• Title/Summary/Keyword: time-resolved fluorescence

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Picosecond Protein Fluorescence and Time-Resolved $Eu^{3+}$ Luminescence Spectroscopic Studies on the Roles of $Ca^{2+}$ in Subtilisin Carlsberg

  • Lee, Sunbae;Jang, Du-Jeon
    • Proceedings of the Korean Biophysical Society Conference
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    • 1997.07a
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    • pp.44-44
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    • 1997
  • Ca$^{2+}$ is one of the most common metal ions associated with proteins, playing more or less well-defined functional roles in biological activities. In protease, the presence of $Ca^{2+}$ slows down autolysis and enhances thermal stability. Subtilisin, one of the best studied proteases, is known to have two $Ca^{2+}$ -binding sites.(omitted)

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Zn(II)porphyrin Helical Arrays: A Strategy to Overcome Conformational Heterogeneity by Host-Guest Chemistry

  • Yoon, Zin-Seok;Easwaramoorthi, Shanmugam;Kim, Dong-Ho
    • Bulletin of the Korean Chemical Society
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    • v.29 no.1
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    • pp.197-201
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    • 2008
  • Conformational heterogeneity of directly linked multiporphyrin arrays with larger molecular length retards their utilities in practical applications such as two-photon absorption and molecular photonic wire. In this regard, here we adopted a way to overcome the conformational heterogeneity through hydrogen bonding by selective binding of meso aryl substituents of porphyrins (host) with urea (guest) to form helical structure. Using steady-state and time-resolved spectroscopy, we observed the enhanced fluorescence quantum yield by ~1.8 to 2.4 times, enhanced anisotropy values and the disappearance of fast fluorescence decay component in the host-guest helical forms. In addition, the enhanced nonlinear optical responses of helical arrays infer the extended inter-porphyrin electronic coupling due to a significant change in dihedral angle between the neighboring porphyrin moieties. The current host-guest strategy will provide a guideline to improve the structural homogeneity of the photonic wire.

Temperature-Dependent Hydrolysis Reactions of U(VI) Studied by TRLFS

  • Lee, J.Y.;Yun, J.I.
    • Journal of Nuclear Fuel Cycle and Waste Technology
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    • v.1 no.1
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    • pp.65-73
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    • 2013
  • Temperature-dependent hydrolysis behaviors of aqueous U(VI) species were investigated with time-resolved laser fluorescence spectroscopy (TRLFS) in the temperature range from 15 to $75^{\circ}C$. The formation of four different U(VI) hydrolysis species was measured at pHs from 1 to 7. The predominant presence of $UO{_2}^{2+}$, $(UO_2)_2(OH){_2}^{2+}$, $(UO_2)_3(OH){_5}^+$, and $(UO_2)_3(OH){_7}^-$ species were identified based on the spectroscopic properties such as fluorescence wavelengths and fluorescence lifetimes. With an increasing temperature, a remarkable decrement in the fluorescence lifetime for all U(VI) hydrolysis species was observed, representing the dynamic quenching behavior. Furthermore, the increase in the fluorescence intensity of the further hydrolyzed U(VI) species was clearly observed at an elevated temperature, showing stronger hydrolysis reactions with increasing temperatures. The formation constants of the U(VI) hydrolysis species were calculated to be $log\;K{^0}_{2,2}=-4.0{\pm}0.6$ for $(UO_2)_2(OH){_2}^{2+}$, $log\;K{^0}_{3,5}=-15.0{\pm}0.3$ for $(UO_2)_3(OH){_5}^+$, and $log\;K{^0}_{3,7}=-27.7{\pm}0.7$ for $(UO_2)_3(OH){_7}^-$ at $25^{\circ}C$ and I = 0 M. The specific ion interaction theory (SIT) was applied for the extrapolation of the formation constants to infinitely diluted solution. The results of temperature-dependent hydrolysis behavior in terms of the U(VI) fluorescence were compared and validated with those obtained using computational methods (DQUANT and constant enthalpy equation). Both results matched well with each other. The reaction enthalpies and entropies that are vital for the computational methods were determined by a combination of the van't Hoff equation and the Gibbs free energy equation. The temperature-dependent hydrolysis reaction of the U(VI) species indicates the transition of a major U(VI) species by means of geothermal gradient and decay heat from the radioactive isotopes, representing the necessity of deeper consideration in the safety assessment of geologic repository.

Photoionization of N,N,N',N'-Tetramethyl-p-phenylenediamine in Polar Solvents

  • Min Yeong Lee;Du Jeon Jang;Minyung Lee;Du-Jeon Jang;Dongho Kim;Sun Sook Lee;Bong Hyun Boo
    • Bulletin of the Korean Chemical Society
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    • v.12 no.4
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    • pp.429-433
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    • 1991
  • The photoinduced electron transfer reactions of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) in various polar solvents were studied by measuring time-resolved fluorescence. The temperature dependence on the fluorescence decay rate in acetonitrile, methanol, ethanol and buthanol was carried out to obtain the activation energy and Arrehnius factor for the photoinduced electron transfer reaction. It was found that as the dielectric constant of the solvent increases, the activation energy and the reaction rate increase. This implys that the Arrehnius factor is important in controlling the photoinduced electron transfer reaction rate. In water, TMPD exists in three forms (cationic, protonated and neutral forms) due to the high dielectric constant and strong proton donating power of water. The photoinduced electron transfer reaction was found to be very fast (< 50 ps) and also the long liverd component in the fluorescence decay profile attributable to the photoexcited protonated form of TMPD was observed. Probably, the reaction pathway and the reaction coordinate seem to be different depending on the solvents studied here.

Picosecond Fluorescence Lifetimes of Hematoporphyrin Derivatives in Solutions and in vitro (용액 및 시험관 실험에서의 헤마토포르피린 유도체 분자의 피코초 형광수명시간 분석)

  • Kim, Hyun-Soo;Chu, Sung-Sil;Kim, Gwi-Eon;Lee, Won-Young;Kim, Ung
    • Progress in Medical Physics
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    • v.6 no.2
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    • pp.61-70
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    • 1995
  • The picosecond time resolved fluorescence spectra of Hematoporphyrin Derivative (HPD) in both solutions and cancer cell are measured by a time correlated single photon counting system with a synchronously mode locked dye laser. Two exoponential decay components in the fluorescence spectra were observed. The slow decay(6.3 ㎱)and the fast one(350 ㎰)are attributed to be originated from monomers and dimers, respectively. The absorption and fluorescence measurements in steady state also showed the presence of a monomeric and dimeric forms of HPD molecules. The monomer lifetime in the cancer cell was measured to be longer than that in solution, which was expected from the blue shift and narrowing of the absorption spectra for HPD-treated in vitro. The relative amplitude of the fast component was found to be enhanced in cancer cell, strongly indicating the higher affinity of the dimer for the cancer cell.

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A Study of Energy Transfer in the Blue Emitting Fluorescence of SrAl12O19:Ce0.093+, Eu0.012+ Phosphor (SrAl12O19:Ce0.093+, Eu0.012+ 형광체에서 청색발광의 에너지 전이에 관한 연구)

  • Kim, Gwang Chul;Choi, Jin Soo
    • Journal of the Semiconductor & Display Technology
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    • v.18 no.1
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    • pp.48-52
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    • 2019
  • The blue emitting fluorescence of $SrAl_{12}O_{19}:Ce_{0.09}{^{3+}}$, $Eu_{0.01}{^{2+}}$ phosphor includes two kinds of independent energy transfer mechanism through electric multipole interactions between donor and acceptor ions. The first energy transfer takes place between the $Ce^{3+}$ ion and the $Eu^{2+}$ion which strongly depends on the concentration $Eu^{2+}$ions. The second energy transfer occurs between the $Ce^{3+}$ ion and the $O_{Me}-Ce^{3+}$ complexes. Both energy transfer mechanisms of blue emitting peak at 410 nm were investigated by fitting of Gaussian functions. The result shows that the peak at 410 nm is two overlapping emissions originated by $Eu^{2+}$ions and $O_{Me}-Ce^{3+}$ complexes and as time elapses $Eu^{2+}$peak remains whereas $O_{Me}-Ce^{3+}$ related peak disappears.

Lipid-binding properties of TRIM72

  • Kim, Sung-Hyen;Seo, Jeong-Hwa;Ko, Young-Gyu;Huh, Young-Duk;Park, Heon-Yong
    • BMB Reports
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    • v.45 no.1
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    • pp.26-31
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    • 2012
  • TRIM72 is known to play a critical role in skeletal muscle membrane repair. To better understand the molecular mechanisms of this protein, we carried out an in vitro binding study with TRIM72. Our study proved that TRIM72 binds various lipids with dissociation constants ($K_d$) ranging from 88.2 ${\pm}$ 9.9 nM to 550.5 ${\pm}$ 134.5 nM. In addition, the intrinsic fluorescence of TRIM72 exponentially decreased when the protein was diluted with stirring. The time-resolved fluorescence decay occurred in a concentration-independent manner. The fluorescence-decayed TRIM72 remained in its secondary structure, but its binding properties were significantly reduced. The dissociation constants ($K_d$) of fluorescence-decayed TRIM72 for palmitate and stearate were 159.1 ${\pm}$ 39.9 nM and 355.4 ${\pm}$ 106.0 nM, respectively. This study suggests that TRIM72 can be dynamically converted by various stimuli. The results of this study also provide insight into the role of TRIM72 in the repair of sarcolemma damage.

The Spray Characteristics of Swirl and Slit Injector to DISI Engine Using LIEF and Mie-scattering Method (LIEE와 Mie 산란 방법을 이용한 직분식 가솔린 엔진의 스월 및 슬릿 인젝터의 분무 특성)

  • Lee Kihyung;Hwang Kyumin;Lee Changhee
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.29 no.3 s.234
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    • pp.356-367
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    • 2005
  • The spray characteristics of DISI injector have a great role in gasoline engine efficiency and emission. Thus, many researchers have studied to investigate the spray characteristics of swirl and slit injectors that are used in a DISI engine. In this study, we tried to provide spray parameters, which affect on the spray characteristics such as injection pressure, ambient pressure and ambient temperature. In addition, we calculated $t_{b}\;and\;t_{c}$ to investigate the break up mechanism of test injectors and obtained $C_{v}$ to evaluate the spray characteristics. As the ambient pressure increases in case of slit injector, $C_{v}$ decreases. The laser-induced exciplex fluorescence (LIEF) technique, which is based on spectrally resolved two-color fluorescent emissions, has applied to measure the liquid and vapor phases for on evaporating spray simultaneously. The TMPD/naphthalene proposed by Melton is used as a dophant to detect exciplex signal. The temporal and spatial distribution of liquid and vapor phases during the mixture formation process was measured by this technique. In the LIEF technique, the vapor phase is detected by the monomer fluorescence while the liquid phase is tracked by the exciplex fluorescence. From this experiment, we found that the spray area of the vapor phase is increased with elapsed time after injection and the area of liquid is decreased when the ambient pressure is 0.1MPa. However, the area tends to increase until the end of injection when the ambient pressure is 1.0MPa.

Energy Transfer between Calixarene and Naphthalene

  • Kook, Seong-Keun
    • Bulletin of the Korean Chemical Society
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    • v.23 no.8
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    • pp.1111-1115
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    • 2002
  • The photoluminescence of calixarene crystals has been studied as functions of temperature, time, and concentration. The vibronic bands shift to longer wavelength and become significantly sharper as temperature decreases. The experimental results r eveal that the structural transformation occur during the annealing process. Time-resolved spectra of calixarene at 12 K are monitored. Spectral features, which demonstrate characteristic of energy transfer processes, are not observed. The depopulation of excited state density is mainly controlled by unimolecular decay process dominating other decay processes. The lifetime was found to be 2.6 $\pm$ 0.1 ns. For the case of calixarene mixed with naphthalene, the fluorescence spectrum shows that the band centered at 340 nm lies 2840 $cm^{-1}$ below the relatively broad 310 nm band found for calixarene crystals. The spectra also exhibit that the emission intensity increases with increasing calixarene concentration. The results are evident that the calixarene emission is quenched by the naphthalene. Phosphorescence of calixarene mixed with naphthalene crystals is observed to determine whether the emission is due to naphthalene. The phosphorescence peaks were compared with the ground-state vibrational frequencies of naphthalene and found to be in good agreement. The results indicate that inter-molecular energy transfer occurs between calixarene and naphthalene.

Visualization of oxygen distribution on leaf surfaces using VisiSens oxygen planar optode system (VisiSens 산소 평면광 센서 시스템을 이용한 식물 잎 표면의 산소분포 가시화)

  • Hwang, BaeGeun;Kim, HyeJeong;Lee, SangJoon
    • Journal of the Korean Society of Visualization
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    • v.14 no.1
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    • pp.51-56
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    • 2016
  • Oxygen is a key factor in aerobic reactions and most biological activities. Visualization of oxygen distribution of a chemical process or biological system has been a very challenging object despite of its significance and potential impact. To monitor and visualize the spatial distribution of oxygen concentration, various techniques such as electro-chemical probe, polarographic electrode, LIF(laser-induced fluorescence) and so on have been introduced. Oxygen planar optode which utilizes the oxygen quenching of fluorescence light is one of the currently available methods for time-resolved visualization of oxygen distribution on a planar surface. In this study, we utilized VisiSens oxygen planar optode system to visualize the spatial distribution of oxygen concentration on leaves of Korean azalea. As a result, temporal variation of oxygen concentration distribution caused by respiratory activity of the leaf could be quantitatively monitored.