• 제목/요약/키워드: picosecond spectra

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

  • Kim, Hyun-Soo;Chu, Sung-Sil;Kim, Gwi-Eon;Lee, Won-Young;Kim, Ung
    • 한국의학물리학회지:의학물리
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    • 제6권2호
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    • pp.61-70
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    • 1995
  • 헤마토포르피린 유도체는 광역학 치료를 위한 활성감응제로 이용되고 있다. 본 연구는 헤마토포르피린 유도체 분자의 암세포와의 에너지 전달과정을 조사하기 위하여 동시 모드록킹된 색소 레이저와 ~70 피코초 ($10^{-12}$ sec) 시산 분해능을 갖는 단일광자 계수장치 장치를 이용하여 용액에서와 암세포에서 각각 시간분해 형광 스펙트럼을 측정 분석하였다. 측정된 스펙트럼은 deconvolution 방법으로 곡선맞춤되었는데 단량체의 느린 소멸 ($\tau$$_1$=6.3 ㎱)과 이량체의 빠른 소멸 ($\tau$$_1$= 250 ㎰)로 분석되었으며 정상상태에서의 흡수 및 형과 스펙트럼의 결과와 일치하였다. 농도를 일정하게 하고 극성 분자를 5%에서 95%까치 증가시키면서 형광 소멸 곡선을 측정하여 곡선 맞춤과 결과 빠른 소멸성분 ( $A_2$) 값이 증가하였으며 그 증가 폭이 비극성 분자인 메탄올에서 보다 현저하게 나타났다. 헤마토포르피린 유도체 용액에 암세포를 자연 부유시켜 형광 소멸 곡선을 비교 분석한 결과 암세포에 흡착되었을 때 유효 형광 수명 시간이 감소하였다. 이것은 단량체에 비하여 이량체가 암세포의 흡착에 관여하고 있다는 증거로 분석되었다.

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Picosecond Photoionization Processes of N,N,N',N'-Tetramethyl-p-phenylenediamine (TMPD) in Water

  • Lee, Min-Yung;Jang, Du-Jeon;Kim, Dong-Ho;Lee, Sun-Sook;Boo, Bong-Hyun
    • Bulletin of the Korean Chemical Society
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    • 제13권1호
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    • pp.17-20
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    • 1992
  • Photoionization processes of TMPD in $H_2O$ and $D_2O$ were studied, by measuring steady-state absorption, emission, fluorescence excitation spectra, and fluorescence lifetimes on picosecond time scale. The steady-state absorption spectra showed that there exists a cation-ion pair (Wurster's Blue) in $H_2O$ and in $D_2O$ in the electronic ground state. Temperature and excitation wavelength dependence were also studied and the results show that the photoionization reaction in water is an activated process and the fluorescence lifetime is independent of the vibrational excess energy in the uv excitation range of 283-310 nm.

평행판 도파관 THz 분광을 이용한 폭발물 RDX 검출 (Detection of Explosive RDX using Parallel Plate Waveguide THz-TDS)

  • 유병화;정동철;강승범;곽민환;강광용
    • 전기학회논문지
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    • 제61권12호
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    • pp.1939-1943
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    • 2012
  • In this paper we presented the detection of the explosive material RDX using a parallel plate waveguide (PPWG) THz time domain spectroscopy (TDS). Normally the explosive materials have been characterized through identification of vibrational fingerprint spectra. Until now, most of all THz spectroscopic measurements have been made using pellet samples where disorder effects contribute to line broadening such that individual resonances merge into relatively broad absorption features. In order to avoid such disadvantages we used the technique of PPWG THz-TDS to achieve sensitive characterization of explosive material RDX. The PPWG THz-TDS used in this work well established ultrafast optoelectronic techniques to generate and detect sub-picosecond THz pulses. The explosive material was analyzed as powder layers in $112{\mu}m$ gap of metal PPWG. The thin later mass was estimated to be about $700{\mu}g$. Finally, we showed spectra of explosives from 0.2 to 2.4 THz measured using PPWG THz-TDS.

PROTEIN CONFORMATIONS OF OCTOPUS RHODOPSIN AND ITS DEPROTONATED PHOTOCYCLE INTERMEDIATE MONITORED BY ABSORPTION AND PROTEIN FLUORESCENCE

  • Jang, Du-Jeon;Lee, SunBae
    • Journal of Photoscience
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    • 제2권1호
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    • pp.19-25
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    • 1995
  • Picosecond time-resolved and static protein fluorescence spectra and absorption spectra of octopus rhodopsin, a photorecepting protein, are measured and compared with those of bacteriorhodopsin, a photon-induced proton pumping protein, to understand the protein conformations and functions of octopus rhodopsin and its deprotonated photocycle intermediate. The bluer and weaker absorption of retinal indicates that octopus rhodopsin is better in thermal noise suppression but less efficient in light harvesting than bacteriorhodopsin. The protein fluorescence of octopus rhodopsin shows the characteristic of Trp only and the uantum efficiency and lifetime variations may result primarily from variations in the coupling strength with the retinal. The stronger intensity by four times and larger red shift by 12 nm of fluorescence suggest that octopus rhodopsin has more open and looser structure compared with bacteriorhodopsin. Fluorescence decay profiles reveal two decay components of 300 ps (60%) and 2 ns (40%). The deprotonation of protonated Schiff's base increases the shorter decay time to 500 ps and enhances the fluorescence intensity by 20%. The fluorescence and its decay time from Trp residues near retinal are influenced more by the deprotonation. The increase of fluorescence intimates that protein structure becomes loosened and relaxed further by the deprotonation of protonated Schiff's base. The driving force of sequential changes initiated by absorption of a photon is too exhausted after the deprotonation to return the intermediate to the ground state of the begun rhodopsin form.

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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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    • 제31권12호
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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.

Guided Wave THz Spectroscopy of Explosive Materials

  • Yoo, Byung-Hwa;Kang, Seung-Beom;Kwak, Min-Hwan;Kim, Sung-Il;Kim, Tae-Yong;Ryu, Han-Cheol;Jun, Dong-Suk;Paek, Mun-Cheol;Kang, Kwang-Yong;Chung, Dong-Chul
    • Journal of electromagnetic engineering and science
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    • 제11권1호
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    • pp.42-50
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    • 2011
  • One of the important applications of THz time-domain spectroscopy (TDS) is the detection of explosive materials through identification of vibrational fingerprint spectra. Most recent THz spectroscopic measurements have been made using pellet samples, where disorder effects contribute to line broadening, which results in the merging of individual resonances into relatively broad absorption features. To address this issue, we used the technique of parallel plate waveguide (PPWG) THz-TDS to achieve sensitive characterization of three explosive materials: TNT, RDX, and HMX. The measurement method for PPWG THz-TDS used well-established ultrafast optoelectronic techniques to generate and detect sub-picosecond THz pulses. All materials were characterized as powder layers in 112 ${\mu}m$ gaps in metal PPWG. To illustrate the PPWG THz-TDS method, we described our measurement by comparing the vibrational spectra of the materials, TNT, RDX, and HMX, applied as thin powder layers to a PPWG, or in conventional sample cell form, where all materials were placed in Teflon sample cells. The thin layer mass was estimated to be about 700 ${\mu}g$, whereas the mass in the sample cell was ~100 mg. In a laboratory environment, the absorption coefficient of an explosive material is essentially based on the mass of the material, which is given as: ${\alpha}({\omega})=[ln(I_R({\omega})/I_S({\omega}))]m$. In this paper, we show spectra of 3 different explosives from 0.2 to 2.4 THz measured using the PPWG THz-TDS.

Suppression of the Methyl Radical Loss from Acetone Cation within (CH3COCH3)n{CH3COCH3}+ Clusters

  • Lee, Yong-Hoon;Oh, Myoung-Kyu;Choi, Sung-Chul;Ko, Do-Kyeong;Lee, Jong-Min
    • Bulletin of the Korean Chemical Society
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    • 제29권8호
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    • pp.1519-1524
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    • 2008
  • We have investigated the photophysics of the acetone radical cation in the vacuum ultraviolet energy region by multiphoton ionization combined with time-of-flight mass spectrometry in a cluster beam. We have found that the loss of methyl radical from the acetone radical cations is remarkably suppressed at 10.5 eV when they are solvated by a few neutral acetone molecules. The cluster ion mass spectra obtained by nanosecond and picosecond laser pulses reveal that there are intermolecular processes, occurring in several tens of picoseconds, which are responsible for the survival of the acetone cations in clusters. This remarkable solvation effect on the yield of the methyl radical loss from the acetone cation can be rationalized by the intracluster vibrational energy redistribution and the self-catalyzed enolization which compete with the methyl radical loss process.