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Conformational Dynamics of Heme Pocket in Myoglobin and Hemoglobin

  • Kim, Seong-Heun;Heo, Jeong-Hee;Lim, Man-Ho
    • Bulletin of the Korean Chemical Society
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    • v.26 no.1
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    • pp.151-156
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    • 2005
  • The conformational dynamics of heme pocket, a small vacant site near the binding site of heme proteins -myoglobin (Mb) and hemoglobin (Hb), was investigated after photolysis of carbon monoxide from MbCO and HbCO in D$_2$O solution at 283 K by probing time-resolved vibrational spectra of photolyzed CO. Two absorption bands, arising from CO in the heme pocket, evolve nonexponentially in time. The band at higher energy side blue shifts and broadens with time and the one at lower energy side narrows significantly with a negligible shift. These spectral evolutions are induced by protein conformational changes following photolysis that modify structure and electric field of heme pocket, and ligand dynamics in it. The conformational changes affecting the spectrum of photolyzed CO in heme pocket likely modulates ligand-binding activity.

Time Resolved Infrared Spectroscopy of Electro-optic Switching of 5CB

  • Jang, Won-Gun
    • Journal of Information Display
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    • v.5 no.1
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    • pp.34-40
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    • 2004
  • Time resolved infrared IR absorption spectroscopy is carried out to investigate the dynamics of electric field induced reorientation of the biphenyl molecular core and alkyl tail sub-fragments of the nematic liquid crystal 5CB (4-pentyl-4-cyano-biphenyl). The planar to homeotropic transition for high pre-tilt planar aligned cells, is studied for switching times ranging from 200 ${\mu}sec$ down to 80 ${\mu}sec$, the latter a factor of 1000 times faster than any previous nematic IR study. The reorientation rates of the core and tail are found to be the same to within experimental error and scale inversely with applied field squared, as expected for the balance of field and viscous torques. Thus any molecular conformation change during switching must relax on a shorter time scale. A simple model shows that no substantial differences exist between the reorientational dynamics of the tails and cores on the time scales longer than on the order of 10 ${\mu}s$.

Structural Dynamics of Myoglobin Probed by Femtosecond Infrared Spectroscopy of the Amide Band

  • Kim, Seong-Heun;Jin, Geun-Young;Lim, Man-Ho
    • Bulletin of the Korean Chemical Society
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    • v.24 no.10
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    • pp.1470-1474
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    • 2003
  • The dynamics of the tertiary conformation of myoglobin (Mb) after photolysis of carbon monoxide was investigated at 283 K solution by probing amide I and II bands using femtosecond IR absorption spectroscopy. Time-resolved spectra in the amide region evolve with 6-12 ps time scale without noticeable subpicosecond dynamics. The spectra measured at 100 ps delay after photolysis is similar to the difference FTIR spectrum at equilibrium. Time-resolved spectra of photoexcited Mb evolve modestly and their amplitudes are less than 8% of those of photolyzed MbCO, indicating that thermal contribution to the spectral evolution in the amide region is negligible. These observations suggest that the conformational relaxation ensuing photolysis of MbCO be complex and the final deoxy protein conformation have been substantially formed by 100 ps, probably with 6- 12 ps time constant.

Delayed auger recombination in silicon measured by time-resolved X-ray scattering

  • Jo, Wonhyuk;Landahl, Eric C.;Kim, Seongheun;Lee, Dong Ryeol;Lee, Sooheyong
    • Current Applied Physics
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    • v.18 no.11
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    • pp.1230-1234
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    • 2018
  • We report a new method of measuring the non-radiative recombination rate in bulk Silicon. Synchrotron timeresolved x-ray scattering (TRXS) combines femtometer spatial sensitivity with nanosecond time resolution to record the temporal evolution of a crystal lattice following intense ultrafast laser excitation. Modeling this data requires an Auger recombination time that is considerably slower than previous measurements, which were made at lower laser intensities while probing only a relatively shallow surface depth. We attribute this difference to an enhanced Coulomb interaction that has been predicted to occur in bulk materials with high densities of photoexcited charge carriers.

Time-resolved Analysis for Electroconvective Instability under Potentiostatic Mode (일정 전위 모드에서의 전기와류 불안정성에 대한 시간-분해 해석)

  • Lee, Hyomin
    • Korean Chemical Engineering Research
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    • v.58 no.2
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    • pp.319-324
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    • 2020
  • Electroconvective instability is a non-linear transport phenomenon which can be found in ion-selective transport system such as electrodialysis, Galvanic cell and electrolytic cell. The instability is triggered by the fluctuation of space charge layer in adjacent of ion-selective surface, leading to increase of mass transport rate. Thus, in the aspect of mass transport, the instability has an important meaning. Although recent experimental techniques have opened up an avenue to direct visualize the instability, fundamental investigations have been conducted in limited area due to several experimental limitations. In this work, the electroconvective instability under potentiostatic mode was solved by numerical method in order to demonstrate correlation between current-time curve and the instability behavior. By rigorous time-resolved analysis, the transition behaviors can be divided into three stages; formation of space charge layer - growth of electroconvective instability - steady state. Furthermore, scaling laws of transition time were numerically obtained according to applied voltage as well.

Picosecond Dynamics of CN--Ligated Ferric Cytochrome c after Photoexcitation Using Time-resolved Vibrational Spectroscopy

  • Kim, Joo-Young;Park, Jae-Heung;Chowdhury, Salina A.;Lim, Man-Ho
    • Bulletin of the Korean Chemical Society
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    • v.31 no.12
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    • pp.3771-3776
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    • 2010
  • The dynamics of the $CN^-$-ligated ferric cytochrome c (CytcCN) in $D_2O$ at 283 K following Q-band photoexcitation at 575 nm was observed using femtosecond time-resolved vibrational spectroscopy. The equilibrium vibrational spectrum of the CN stretching mode of CytcCN shows two overlapping bands: one main band (82%) at $2122\;cm^{-1}$ with $23\;cm^{-1}$ full width at half maximum (fwhm) and the other band (18%) at $2116\;cm^{-1}$ with $7\;cm^{-1}$ fwhm. The time-resolved spectra show bleaching of the CN fundamental mode of CytcCN and two absorption features at lower energies. The bleach signal and both absorption features are all formed within the time resolution of the experiment (< 200 fs) and decay with a life time of 1.9 ps. One transient absorption feature, appearing immediately red to the bleach signal, results from the thermal excitation of low-frequency modes of the heme that anharmonically couple to the CN fundamental mode, thereby shifting the CN mode to lower energies. The shift of the CN mode decays with a lifetime of 2 ps, equivalent to the time scale for vibrational cooling of the low-frequency heme modes. The other transient absorption feature, which is 3.3 times weaker than the bleach signal and shifted $27\;cm^{-1}$ toward lower energies, is attributed to the CN mode in an electronically excited state where the CN bond is weakened with a lowered extinction coefficient. These observations suggest that photoexcited CytcCN mainly undergoes ultrafast radiationless relaxation, causing photo-deligation of $CN^-$ from CytcCN highly inefficient. As also observed in $CN^-$-ligated myoglobin, inefficient ligand photodissociation might be a general property of $CN^-$-ligated ferric hemes.

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.

Measurements of Optical Constants of Biomedical Media Based on Time-Resolved Reflectance (시간 분해 반사율 측정에 의한 다중산란 매질의 광학 계수 측정)

  • Jeon, K.J.;Park, S.H.;Kim, U.;Yoon, K.W.;Kim, W.K.
    • Proceedings of the KOSOMBE Conference
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    • v.1996 no.05
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    • pp.235-239
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    • 1996
  • In recent years, the optical properties of multiple-scattering media like tissue have been studied for their potential applications in medicine. In this work the optical properties of multiple scattering media were investigated using the time-resolved reflectance measurement. The reflected light was measured by time-correlated single photon counting system. The transport scattering and absorption coefficient are related to the initial rapid decay and the subsequent decay in reflected light, respectively. Also the optical properties of the samples were measured by conventional method, ie., using continuous wave light. When the distance between the light source and the detector is over 8mm, the optical coefficient can be measured accurately using the suggested method.

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Nonlinear Optical Properties and Photoluminescence of CuCl Nanocrystals Embedded in Silica Glass

  • 이민영
    • Bulletin of the Korean Chemical Society
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    • v.16 no.2
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    • pp.126-129
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    • 1995
  • Linear and nonlinear optical properties of CuCl nanocrystals in silica glass have been studied using low temperature absorption, degenerate four wave mixing (DFWM), and time-resolved photoluminescence spectroscopy. Assuming a spherical shape, effective radius of the CuCl quantum dots was estimated to be 2.5 nm, which is obtained from low temperature absorption data. The DFWM experiment was performed in 380-386 nm wavelength region, and the diffracted signal was measured as a function of wavelength with 1.0 nm interval. Time-resolved photoluminescence measurement was also carried out at 77 K to obtain the time response of CuCl nanocrystals. The experimental results on the large third order nonlinear optical of CuCl quantum dots are explained in terms of crystal size and oscillator strength of quantum spheres.