• 제목/요약/키워드: Fluorescence spectra

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Photohysical Properties of New Psoralen Derivatives:Psoralens Linked to Adenine through Polymethylene Chains

  • Yoo, Dong-Jin;Park, Hyung-Du;Kim, Ae-Rhan;Rho, Young S.;Shim, Sang-Chul
    • Bulletin of the Korean Chemical Society
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    • 제23권9호
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    • pp.1315-1327
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    • 2002
  • The model compounds, 8-methoxypsoralen-CH2O(CH2)n-adenine (MOPCH2OCnAd, n=2, 3, 5, 6, 8, and 10) in which 5 position of 8-methoxypsoralen (8-MOP) is linked by various lengths of polymethylene bridge to N9 of adenine. UV absorption spectra are identical with the sum of MOPCH2OC3 and adenine absorption spectra. Solvent effects on the UV absorption and fluorescence emission spectra indicate that the lowest excited singlet state is the $(\pi${\rightarrow}$\pi*)$ state. The spectral characteristics of the fluorescence of MOPCH2OCnAd are strongly dependent upon the nature of the solvents. The fluorescence emission spectra in aprotic solvents are broad and structureless due to the excimer formation through the folded conformation accelerated by hydrophobic ${\pi}-{\pi}$ stacking interaction. Increasing polarity of the protic solvents leads to higher population of unfolded conformation stabilized through favorable solvation and H-bonding, and consequently to an increase in the fluorescence intensity, fluorescence lifetime, and a shift of fluorescence maximum to longer wavelengths. The decay characteristics of the fluorescence in polar protic solvents shows two exponential decays with the lifetimes of 0.6-0.8 and 1.6-1.9 ns in 5% ethanol/water, while MOPCH2OC3 shows 0.5 and 1.7 ns fluorescence lifetimes. The long-lived component of fluorescence can be attributed to the relaxed species (i.e., the species for which the solvent reorientation (or relaxation) has occurred), while the short-lived components can be associated with the unrelaxed, or only partially relaxed, species.

실시간 광학적 생검에서 형광분광법의 산란과 흡수에 대한 영향 (The Scattering and Absorption Effects of Fluorescence Spectroscopy in a Real Time Optical Biopsy)

  • Han, Seunghee;Muller, Markus G.;Kang, Seunghee;Kang, Haejin
    • 한국의학물리학회지:의학물리
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    • 제12권1호
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    • pp.79-94
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    • 2001
  • 생물학적 조직(Biological Tissue)에서 얻어내는 형광(Fluorescence)은 산란(Scattrering), 흡수(Absorption), 그리고 형광체(Fluorophores)가 원인이 되는, 인트린식 형광(Intrinsic Fluorescence)들에 관한 정보를 갖고 있다. 생물학적 조직의 형광스펙트럼은 조직 내에 존재하는 흡수체(Absorber)와 산란물질(Scatters)들의 영향을 받기 때문에 다른 조직의 생화학적인 인트린식 형광을 선형적인 조합으로 해석할 수 없었다. 생물학적 조직 같은 터비드 매질(Turbid Media)로부터 실험적으로 형광을 얻어서 산란과 흡수의 영향을 조사하기 위하여 본 연구소에서 제작한 장치를 소개하고, 넓은 범위의 흡수체와 산란물질의 농도를 갖고 제작한 조직 팬텀(Tissue Phantom)에 대한 형광과 반사(Reflectance) 스펙트럼을 측정하였다. 형광스펙트럼에 존재하는 산란과 흡수의 왜곡(Distortion)을 제거하기 위하여, 반사스펙트럼에 포함된 산란과 흡수 정보를 이용하는 ‘광자 이동 모델(Photon Migration Model)’을 적용하였고, 이러한 조직모델에 대한 인트린식 형광을 얻었다 연구 결과, 모델 값과 실제 인트린식 형광 스펙트럼이 훌륭하게 일치함을 확인하였다. 이런 연구를 하게된 동기는, 인간의 조직이 병들어서 진화하면 조직의 생화학적 구성의 변화가 발생하고 이때 인트린식 형광의 변화가 생기기 때문이다 결론적으로, 조직에 대한 실시간 광학적 생검에서 병든 조직과 정상조직을 단지 형광스펙트럼만으로 구분하는 것은 어렵지만, 인트린식 형광을 이용하면 가능하다.

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하천수 BOD 예측을 위한 용존 자연유기물질의 synchronous 형광 스펙트럼 분석 (Examining Synchronous Fluorescence Spectra of Dissolved Organic Matter for River BOD Prediction)

  • 허진;박민혜
    • 한국물환경학회지
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    • 제23권2호
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    • pp.236-243
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    • 2007
  • Fluorescence measurements of dissolved organic matter (DOM) have the superior advantages over other analysis tools for the applications to water quality management due to their rapid analysis. It is known that protein-like fluorescence characteristics are well corelated with microbial activities and biodegradable organic matter. In this study, potential biochemical oxygen demand (BOD) predictor were explored using the fluorescence peak intensities and/or the integrated fluorescence intensities derived from synchronous fluorescence spectra and the first derivative spectra of river samples. A preliminary study was conducted using a mixture of a river and a treated sewage to test the feasibility of the approach. It was demonstrated that the better BOD predictor can be derived from synchronous fluorescence spectra and the derivatives when the difference between the emission and the excitation wavelengths (${\Delta}{\gamma}$) was large. The efficacy of several selected fluorescence parameters was rivers in Seoul. The fluorescence parameters exhibited relatively good correlation coefficients with the BOD values, ranging from 0.59 to 0.90. Two parameters were suggested to be the optimum BOD predictors, which were a fluorescence peak at a wavelength of 283 nm from the synchronous spectrum at the ${\Delta}{\gamma}$ value of 75 nm, and the integrated fluorescence intensity of the first derivatives of the spectra at the wavelength range between 245 nm and 280 nm. Each BOD predictor showed the correlation coefficients of 0.89 and 0.90, respectively. It is expected that the results of this study will provide important information to develop a real-time efficient sensor for river BOD in the future.

Fluorescence Characteristic Spectra of Domestic Fuel Products through Laser Induced Fluorescence Detection

  • Wu, Ting-Nien;Chang, Shui-Ping;Tsai, Wen-Hsien;Lin, Cian-Yi
    • 한국지하수토양환경학회지:지하수토양환경
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    • 제19권5호
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    • pp.18-25
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    • 2014
  • Traditional investigation procedures of soil and groundwater contamination are followed by soil gas sampling, soil sampling, groundwater sampling, establishment of monitoring wells, and groundwater monitoring. It often takes several weeks to obtain the analysis reports, and sometimes, it needs supplemental sampling and analysis to delineate the polluted area. Laser induced fluorescence (LIF) system is designed for the detection of free-phase petroleum pollutants, and it is suitable for on-site real-time site investigation when coupling with a direct push testing tool. Petroleum products always contain polycyclic aromatic hydrocarbon (PAH) compounds possessing fluorescence characteristics that make them detectable through LIF detection. In this study, LIF spectroscopy of 5 major fuel products was conducted to establish the databank of LIF fluorescence characteristic spectra, including gasoline, diesel, jet fuel, marine fuel and low-sulfur fuel. Multivariate statistical tools were also applied to distinguish LIF fluorescence characteristic spectra among the mixtures of selected fuel products. This study successfully demonstrated the feasibility of identifying fuel species based on LIF characteristic fluorescence spectra, also LIF seemed to be uncovered its powerful ability of tracing underground petroleum leakages.

Intramolecular Excimer Formation Processes of 1,3-Dipyrenylpropane in Silicate Sol-Gel

  • 권미수;이윤희;안병태;이민영
    • Bulletin of the Korean Chemical Society
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    • 제17권2호
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    • pp.158-162
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    • 1996
  • The steady-state emission and fluorescence lifetimes of 1,3-dipyrenylpropane were measured in silicate sol-gel and xerogel matrices. In sol solution, the fluorescence emission spectra of monomer and excimer resemble those in hydrocarbon solvents. In gel and xerogel condition, however, the fluorescence spectra exhibit significant change, largely confirming the intramolecular motions in gel pores are influenced by microviscosity. The rate constants for intramolecular excimer formation were obtained from the measured fluorescence lifetimes and the rate processes for excimer forming in silicate sol-gel are described by a simple kinetic scheme.

Seasonal Variation of Attenuation Coefficient Spectra Extracted from Yamato Bank Optical Moored Buoy Data

  • Senga, Yasuhiro;Horiuchi, Tomohiro
    • 대한원격탐사학회:학술대회논문집
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    • 대한원격탐사학회 1998년도 Proceedings of International Symposium on Remote Sensing
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    • pp.89-94
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    • 1998
  • Seasonal variation of attenuation coefficient spectra in Japan sea was extracted from underwater radiance/irradiance spectra observed by a moored buoy system developed by National Space Development Agency of Japan (NASDA). The buoy was deployed 9 months from August 31, 1996 to June 1, 1997. Throughout this period, it was collecting downward irradiance and upward radiance spectra under water at the depth of 1.5m and 6.5m everyday. The dairy averaged diffused attenuation coefficient spectra and underwater reflectance spectra were calculated. The results were compared with the absorption spectra of filtered samples obtained by validation cruises, which carried out 5 times during the moored period. Also, the natural fluorescence of chlorophyll a were extracted from the upward radiance spectra observed at 1.5m depth. The seasonal variation of the calculated attenuation coefficient spectra and the natural fluorescence were examined. The result shows a weak blooming of phytoplankton on November and a large blooming on April.

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Synthesis, Crystal Structure, Spectra Characterization and DFT Studies on a Di-Cycle Pyrazoline Derivative

  • Song, Jie;Zhao, Pu Su;Zhang, Wei Guang
    • Bulletin of the Korean Chemical Society
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    • 제31권7호
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    • pp.1875-1880
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    • 2010
  • A dicycle pyrazoline derivative, 1-phenyl-5-(p-fluorophenyl)-3,4-($\alpha$-p-fluoro-tolylenecyclohexano) pyrazoline, was synthesized and characterized by elemental analysis, IR, UV-vis, fluorescence spectra and X-ray single crystal diffraction. Density function theory (DFT) calculations were performed by using B3LYP method with 6-$311G^{**}$ basis set. The optimized geometry can well simulate the molecular structure. Vibrational frequencies were predicted, assigned and compared with the experimental values, which suggest that B3LYP/6-$311G^{**}$ method can well predict the IR spectra. Both the experimental electronic absorption spectra and the predicted ones by B3LYP/6-$311G^{**}$ method reveal three electron-transition bands, with the theoretical ones having some red shifts compared with the experimental data. Natural bond orbital analyses indicate that the absorption bands are mainly derived from the contribution of n $\rightarrow\pi^*$ and $\pi\rightarrow\pi^*$ transitions. Fluorescence spectra determination shows that the title compound can emit blue-light at about 478 nm. On the basis of vibrational analysis, the thermodynamic properties of title compound at different temperature have been calculated, revealing the correlations between $C^0_{p,m}$, $S^0_m$, $H^0_m$ and temperature.

Fluorescence Spectroscopic and Time-Dependent Density-Functional Theory Studies of Diphenylsilane

  • Boo, Bong-Hyun;Lee, Jae-Kwang
    • Bulletin of the Korean Chemical Society
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    • 제33권3호
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    • pp.993-996
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    • 2012
  • We investigated fluorescence and fluorescence excitation of diphenylsilane (DPS) in a solution and molecular beams in combination with the aid of the DFT method. When the molecule was photoexcited at 250 nm in a cyclohexane solution, normal and excimer fluorescences were observed in the ranges of 260-320 and 330-450 nm, respectively. The fluorescence excitation spectrum indicates that the channel leading to the intramolecular excimer formation is not efficient in comparison with the normal fluorescence. Vibrationally resolved fluorescence excitation spectra were measured for the DPS molecules cooled in pulsed supersonic expansion of He in the range 262.2-271.7 nm, in which we can see several electronic excitation spectra exhibiting the electronic band origins. We found that the simulated absorption spectrum based on the time-dependent densityfunctional theory calculations accords well with the absorption spectrum.

Photophysical Behaviors of Biphenylcarboxylic Acids in Various Solvents; Excited-State Geometry Change and Intramolecular Charge Transfer

  • Yoon Minjoong;Cho Dae Won;Lee Jae Young
    • Bulletin of the Korean Chemical Society
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    • 제13권6호
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    • pp.613-620
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    • 1992
  • The solvent-dependent photophysical properties of 2-biphenylcarboxylic acid (2BPCA) and 4-biphenylcarboxylic acid(4BPCA), which have a pre-twisted conformation in the ground state, have been investigated. The fluorescence spectra of 4BPCA show vibrational structure with a non-mirror image to the absorption spectra in nonpolar solvent while those of 2BPCA show no structure even in nonpolar solvents. As the solvent polarity increases, the fluorescence spectra become diffuse and broad with a strong red shift resulting in the large Stokes shift. The large fluorescence Stokes shift of BPCA's in polar solvent is also partially due to an intramolecular charge transfer (ICT) interaction in the excited state, as demonstrated by the large dipole moment in the excited state (7.6-10.6 D). The fluorescence decay behaviors of BPCA's (decay-times and their pre-exponential factors) also depend on solvent polarity in agreement with the solvent-dependent properties of the steady-state fluorecence. The data have been discussed in terms of change in the excited-state potential energy surface with respect to change of the dihedral angle of biphenyl moiety.

Absorption and Fluorescence Spectra of Dy(Ⅲ) Complexes with Some Terdentate Ligands

  • 정승희
    • Bulletin of the Korean Chemical Society
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    • 제13권6호
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    • pp.650-654
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    • 1992
  • Absorption and fluorescence spectra are reported for four different 1 : 3 $Dy^{3+}$ : ligand systems in aqueous solution under mild alkaline pH conditions. The ligands included in this study are oxidiacetate, dipicolinate, iminodiacetate and methyliminodiacetate. The oscillator strengths for the 4f→4f multiplet-to-multiplet transitions are empirically determined from the absorption spectra and the intensity parameters ${\Omega}_{\lambda}$}(${\lambda}$ = 2, 4, 6) for the systems are also obtained by applying the Judd-Ofelt theorem to the observed oscillator strengths. The values of the intensity parameters for the systems are compared and discussed in terms of ligand structural properties to investigate how the intensity parameters can response to the minor changes in the ligand environment. In addition, the relative oscillator strengths for fluorescence are evaluated and compared to the results obtained from absorption spectra.