• 제목/요약/키워드: fluorescence yield

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Photochemical synthesis of diphenylphenanthrenes, and the photophysical properties studied by emission and transient absorption measurements

  • Yamaji, Minoru;Hakoda, Yuuma;Horimoto, Ami;Okamoto, Hideki
    • Rapid Communication in Photoscience
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    • 제3권4호
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    • pp.73-75
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    • 2014
  • Novel diphenylphenanthrenes (DPPs) were prepared by a photocyclization method, and the substituent effects of the phenyl groups on the photophysical properties of the phenanthrene chromophore were investigated based on measurements of fluorescence yields, lifetimes, and transient absorption. Fluorescence activities in DPPs are increased by introducing phenyl rings that can enhance the transition moment along the short axis of the phenanthrene skeleton. Intersystem crossing from the fluorescent states to the triplet manifolds is shown to be operative through the triplet-triplet absorption spectra obtained by laser photolysis techniques.

EFFECT OF NITROGEN POSITION ON EXCITED STATE PROPERTIES OF 1-(9- ANTHRYL )-2-(n-QUINOLINYL)ETHENES

  • Shin, Eun-Ju
    • Journal of Photoscience
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    • 제6권2호
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    • pp.61-65
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    • 1999
  • The fluorescence properties and photoisomerization behavior of 1-(9-anthryl)-2-(n-quinolinyl)ethene (n-AQE, n=2-4) have been investigated in various solvents. t-3-AQE is strongly fluorescent, but does not accomplish photoisomerization, similar to parent hydrocarbon compound, t-1-(9-anthryl)-2-phenylethene (t-9-APE) or t-1-(9-anthryl)-2-(1-naphthyl)ethene (t-1-ANE). Fluorescence and photoisomerization oft-2-AQE and t-4-AQE are strongly affected by solvent polarity. Dependence of fluorescence quantum yield on the solvent polarity is moderate for t-2-AQE and large for t-4-AQE. In nonpolar solvent (in n-hexane), they exhibit relatively strong fluorescence, but do not isomerize to cis isomer on irradiation, even if inefficient isomerization is observed for t-4-AQE. However, as solvent polarity increases, their fluorescences become weak with efficient photoisomerization to corresponding cis isomer. Intramolecular charge-transfer excited state is presumed to contribute to photoisomerization. The S$_1$ decay parameters were found to be solvent-dependent due to the charge-transfer character of lowest S$_1$ state. In polar solvents, the activation barrier to twisting is reduced enhancing the isomerization of r-2-AQE and t-4-AQE in the singlet manifold.

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SPECTRAL AND PROTOPHYSICAL PROPERTIES OF 1-PYRAZINYL-2-(3- QUINOLINYL)ETHYLENE

  • Bong, Pill-Hoon;Ryoo, Jae-Hwan
    • Journal of Photoscience
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    • 제6권4호
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    • pp.171-176
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    • 1999
  • The spectral and photophysical properties of trans-1-pyrazinyl-2-(3-quinolinyl)ethylene (trans-3- PyQE) are investigated under various conditions in order to obtain information on ground and excited states. The absorption spectrum of trans-3-PyQE changes slightly with varying degree of solvent polarity ; the. fluorescence spectrum is shifted to the red and becomes broad and structureless as the solvent polarity increases. The fluorescence quantum yield increases with increasing solvent polarity. The fluorescence intensity of trans-3-PyQE decreases as the concentration of methyl iodide increases. The fluorescence spectra of trans-3-PyQE changes markedly upon the variation of the excitation wavelength, presumably due to an equilibrium between conformers originating from the rotation of a quasi-single bond between the quinolinyl group and ethylenic carbon atom. These results indicate that the spectral and photophysical properties of trans-3-PyQE are strongly influenced by solvent, heavy atom, and an equilibrium between conformers

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PHOTOPHYSICAL AND OPTICAL PROBE PROPERTIES OF 1-(p-N,N-DIMETHYLAMINOPHENYL)-4-PHENYL-2-METHYL-1E,3E-BUTADIENE

  • Singh, A.K.;Krishna, T.S.R.
    • Journal of Photoscience
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    • 제4권1호
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    • pp.1-5
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    • 1997
  • A hitherto unknown diphenylbutadiene analog viz. 1-(p-N,N-dimethylaminophenyl)-4-phenyl-2-methyl-1E,3E-butadiene (10) has been prepared and its absorption, excitation, and fluorescent emission properties in different media including various organic solvents and aqueous bovine serum albumin (BSA) have been studied. For comparision, these properties have also been investigated for the parent diphenylbutadiene (2). Diene 10 exhibits solvent polarity/polarizability-sensitive fluorescence properties ($\lambda$$_{max}$, $\Phi$$_f$, $\tau$$_f$, K$_f$, f). It also binds to the hydrophobic domains of aqueous bovine serum albumin (BSA) with a binding constant of 3.89 x 10$^4$ M$^{-1}$. The relative fluorescence quantum yield of 10 increases, while, the fluorescence lifetime decreases with increasing concentration of-BSA. The results highlight the polar character of the singlet excited state of diphenylpolyenes and the utility of 10 as fluorescence probe for studying microenvironments of organized assemblies and biological supramolecular structures.

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Effect of Deuterated Solvents on the Excited State Photophysical Properties of Curcumin

  • Barik, A.;Goel, N.K.;Priyadarsini, K.I.;Mohan, Hari
    • Journal of Photoscience
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    • 제11권3호
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    • pp.95-99
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    • 2004
  • Optical absorption and emission studies have been carried out to understand the effect of deuterium on the solvent dependent photophysical properties of curcumin in deuterated solvents such as $CDCl_3,\;(CD_3)_2SO,\;(CD_3)_2CO,\;CD_3OD\;and\;CD_3CN$. Optical absorption spectral studies showed that there is no significant shift in absorption maxima compared to the non-deuterated solvent. The fluorescence maxima shows significant shift with polarity of solvent but not much affected by the deuteration. The fluorescence quantum yield of curcumin increased marginally in almost all the deuterated solvents, indicating reduction in the non-radiative pathways. The fluorescence decay was biexponential in all the solvents and the average fluorescence lifetime was not much affected with deuteration, but showed decrease with increasing solvent polarity. Based on these studies, it is concluded that intermolecular hydrogen transfer is only partially responsible for the excited state deactivation of curcumin.

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Photoisomerization of Symmetric Carbocyanines

  • 민형식;강유남;박정희
    • Bulletin of the Korean Chemical Society
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    • 제19권7호
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    • pp.747-753
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    • 1998
  • The phoisomerization process of symmetric carbocyanine dyes such as 3,3'-diethyloxadicarbocyanine iodide (DODCI), 3,3'-diethylthiadicarbocyanine iodide (DfDCI), 1,1'-diethyl-2,2'-dicarbocyanine iodide (DDI), 1,1'-diethyl-2,2'-carbocyanine iodide (DCI), and cryptocyanine (1,1'-diethyl-4,4'-carbocyanine) iodide (CCI) have been studied by measuring the steady state and time resolved fluorescence spectra and the ground-state recovery profiles. The steady-state fluorescence spectrum of photoisomer as a function of concentration and excitation wavelength provides the evidence that the fluorescence of photoisomer is formed by the radiative energy transfer from the normal form and the quantum yield for the formation of photoisomer is increased by decreasing the excitation wavelength. The fluorescence decay profiles have been measured by using the time correlated single photon counting (TCSPC) technique, showing a strong dependence on the concentration and the detection wavelength, which is due to the formation of excited photoisomers produced either by the radiative energy transfer from the non-nal form or by absorbing the 590 nm laser pulse. We first report the fluorescence decay time of photoisomers for these cyanine dyes. The experimental results are explained by introducing the semiempirical calculations. The ground state recovery profiles of DTDCI, DDI, and CCI normal forms have been measured, showing that the recovery time from the singlet excited state is similar with the fluorescence decay time.

Effects of Ozone on $CO_2$ Assimilation and PSII Function in Two Tobacco Cultivars with Different Sensitivities

  • Yun, Myoung-Hui
    • Journal of Korean Society for Atmospheric Environment
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    • 제22권E2호
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    • pp.89-98
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    • 2006
  • Two tobacco cultivars (Nicotiana tabacum L.), Bel-B and Bel-W3, tolerant and sensitive to ozone, respectively, were grown in a greenhouse supplied with charcoal filtered air and exposed to 200 ppb ozone for 4 hr. Effects on chlorophyll fluorescence, net photosynthesis, and stomatal conductance are described. Quantum yield was calculated from chlorophyll fluorescence and the initial slope of the assimilation-light curve measured by the gas exchange method. Only the sensitive cultivar, Bel-W3, developed visual injury symptoms on up to 50% of the $5^{th}$ leaf. The maximum net photosynthetic rate of ozone-treated plants was reduced 40% compared to control plants immediately after ozone fumigation in the tolerant cultivar; however, photosynthesis recovered by 24 hr post fumigation and remained at the same level as control plants. On the other hand, ozone exposure reduced maximum net photosynthesis up to 50%, with no recovery, in the sensitive cultivar apparently causing permanent damage to the photosystem. Reductions in apparent quantum efficiency, calculated from the assimilation-light curve, differed between cultivars. Bel-B showed an immediate depression of 14% compared to controls, whereas, Bel-W3 showed a 27% decline. Electron transport rate (ETR), at saturating light intensity, decreased 58% and 80% immediately after ozone treatment in Bel-B and Bel-W3, respectively. Quantum yield decreased 28% and 36% in Bel-B and Bel-W3, respectively. It can be concluded that ozone caused a greater relative decrease in linear electron transport than maximum net photosynthesis, suggesting greater damage to PSII than the carbon reduction cycle.

Symmetric Bis-Azospiropyrans: Synthesis, Characterization and Colorimetric Study

  • Nourmohammadian, Farahnaz;Abdi, Ali Ashtiani
    • Bulletin of the Korean Chemical Society
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    • 제34권6호
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    • pp.1727-1734
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    • 2013
  • Synthesis and characterization of some novel symmetric bis-azospiropyrans are reported in this study. These bis-azospiropyrans are bifunctional chromophores with two spiropyrans linked by a bis-azo extended aromatic system that produce more color strength (large molar absorption coefficient in mero forms) due to appending two azospiropyran chromophores on one molecule. Comparing to the molar absorption coefficients of the conventional spiropyran chromophores (${\varepsilon}=0.31{\times}10^4\;M^{-1}{\cdot}cm^{-1}$) and mono-azospiropyran chromophores ($1.35{\times}10^4\;M^{-1}{\cdot}cm^{-1}$), the novel synthesized photochromes showed astonishingly increased molar absorption coefficients ($2.3-3.8{\times}10^4\;M^{-1}{\cdot}cm^{-1}$) at the same conditions. Such high molar absorption coefficients confers high sensitivity to light and more color intensity of mero form, that leads to improvement of their light sensitivity and better discrimination of spiro (OFF) form from mero (ON) ones in molecular switches. The structures were deduced from their MS, FT-IR, and $^1H$-NMR spectroscopic data and CHN analysis. All the synthesized photochemically bifunctional compounds revealed fluorescent emission in their colorless form which was faded out after exposing to UV light. Fluorescence quantum yield values of the mero forms were 0.25-0.81 and two high fluorescence quantum yield values (0.60 and 0.81) were found in these series.

Isolation and Physical Properties of Photochemical 8-Methoxypsoralen-thymidine 4$^\prime,5^\prime-C_4$-Monoadducts

  • Shim, Sang-Chul;Kang, Ho-Kwon
    • Bulletin of the Korean Chemical Society
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    • 제5권6호
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    • pp.219-223
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    • 1984
  • The 8-methoxypsoralen$<^{4',5'}_{5',6}>$ thymidine monoadducts are isolated from the irradiation mixture of 8-methoxypsoralen and thymidine in a dry film state by a flash column followed by lobar column chromatography. Some physical properties of the adducts were determined. The fluorescence maximum and quantum yield of the monoadduct are dependent on the solvent polarity and the phosphorescence to fluorescence quantum yield ratio was 2.10 which was significantly increased by external heavy atoms. The phosphorescence lifetime was 1.2s which is relatively large compared to other coumarin derivatives. Accurate spectral data of the monoadducts are presented.

Fluorescence Tuning Using Conjugated Aromatic Imine Systems

  • Lee, Ki-Hwan;Park, Chang-Shik;Jeon, Ki-Seok
    • Journal of Photoscience
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    • 제9권3호
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    • pp.71-74
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    • 2002
  • The fluorescent conjugated aromatic imine derivatives are systematically designed and synthesized as the high yield through the simple one-pot condensation reaction. The emission of the synthesized conjugated aromatic imine derivatives can be tuned efficiently in the range of about 100 nm by the change of electron donating groups constituting parent molecule, which shows the considerable quantum yields from 0.38 to 0.56.

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