• Title/Summary/Keyword: Excited state lifetime

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An Immobilized Fenton Catalyst$^1$

  • Song, Pill-Soon;Choi, Jung-Do
    • Bulletin of the Korean Chemical Society
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    • v.1 no.3
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    • pp.113-114
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    • 1980
  • Lumichrome (7,8-dimethylalloxazine) exhibits two fluorescence emission maxima at 440 and 540 nm in pyridine-dioxane. These emission band maxima are attributable to radiative decays from the excited states of lumichrome and its flavin tautomer, 7,8-dimethylisoalloxazine, respectively. The growth of the latter can be followed upon excitation of the former with a 2-nanosecond light pulse generated from the nitrogen plasma discharge lamp. The excited state tautomerism results from proton transfer from N-1 to N-10 position during the lifetime of the lumichrome singlet excited state. The rate depends on the concentration of general base, pyridine, and it is an order of magnitude slower than diffusion-controlled processes.

The investigation of a new fast timing system based on DRS4 waveform sampling system

  • Zhang, Xiuling;Du, Chengming;Chen, Jinda;Yang, Herun;kong, Jie;Yang, Haibo;Ma, Peng;Shi, Guozhu;Duan, limin;Hu, Zhengguo
    • Nuclear Engineering and Technology
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    • v.51 no.2
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    • pp.432-438
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    • 2019
  • In the study of nuclear structure, the fast timing technique can be used to measure the lifetime of excited states. In the paper, we have developed a new fast timing system, which is made up of two $LaBr_3:Ce$ detectors and a set of waveform sampling system. The sampling system based on domino ring sampler version 4 chip (DRS4) can digitize and store the waveform information of detector signal, with a smaller volume and higher timing accuracy, and the waveform data are performed by means of digital waveform analysis methods. The coincidence time resolution of the fast timing system for two annihilation 511 keV ${\gamma}$ photon is 200ps (FWHM), the energy resolution is 3.5%@511 keV, and the energy linear response in the large dynamic range is perfect. Meanwhile, to verify the fast timing performance of the system, the $^{152}Gd-2_1^+$ state form ${\beta}^+$ decay of $^{152}Eu$ source is measured. The measured lifetime is $45.3({\pm}5.0)ps$, very close to the value of the National Nuclear Data Center (NNDC: $46.2({\pm}3.9)ps$). The experimental results indicate that the fast timing system is capable of measuring the lifetime of dozens of ps. Therefore, the system can be widely used in the research of the fast timing technology.

Elucidation of photo-induced electron transfer in a loop-forming peptide: Dye-Ala-Gly-Gln-Tyr

  • Lee, Hwiin;Kim, Jeongyun;Kwon, Yong-Uk;Lee, Minyung
    • Rapid Communication in Photoscience
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    • v.4 no.3
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    • pp.59-62
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    • 2015
  • We investigated photo-induced electron transfer (PET) in a dye-labeled peptide, fluorophore-Ala-Gly-Gln-Tyr, employing time-resolved fluorescence. As an effort to develop new functional dyes, we studied an acriflavine derivative for the electron-acceptor in the excited state from tyrosine, an electrondonor in the ground-state. The pH dependence of the fluorescence lifetime of the model peptide indicates that electron transfer between the excited dye and tyrosine occurs when the tyrosine is deprotonated. The proton-coupled electron transfer appears to be sequential rather than concerted. We also report direct time measurements on the end-to-end loop formation processes of the peptide in water.

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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    • v.11 no.3
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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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Spectroscopic Properties of Quercetin in AOT Reverse Micelles

  • Park, Hyoung-Ryun;Im, Seo-Eun;Seo, Jung-Ja;Bark, Ki-Min
    • Bulletin of the Korean Chemical Society
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    • v.35 no.3
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    • pp.828-832
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    • 2014
  • The spectroscopic properties of quercetin (QCT) were studied in the AOT reverse micelle by fluorescence spectroscopy. Because the molecular structure of QCT is completely planar, excited state intramolecular proton transfer (ESIPT) occurs between the -OH at C(5) and carbonyl oxygen via intramolecular hydrogen bonding. This ESIPT happens at the $S_1$ state but not at the $S_2$ state. Because QCT is a good donor-acceptor-conjugated molecule at the excited state, this molecule can emit strong fluorescence but shows no $S_1{\rightarrow}S_o$ emission due to this ESIPT. Since the $S_2{\rightarrow}S_1$ internal conversion was very slow due to the small Franck-Condon factors, $S_2{\rightarrow}S_o$ fluorescence emission was observed. All of the experimental results indicated that the QCT resided at the bound water interface and that the position of solute did not change significantly in the micelle at various water concentrations.

Synthesis and Characterization of Peripherally Ferrocene-modified Zinc Phthalocyanine for Dye-sensitized Solar Cell

  • An, Min-Shi;Kim, Soon-Wha;Hong, Jong-Dal
    • Bulletin of the Korean Chemical Society
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    • v.31 no.11
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    • pp.3272-3278
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    • 2010
  • Synthesis and structural characterization of peripherally ferrocene-substituted zinc phthalocyanine (ZnPc-Fc) were carried out for efficient far-red/near-IR performance in dye-sensitized nanostructured $TiO_2$ solar cells. Incorporating ferrocene into phthalocyanine strongly improved the dye solubility in polar organic solvents, and reduced surface aggregation due to the steric effect of bulky ferrocene substituents. The involvement of electron transfer reaction pathways between ferrocene and phthalocyanine in ZnPc-Fc was evidenced by completely quenched fluorescence from S1 state (< 0.08% vs ZnPc). Strong absorption bands at 542 and 682 nm were observed in the transient absorption spectroscopy of ZnPc-Fc in DMSO, which was excited at a 670 nm laser pulse with a 15 ps full width at half maximum. Also, the excited state absorption signals at 450 - 600 and 750 - 850 nm appeared from the formation of charge separated state of phthalocyanine's anion. The lifetime of the charge separate state in ZnPc-Fc was determined to be $170{\pm}8$ ps, which was almost 17 times shorter than that of the ZnPc.

Lifetime and Anisotropy Measurements of DODCI in the excited state by TCSPC (TCSPC에 의한 DODCI의 형광 소멸시간 및 비등방성 측정 연구)

  • 이민영;김동호
    • Korean Journal of Optics and Photonics
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    • v.1 no.1
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    • pp.52-57
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    • 1990
  • Employing a picosecond laser and fast electronics. we developed a time -correlated single photon counting (TCSPC) system by which ltuninescence lifetimes can be measured in the subnanosecond to microsecond scale. We also studied non-radiative decay dynamics and rotational motion of DODC! laser dye in solution using this system. ystem.

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Vacuum Ultraviolet Photolysis of Ethyl Bromide at 104.8-106.7 nm

  • Kim, Hong-Lae;Yoo, Hee-Soo;Jung, Kyung-Hoon
    • Bulletin of the Korean Chemical Society
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    • v.2 no.2
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    • pp.71-75
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    • 1981
  • Vacuum ultraviolet photolysis of ethyl bromide was studied at 104.8-106.7 nm (11.4-11.6 eV) in the pressure range of 0.2-18.6 torr at $25^{\circ}$ using an argon resonance lamp with and without additives, i.e., NO and He. Since the ionization potential of $CH_3CH_2Br$ is lower than the photon energy, the competitive processes between the photoionization and the photodecomposition were also investigated. The observations indicated that 50% of absorbed light leads to the former process and the rest to the latter one. In the absence of NO the principal reaction products for the latter process were found to be $CH_4, C_2H_2, C_2H_4, C_2H_6, and C_3H_8$. The product quantum yields of these reaction products showed two strikingly different phenomena with an increase in reactant pressure. The major products, $C_2H_4$ and $C_2H_6$, showed positive effects with pressure whereas the effects on minor products were negative in both cases, i.e., He and reactant pressures. Addition of NO completely suppresses the formation of all products except $C_2H_4$ and reduces the $C_2H_4$ quantum yield. These observations are interpreted in view of existence of two different electronically excited states. The initial formation of short-lived Rydberg transition state undergoes HBr molecular elimination and this state can across over by collisional induction to a second excited state which decomposes exclusively by carbon-bromine bond fission. The estimated lifetime of the initial excited state was ${\sim}4{\times}10^{-10}$ sec. The extinction coefficient for $CH_3CH_2Br$ at 104.8-106.7 nm and $25{\circ}$ was determined to be ${varepsilon} = (1/PL)ln(I_0/I_t) = 2061{\pm}160atm^{-1}cm6{-1}$ with 95% confidence level.

Photophysical Properties of Khellin-Dimethylfumarate C$_4$-Cyclomonoadduct

  • Shim, Sang-Chul;Kang, Ho-Kwon
    • Bulletin of the Korean Chemical Society
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    • v.7 no.6
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    • pp.458-461
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    • 1986
  • The fluorescence intensity of khellin-dimethylfumarate C$_4$-cycloadduct (KDF) is very sensitive to temperature and to the nature of solvents, especially hydrogen-bonding ability. The fluorescence quantum yields of KDF in ethanol and isopentane at 77K are 0.73 and 0.54, respectively, both of which are much larger than the room temperature values. The phosphorescence lifetime is very long and decreases with decreasing the solvent polarity. The phosphorescence and fluorescence quantum yield ratio is very small and decreases with decreasing solvent polarity. The solvent relaxation plays an important role in the excited states of KDF. The internal conversion is a major decay process of the excited singlet state of KDF in all the solvents used at room temperature.

PHOTOPHYSICAL PROPERTIES OF FLUORENONES WITH CHIRAL SUBSTITUENTS AND THEIR ASYMMETRIC RECOGNITION THROUGH INTERMOLECULAR HYDROGEN BONDING INTERACTIONS IN THE EXCITED STATES

  • Aikawa, Yoshihide;Shimada, Tetsuya;Tachibana, Hiroshi;Inoue, Haruo
    • Journal of Photoscience
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    • v.6 no.4
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    • pp.165-170
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    • 1999
  • Asymmetric recognition of chiral alcohol by fluorenone derivatives with chiral substituents through intermolecular hydrogen bonding interaction in the singlet excited state was attempted. 1-((1S, 2R, 5S)-(+)-Menthyloxycarbonyl)aminofluoren-9-one (1-MAF) and 1-((1S, 2R, 5S)-(+)-menthyloxycarbonyl)oxyfluoren-9-one (1-MOF) were synthesized and their photophysical behaviors were characterized by the measurement of absorption and fluorescence spectra, as well as the quantum yield and the lifetime of fluorescence. The excited singlet states of 1-MAF and 1-MOF were revealed to have characteristics similar to those of fluorenone, though the intramolecular CT nature was fairly suppressed as compared with 3- and 4-substituted aminofluorenones. Fluorescences of 1-MAF and 1-MOF in acetonitrile were quenched by the addition of alcohols. Differences in fluorescence quenching efficiency were hardly observe for rather small chiral alcohols such as (R)-(-)- or (S)-(+)-2-butanol, while bulky alcohols such as menthol and isopinocampheol showed chiral recognition effects in their fluorescence quenching of 1-MAF in either acetonitrile or butyronitrile.

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