• Title/Summary/Keyword: Anisotropy decay

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Time-resolved Anisotropy Study on the Excited-State Intramolecular Proton Transfer of 1-Hydroxyanthraquinone

  • Choi, Jun-Rye;Jeoung, Sae-Chae;Cho, Dae-Won
    • Bulletin of the Korean Chemical Society
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    • v.24 no.11
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    • pp.1675-1679
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    • 2003
  • The photodynamics of excited-state intramolecular proton transfer reaction of 1-hydroxyanthraquinone (1-HAQ) and 1-deuterioanthraquinone was investigated in toluene with time-resolved emission and femtosecond transient transmittance techniques at room temperature. The temporal profiles of transient transmittance of 1-HAQ could be well described with multi-decaying time constants. The ultrafast time constant within ca. 260 fs reflects the dynamics of proton transfer. The decay component of 2 ps is assigned to an additional proton translocation process induced by the intramolecular vibrational relaxation, whereas the decay component of 18 ps is assigned to the vibrational cooling process, while the long component (200 ps) can be explained in terms of the relaxation from excited-state keto-tautomer to its ground state. Time-resolved anisotropy decay dynamics and isotope effects on the photodynamics reveals that the ESIPT from enol-tautomer to keto-one of 1-HAQ is barrierless reaction and coupled to a vibrational relaxation process.

Photophysical Model of 10-Hydroxybenzo[h]quinoline: Internal Conversion and Excited State Intramolecular Proton Transfer

  • Lee, Junghwa;Joo, Taiha
    • Bulletin of the Korean Chemical Society
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    • v.35 no.3
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    • pp.881-885
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    • 2014
  • Photophysics of 10-hydroxybenzo[h]quinoline (HBQ) has been in controversy, in particular, on the nature of the electronic states before and after the excited state intramolecular proton transfer (ESIPT), even though the dynamics and mechanism of the ESIPT have been well established. We report highly time resolved fluorescence spectra over the full emission frequency regions of the enol and keto isomers and the anisotropy in time domain to determine the accurate rates of the population decay, spectral relaxation and anisotropy decay of the keto isomer. We have shown that the ~300 fs component observed frequently in ESIPT dynamics arises from the $S_2{\rightarrow}S_1$ internal conversion in the reaction product keto isomer and that the ESIPT occurs from the enol isomer in $S_1$ state to the keto isomer in $S_2$ state.

Study on electro-optical characteristic of FFS mode using LC with a positive dielectric anisotropy according to the magnitude of dielectric anisotropy (양의 액정을 사용하는 FFS mode에서 액정의 유전율 이방성에 따른 전기 광학 특성 연구)

  • An, Young-Joo;Park, Ji-Woong;Jung, Jun-Ho;Lee, Hee-Kyu;Lee, Seung-Eun;Lee, Seung-Hee
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2008.06a
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    • pp.399-400
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    • 2008
  • The light efficiency of fringe-field switching (FFS) mode when using a liquid crystal (LC) with positive dielectric anisotropy was found to be dependent on the magnitude of dielectric anisotropy, such that the lower dielectric anisotropy, the higher. We studied out not only light efficiency but also response time according to dependence on the magnitude of dielectric anisotropy. Rising and decay time became fast and slow respectively according to decreasing the magnitude of dielectric anisotropy. This paper investigates electro-optical characteristic of FFS mode using LC with a positive dielectric anisotropy dependent on the magnitude of dielectric anisotropy of the LC.

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Size Distribution and Temperature Dependence of Magnetic Anisotropy Constant in Ferrite Nanoparticles

  • Yoon, Sunghyun
    • Proceedings of the Korean Magnestics Society Conference
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    • 2012.11a
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    • pp.104-105
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    • 2012
  • The temperature dependence of the effective magnetic anisotropy constant K(T) of ferrite nanoparticles is obtained based on the measurements of SQUID magnetometry. For this end, a very simple but intuitive and direct method for determining the temperature dependence of anisotropy constant K(T) in nanoparticles is introduced in this study. The anisotropy constant at a given temperature is determined by associating the particle size distribution f(r) with the anisotropy energy barrier distribution $f_A(T)$. In order to estimate the particle size distribution f(r), the first quadrant part of the hysteresis loop is fitted to the classical Langevin function weight-averaged with the log?normal distribution, slightly modified from the original Chantrell's distribution function. In order to get an anisotropy energy barrier distribution $f_A(T)$, the temperature dependence of magnetization decay $M_{TD}$ of the sample is measured. For this measurement, the sample is cooled from room temperature to 5 K in a magnetic field of 100 G. Then the applied field is turned off and the remanent magnetization is measured on stepwise increasing the temperature. And the energy barrier distribution $f_A(T)$ is obtained by differentiating the magnetization decay curve at any temperature. It decreases with increasing temperature and finally vanishes when all the particles in the sample are unblocked. As a next step, a relation between r and $T_B$ is determined from the particle size distribution f(r) and the anisotropy energy barrier distribution $f_A(T)$. Under the simple assumption that the superparamagnetic fraction of cumulative area in particle size distribution at a temperature is equal to the fraction of anisotropy energy barrier overcome at that temperature in the anisotropy energy barrier distribution, we can get a relation between r and $T_B$, from which the temperature dependence of the magnetic anisotropy constant was determined, as is represented in the inset of Fig. 1. Substituting the values of r and $T_B$ into the $N{\acute{e}}el$-Arrhenius equation with the attempt time fixed to $10^{-9}s$ and measuring time being 100 s which is suitable for conventional magnetic measurement, the anisotropy constant K(T) is estimated as a function of temperature (Fig. 1). As an example, the resultant effective magnetic anisotropy constant K(T) of manganese ferrite decreases with increasing temperature from $8.5{\times}10^4J/m^3$ at 5 K to $0.35{\times}10^4J/m^3$ at 125 K. The reported value for K in the literatures is $0.25{\times}10^4J/m^3$. The anisotropy constant at low temperature region is far more than one order of magnitude larger than that at 125 K, indicative of the effects of inter?particle interaction, which is more pronounced for smaller particles.

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Dynamics of RNA Bacteriophage MS2 Observed with a Long-Lifetime Metal-Ligand Complex

  • Kang, Jung Sook;Yoon, Ji Hye
    • Journal of Photoscience
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    • v.11 no.1
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    • pp.35-40
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    • 2004
  • [Ru(2,2'-bipyridine)$_2$(4,4'-dicarboxy-2,2'-bipyridine)]$^{2+}$(RuBDc) is a very photostable probe that possesses favorable photophysical properties including long lifetime, high quantum yield, large Stokes' shift, and highly polarized emission. To evaluate the usefulness of this luminophore (RuBDc) for studying macromolecular dynamics, its intensity and anisotropy decays when conjugated to RNA bacteriophage MS2 were examined using frequency-domain fluorometry with a high-intensity, blue light-emitting diode (LED) as the modulated light source. The intensity decays were best fit by a sum of two exponentials, and the mean intensity decay time was 442.2 ns. The anisotropy decay data showed a single rotational correlation time (2334.9 ns), which is typical for a spherical molecule. The use of RuBDc enabled us to measure the rotational correlation time up to several microseconds. These results indicate that RuBDc can be useful for studying rotational diffusion of biological macromolecules.s.

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DYNAMICS OF $tRNA*{val}$ MEASURED WITH A LONG-LIFETIME METAL-LIGAND COMPLEX

  • Kang, Jung-Sook
    • Journal of Photoscience
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    • v.7 no.4
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    • pp.155-159
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    • 2000
  • [Ru(bpy)$_2$(dppz)]$^2$$^{+}$ (bpy = 2,2'-bipyridine, dppz = dipyrido[3,2-a:2',3'-c]phenazine)(RuBD), a long-lifetime metal-ligand complex displays photophysical properties including long lifetime, polarized emission, and very little background fluorescence. To further show the usefulness of this luminophore(RuBD) for probing nucleic acid dynamics, its intensity and anisotropy decays when bound to tRN $A^{val}$ were examined using frequency-domain fluorometry with a blue light-emitting diode(LED)as the modulated light source. Unexpectedly much longer mean lifetime was obtained at 4$^{\circ}C$(<$\tau$>=178.3 ns) as compared to at $25^{\circ}C$(<$\tau$>=117.0 ns), suggesting more favorable conformation of tRN $A^{val}$ for RuBD when intercalated at 4$^{\circ}C$. The anisotropy decay data showed longer rotational correlation times at 4$^{\circ}C$(52.7 and 13.0 ns) than at $25^{\circ}C$ (32.9 and 10.3 ns). The presence of two rotational correlation times suggests that RuBD reveals both local and overall rotational motion of tRN $A^{val}$. Due to long lifetime of RuBD and small size of tRN $A^{val}$, very low steady-state anisotropy values were observed, 0.048 and 0.036 at 4 and $25^{\circ}C$, respectively. However, a clear difference in the modulated anisotropy values was seen between 4 and $25^{\circ}C$. These results indicate that RuBD can be useful for studying hydrodynamics of small nucleic acids such as tRN $A^{val}$.^{val}$.>.$.>.

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Critical Role of Glu175 on Stability and Folding of Bacterial Luciferase: Stopped-flow Fluorescence Study

  • Shirazy, Najmeh Hadizadeh;Ranjbar, Bijan;Hosseinkhani, Saman;Khalifeh, Khosrow;Madvar, Ali Riahi;Naderi-Manesh, Hossein
    • BMB Reports
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    • v.40 no.4
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    • pp.453-458
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    • 2007
  • Bacterial luciferase is a heterodimeric enzyme, which catalyzes the light emission reaction, utilizing reduced FMN (FMNH2), a long chain aliphatic aldehyde and $O_2$, to produce green-blue light. This enzyme can be readily classed as slow or fast decay based on their rate of luminescence decay in a single turnover. Mutation of Glu175 in $\alpha$ subunit to Gly converted slow decay Xenorhabdus Luminescence luciferase to fast decay one. The following studies revealed that changing the luciferase flexibility and lake of Glu-flavin interactions are responsible for the unusual kinetic properties of mutant enzyme. Optical and thermodynamics studies have caused a decrease in free energy and anisotropy of mutant enzyme. Moreover, the role of Glu175 in transition state of folding pathway by use of stopped-flow fluorescence technique has been studied which suggesting that Glu175 is not involved in transition state of folding and appears as surface residue of the nucleus or as a member of one of a few alternative folding nuclei. These results suggest that mutation of Glu175 to Gly extended the structure of Xenorhabdus Luminescence luciferase, locally.

Comparative Dynamics of $tRNA^{val}$ and pBluescript II SK(+) Phagemid Studied with Ethidium Bromide and a Long-lifetime Metal-ligand Complex

  • Kang, Jung-Sook;Yoon, Ji-Hye
    • Journal of Photoscience
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    • v.11 no.3
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    • pp.133-139
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    • 2004
  • The metal-ligand complex, $[Ru(phen)_2(dppz)]^{2+}$ (phen=1,10-phenanthroline, dppz=dipyrido[3,2-a:2',3'-c]phenazine) (RuPD), was used as a spectroscopic probe for studying nucleic acid dynamics. The RuPD complex displays a long lifetime and a molecular light switch property upon DNA binding due to shielding of its dppz ligand from water. To show the usefulness of this luminophore (RuPD) for probing nucleic acid dynamics, we compared its intensity and anisotropy decays when intercalated into the $tRNA^{val}$ and pBluescript (pBS) II SK(+) phagemid through a comparison with ethidium bromide (EB), a conventional nucleic acid probe. We used frequency-domain fluorometry with a blue light-emitting diode (LED) as the modulated light source. The mean lifetime for the $tRNA^{val}$ (<${\tau}$> = 166.5 ns) was much shorter than that for the pBS II SK(+) phagemid (<${\tau}$> = 481.3 ns), suggesting a much more efficient shielding from water by the phagemid. Because of their size difference, the anisotropy decay data showed a much shorter rotational correlation times for the $tRNA^{val}$ (99.9 and 23.6 ns) than for the pBS II SK(+) phagemid (968.7 and 39.5 ns). These results indicate that RuPD can be useful for studying nucleic acid dynamics.

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Assessment of Incipient Decay of Radiata Pine Wood Using Stress-wave Technique in the Transverse Direction (횡단방향(橫斷方向) 응력파(應力波) 방법(方法)에 의(依)한 라디에타소나무의 초기부후(初期腐朽) 평가(評價))

  • Kim, Gyu-Hyeok;Jee, Woo-Guen;Ra, Jong-Bum
    • Journal of the Korean Wood Science and Technology
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    • v.24 no.3
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    • pp.18-27
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    • 1996
  • The feasibility of using stress-wave technique in the transverse direction for the assessment of early stages of decay was investigated using compression test specimens having different annual ring orientations subjected to decay by Tyromyces palustris for various time intervals. Decay detection, quantitative assessment of decay, and the prediction of residual strength of decayed wood with less than five percent weight loss can be feasible using stress-wave parameters (wave velocity, wave impedance, and stress-wave elasticity) and their percent reduction due to decay, measured by stress-wave technique in the transverse direction. The use of stress-wave technique in the transverse direction for the application of this technique to structural members in service is desirable, when considering the easiness of attachment of accelerometers of stress-wave measuring device on the surface of members and also accurate detection of localized decayed areas. In stress-wave technique in the transverse direction, stress-wave parameters measured were different according to the angles between wave propagation path and annual ring, due to the anisotropy of wood structure. Therefore, it is recommended to use percent reduction in stress-wave parameters instead of stress-wave parameters. This evaluation method using percent reduction in stress-wave parameters is ideal when it is impossible to observe annual ring orientation on the transverse surface of wood.

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Enhanced Electro-optical Characteristics of Liquid Crystal Shutter with a Dual Frequency Liquid Crystal Material (이중 주파수 액정을 적용한 액정 셔터의 고속 응답 특성)

  • Kim, Dae Soo;Han, Seung Hwan;Bae, Geon;Jhun, Chul Gyu
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.27 no.5
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    • pp.303-306
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    • 2014
  • In this paper, by using a dual frequency liquid crystal material, we propose a liquid crystal device with a fast response characteristics. The dual frequency liquid crystal material has a positive dielectric anisotropy value at a low frequency. With a high frequency, the dielectric anisotropy becomes negative. Therefore, the relaxation process is governed by not only the elastic deformation, but also the dielectric interaction. The measured decay time and rise time were 0.88 ms and 0.33 ms, respectively.