reaction areas, continuous enriching, and transferring the adsorbed MB molecules to the surface of supported photocatalysts, and the Ag/AgBr/TiO2 acts as a highly active photocatalyst for degrading MB molecules under visible‐light irradiation.  相似文献   

7.
Two aggregation‐induced emission active luminogens (TPE–pTPA and TPE–mTPA) were successfully synthesized. For comparison, another six similar compounds were prepared. Because of the introduced hole‐dominated triphenylamine (TPA), fluorene groups with high luminous efficiency, and unconjugated linkages, the π conjugation length of the obtained luminogens is effectively restricted to ensure their blue emission. The undoped organic light‐emitting diodes based on TPE–pTPA and TPE–mTPA exhibited blue or deep‐blue emissions, low turn‐on voltages (3 V), and high electroluminescence efficiencies with Lmax, ηC,max, and ηP,max values of up to 26 697 cd m?2, 3.37 cd A?1, and 2.40 Lm W?1.  相似文献   

8.
Bis(N‐(pyrrol‐2‐ylmethyl)‐N‐butyldithiocarbamato‐S,S′)copper(II) ( 1 ), bis(N‐(pyrrol‐2‐ylmethyl)‐N‐(2‐phenylethyl)dithiocarbamato‐S,S′)copper(II) ( 2 ), bis(N‐methylferrocenyl‐N‐(2‐phenylethyl)dithiocarbamato‐S,S′)copper(II) ( 3 ) and bis(N‐furfuryl‐N‐methylferrocenyldithiocarbamato‐S,S′)copper(II) ( 4 ) were prepared and characterized using elemental analysis and infrared and UV–visible spectroscopies. X‐ray diffraction (XRD) studies on 3 show that each copper centre adopts the square planar geometry by the coordination of four sulfur atoms of the metalloligand N‐methylferrocenyl‐N‐(2‐phenylethyl)dithiocarbamate. The Cu? S distances are symmetrical and are in the range 2.293–2.305 Å. The supramolecular architecture in complex 3 is sustained in the solid state by C? H???π, C? H???S, Fe???Fe and H???H interactions. Density functional theory calculations were carried out for 3 . Anion (F?, Cl?, Br? and I?) binding studies with complex 1 were performed using cyclic voltammetry. Copper sulfide, copper–iron sulfide‐ 1 and copper–iron sulfide‐ 2 nanoparticles were prepared from complexes 2 , 3 and 4 , respectively, and they were characterized using powder XRD, transmission electron microscopy (TEM) and energy‐dispersive X‐ray, UV–visible, photoluminescence and infrared spectroscopies. TEM images of copper–iron sulfide‐ 1 and copper–iron sulfide‐ 2 reveal that the particles are spherical and oval shaped, respectively. Photocatalytic activities of as‐prepared nanoparticles were studied by decolourization of methylene blue and rhodamine‐B under UV light. It was found that copper–iron sulfide degrades methylene blue and rhodamine‐B much better than does copper sulfide.  相似文献   

9.
Novel electrochromic polymers were prepared by the click postfunctionalization of poly(4‐azidomethylstyrene) with alkyne‐containing aromatic amine units in the presence of Cu(I) catalysts. Two kinds of aromatic amine units, tris(4‐alkoxyphenyl)amine and N,N,N′,N′‐tetraphenyl‐p‐phenylenediamine, were introduced into polystyrene side chains, which were completely characterized by gel permeation chromatography–multiangle light scattering, nuclear magnetic resonance, and infrared spectroscopies, and elemental analysis. Thermal analyses demonstrated the high stability with the decomposition temperatures exceeding 300 °C even after postfunctionalization. The UV–vis absorption spectra of the polymer thin films revealed negligible absorption in the visible region, as reasonably confirmed by visual observation. The polymer thin films were prepared by spray‐coating on an indium tin oxide‐coated glass plate. Cyclic voltammograms of these films exhibited anodic peaks ascribed to the oxidation of the side‐chain aromatic amine moieties. The tris(4‐alkoxyphenyl)amine unit displayed one‐step oxidation at 0.287 V (vs. Ag/AgCl), while the N,N,N′,N′‐tetraphenyl‐p‐phenylenediamine unit showed two‐step oxidations at 0.297 and 0.641 V. These oxidation processes produced new colors of the polymer films. The former triarylamine‐based chromophore provided a blue color after the oxidation, while the latter phenylenediamine‐based chromophore showed a potentially controlled green and dark blue colors. The reversibility and switching behaviors of these color changes were also comprehensively investigated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

10.
Three novel poly(2,7‐carbazole)s having hole injection and transporting pendent moieties of carbazole and triphenylamine at the N‐position were synthesized for achieving pure blue electroluminescence. The N‐pendants in the polymers correspond to N‐phenylcarbazol‐2‐yl ( P1 ), N,N‐diphenylamino‐N‐phenylcarabazol‐2‐yl ( P2) , and 4‐phenyl having a hydrocarbon chain with a triphenylamine terminal ( P3 ), respectively. Electronic, optical, and electroluminescence properties of these polymers were compared with those of a poly(2,7‐carbazole) directly connected with triphenylamine at the N‐position ( P0 ) having an aggregation‐induced emissive property. The photoluminescence (PL) spectra suggested that they could emit in the region of blue light in the film state. Especially, P2 that has the fixed and large diphenylaminocarbazolyl pendant showed a deep‐blue fluorescence with CIE(x, y) = (0.15, 0.07). The P0 , P2 , and P3 based light emitting diode devices showed maximum electroluminescence wavelengths in the range of 430–450 nm. The P2 device showed pure blue emission (CIE[x, y] = [0.18, 0.16]), high luminance (1130 cd/m2) and current density (628 mA/cm2) at 8 V, whereas low‐energy emissions around 500–600 nm were emerged at higher than 9 V. The P0 and P3 devices also showed a blue electroluminescence in the range of 8–11 V, but their luminance and efficiency were low. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2526–2534  相似文献   

11.
Photodynamic inactivation of bacteria (PIB ) is based on photosensitizers which absorb light and generate reactive oxygen species (ROS ), killing cells via oxidation. PIB is evaluated by comparing viability with and without irradiation, where reduction of viability in the presence of the photosensitizer without irradiation is considered as dark toxicity. This effect is controversially discussed for photosensitizers like TMP yP (5,10,15,20‐Tetrakis(1‐methyl‐4‐pyridinio)porphyrin tetra(p‐toluensulfonate). TMP yP shows a high absorption coefficient for blue light and a high yield of ROS production, especially singlet oxygen. Escherichia coli and Bacillus atrophaeus were incubated with TMP yP and irradiated with different light sources at low radiant exposures (μW per cm²), reflecting laboratory conditions of dark toxicity evaluation. Inactivation of E. coli occurs for blue light, while no effect was detectable for wavelengths >450 nm. Being more susceptible toward PIB , growth of B. atrophaeus is even reduced for light with emission >450 nm. Decreasing the light intensities to nW per cm² for B. atrophaeus , application of TMP yP still caused bacterial killing. Toxic effects of TMP yP disappeared after addition of histidine, quenching residual ROS . Our experiments demonstrate that the evaluation of dark toxicity of a powerful photosensitizer like TMP yP requires low light intensities and if necessary additional application of substances quenching any residual ROS .  相似文献   

12.
A blue fluorescent polymer based on poly(vinyl carbazole) (PVK) and terfluorene, combined to make a chemical hybrid at the carbazole unit (PVK‐TF), is fully characterized in this study. PVK‐TF shows useful emission features, such as peaks at 400, 420, 437, 460, and 496 nm, depending on the processing conditions. It possesses a relatively high triplet energy level (2.23 eV), electrochemical stability, good film‐forming ability, and morphological stability. Based on this blue fluorescent material, highly efficient orange phosphorescent polymer light‐emitting diodes (PLEDs) were fabricated with a maximum efficiency of 21.99 cd A?1, and a maximum luminance of 19552.3 cd m?2. Single‐layer hybrid white PLEDs were developed, with a high color rendering index of 81.9 that emitted across the whole visible spectrum from 380 to 780 nm, corresponding to the Commission International de L'Eclairage coordinates x, y values of around (0.38, 0.40) and CCT = 3774, with a maximum current efficiency of 10.69 cd A?1, and a maximum brightness of 15723.3 cd m?2. © 2014 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys. 2014 , 52, 587–595  相似文献   

13.
The effects of light on arsenic accumulation of Thraustochytrium CHN‐1 were investigated. Thraustochytrium CHN‐1, when exposed to blue light from light‐emitting diodes (LEDs), accumulated arsenate added to its growth medium to a much greater extent than Thraustochytrium cells exposed to fluorescent or red light, or when cultured in the dark. Arsenic compounds in Thraustochytrium CHN‐1 were analyzed by high‐performance liquid chromatography, with an inductively coupled plasma mass spectrometer serving as an arsenic‐specific detector. Arsenate, arsenite, monomethylarsonic acid (MMAA), dimethylarsinic acid (DMAA) and arsenosugar were identified. The order of arsenic species in Thraustochytrium CHN‐1 was arsenic(V)> arsenic(III)> MMAA > DMAA at an arsenic concentration of 10 mg dm?3 in the medium in blue LED light. As it is known that blue light induces the synthesis of certain metabolites in plants and microorganisms, this indicates that the accumulation of arsenic is an active metabolic process. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

14.
A series of blue light‐emitting hyperbranched polymers comprising poly(fluorene‐co‐dibenzothiophene‐S,S‐dioxide) as the branch and benzene, triphenylamine, or triphenyltriazine as the core were synthesized by an “A2 + A2' + B3” approach of Suzuki polymerization, respectively. All resulted copolymers exhibited quite comparable thermal properties with the glass transition temperatures in the range of 59–68 °C and relatively high decomposition temperatures over 420 °C. Photoluminescent spectra exhibited slight variation with the molar ratio of the dibenzothiophene‐S,S‐dioxide unit and the size of the core units. Polymer light‐emitting devices demonstrated blue emission with excellent stability of electroluminescence. Copolymers based on smaller core units of benzene and triphenylamine exhibited enhanced device performances regarding to that of triphenyltriazine. With the device configuration of ITO/PEDOT:PSS/polymer/CsF/Al, a maximum luminous efficiency of 4.5 cd A?1 was obtained with Commission Internationale de L'.Eclairage (CIE) coordinates of (0.16, 0.19) for the copolymer PFSO15B. These results indicated that hyperbranched structure can be a promising strategy to attain spectrally stable blue‐light‐emitting polymers with high efficiency. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1043–1051  相似文献   

15.
The crystal structure and in vitro cytotoxicity of the amphiphilic ruthenium complex [ 3 ](PF6)2 are reported. Complex [ 3 ](PF6)2 contains a Ru?S bond that is stable in the dark in cell‐growing medium, but is photosensitive. Upon blue‐light irradiation, complex [ 3 ](PF6)2 releases the cholesterol–thioether ligand 2 and an aqua ruthenium complex [ 1 ](PF6)2. Although ligand 2 and complex [ 1 ](PF6)2 are by themselves not cytotoxic, complex [ 3 ](PF6)2 was unexpectedly found to be as cytotoxic as cisplatin in the dark, that is, with micromolar effective concentrations (EC50), against six human cancer cell lines (A375, A431, A549, MCF‐7, MDA‐MB‐231, and U87MG). Blue‐light irradiation (λ=450 nm, 6.3 J cm?2) had little influence on the cytotoxicity of [ 3 ](PF6)2 after 6 h of incubation time, but it increased the cytotoxicity of the complex by a factor 2 after longer (24 h) incubation. Exploring the unexpected biological activity of [ 3 ](PF6)2 in the dark elucidated an as‐yet unknown bifaceted mode of action that depended on concentration, and thus, on the aggregation state of the compound. At low concentration, it acts as a monomer, inserts into the membrane, and can deliver [ 1 ]2+ inside the cell upon blue‐light activation. At higher concentrations (>3–5 μm ), complex [ 3 ](PF6)2 forms supramolecular aggregates that induce non‐apoptotic cell death by permeabilizing cell membranes and extracting lipids and membrane proteins.  相似文献   

16.
The new poly(arylene vinylene) derivatives, which are composed of biphenylene vinylene phenylene vinylene, biphenylene vinylene m‐phenylene vinylene, terphenylene vinylene phenylene vinylene, and terphenylene vinylene m‐phenylene vinylene as backbone and bulky fluorene pendants at each vinyl bridge, were designed, synthesized, and characterized. The obtained polymers showed weight‐average molecular weights of 11,100–39,800 with polydispersity indexes ranging from 1.5 to 2.1. The resulting polymers were amorphous with high thermal stability and readily soluble in common organic solvents. The obtained polymers showed blue emission (λmax = 456–475 nm) in PL spectra, and polymer 4 containing terphenylene vinylene m‐phenylene vinylene showed the most blue shifted blue emission (λmax = 456 nm). The double layer light‐emitting diode devices fabricated by using obtained polymers as emitter emitted bright blue light. The device showed turn on voltage around 6.5 V and brightness of 70–250 cd/m2. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4923–4931, 2006  相似文献   

17.
18.
Novel conjugated polymers containing 3,9‐ or 2,9‐linked carbazole units in the main chain were synthesized by the polycondensation of ethynyl‐ and iodo‐substituted 9‐arylenecarbazolylene monomers, and their optical and electrical properties were studied. Polymers with weight‐average molecular weights of 3400–12,000 were obtained in 76–99% yields by the Sonogashira coupling polycondensation in piperidine or tetrahydrofuran (THF)/piperidine at 30 °C for 48 h. All the 3,9‐linked polymers absorbed light around 300 nm. The para‐phenylene‐linked polymer also absorbed light around 350 nm, while meta‐phenylene‐linked one did not. The 3,9‐linked polymers absorbed light at a wavelength longer than the 2,9‐linked one. The polymers emitted blue fluorescence with high quantum yields (0.21–0.78) upon excitation at the absorption maxima. The polymers were oxidized around 0.6 V, and reduced around 0.5 V. Poly( 1 ) showed the dark conductivity of 3.7 × 10?11 S/cm (103 V/cm). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3506–3517, 2009  相似文献   

19.
A series of novel, fluorene‐based conjugated copolymers, poly[(9,9‐bis{propenyl}‐9H‐fluorene)‐co‐(9,9‐dihexyl‐9H‐fluorene)] ( P1 ), poly[(9,9‐bis{carboxymethylsulfonyl‐propyl}fluorenyl‐2,7‐diyl)‐co‐(9,9‐dihexyl‐9H‐fluorene)] ( P2 ) and poly[(9,9‐dihexylfluorene)‐co‐alt‐(9,9‐bis‐(6‐azidohexyl)fluorene)] ( P3 ), are synthesized by Suzuki coupling reactions and their electrochemical properties, in the form of films, are investigated using cyclic voltammetry. The results reveal that the polymer films exhibit electrochromic properties with a pseudo‐reversible redox behavior; transparent in the neutral state and dark violet in the oxidized state. Among the three polymers, P2 possesses the shortest response time and the highest coloration efficiency value. These polymers emit blue light with a band gap value of around 2.9 eV and have high fluorescent quantum yields. Their metal ion sensory abilities are also investigated by titrating them with a number of different transition metal ions; all of these polymers exhibit a higher selectivity toward Fe3+ ions than the other ions tested with Stern–Volmer constants of 4.41 × 106M?1, 3.28 × 107M?1, 1.25 × 106M?1, and 6.56 × 106M?1 for P1 , P2 , water soluble version of P2 ( P2S ) and P3 , respectively. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013  相似文献   

20.
The blue‐light (BL) absorbing protein Xcc‐LOV from Xanthomonas citri subsp. citri is composed of a LOV‐domain, a histidine kinase (HK) and a response regulator. Spectroscopic characterization of Xcc‐LOV identified intermediates and kinetics of the protein's photocycle. Measurements of steady state and time‐resolved fluorescence allowed determination of quantum yields for triplet (ΦT = 0.68 ± 0.03) and photoproduct formation (Φ390 = 0.46 ± 0.05). The lifetime for triplet decay was determined as τT = 2.4–2.8 μs. Fluorescence of tryptophan and tyrosine residues was unchanged upon light‐to‐dark conversion, emphasizing the absence of significant conformational changes. Photochemistry was blocked upon cysteine C76 (C76S) mutation, causing a seven‐fold longer lifetime of the triplet state (τT = 16–18.5 μs). Optoacoustic spectroscopy yielded the energy content of the triplet state. Interestingly, Xcc‐LOV did not undergo the volume contraction reported for other LOV domains within the observation time window, although the back‐conversion into the dark state was accompanied by a volume expansion. A radioactivity‐based enzyme function assay revealed a larger HK activity in the lit than in the dark state. The C76S mutant showed a still lower enzyme function, indicating the dark state activity being corrupted by a remaining portion of the long‐lived lit state.  相似文献   

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