• Title/Summary/Keyword: polarity shift

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Solvent Effects on the Solvatochromism of 7-Aminocoumarin Derivatives in Neat and Binary Solvent Mixtures: Correlation of the Electronic Transition Energies with the Solvent Polarity Parameters

  • Choi, Jin-Yeong;Park, Eun-Ju;Chang, Seung-Hyun;Kang, Tai-Jong
    • Bulletin of the Korean Chemical Society
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    • v.30 no.7
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    • pp.1452-1458
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    • 2009
  • The change in the electronic absorption and emission energy of 7-aminocoumarin derivatives in binary solvent mixtures has been studied. The electronic transition energy along with the Stokes' shift is correlated with the orientation polarizability of the solvent as well as the empirical solvent polarity parameters $E_T$ (30). It is observed that the emission peak shift traces the change of $E_T$ (30) value very closely in binary solvent mixtures. The emission transition more strongly depends on the solvent polarity than the absorption, which indicates the dipole moment gets larger on excitation. From the dependence of the Stokes’ shift of 7-aminocoumarins with the solvent polarity parameters and the ground state dipole moment obtained by the semi-empirical calculations, the excited state dipole moment was estimated. The fluorescence lifetime change of 7-aminocoumarins in binary solvent mixtures was measured and the results are explained in terms of molecular conformation and solvent polarity. The study indicates the empirical solvent polarity $E_T$ (30) is a good measure of microscopic solvent polarity and it probes in general the non-specific solvent interactions.

Extracting Multiword Sentiment Expressions by Using a Domain-Specific Corpus and a Seed Lexicon

  • Lee, Kong-Joo;Kim, Jee-Eun;Yun, Bo-Hyun
    • ETRI Journal
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    • v.35 no.5
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    • pp.838-848
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    • 2013
  • This paper presents a novel approach to automatically generate Korean multiword sentiment expressions by using a seed sentiment lexicon and a large-scale domain-specific corpus. A multiword sentiment expression consists of a seed sentiment word and its contextual words occurring adjacent to the seed word. The multiword sentiment expressions that are the focus of our study have a different polarity from that of the seed sentiment word. The automatically extracted multiword sentiment expressions show that 1) the contextual words should be defined as a part of a multiword sentiment expression in addition to their corresponding seed sentiment word, 2) the identified multiword sentiment expressions contain various indicators for polarity shift that have rarely been recognized before, and 3) the newly recognized shifters contribute to assigning a more accurate polarity value. The empirical result shows that the proposed approach achieves improved performance of the sentiment analysis system that uses an automatically generated lexicon.

Estimation of Ground and Excited State Dipole Moments of Coumarin 450 by Solvatochromic Shift Method

  • Naik, L.R.;Math, N.N.
    • Journal of Photoscience
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    • v.12 no.2
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    • pp.57-61
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    • 2005
  • The ground and excited state dipole moments of Coumarin 450 (C 450) laser dye were measured at room temperature in several solvents of varying dipole moments. The ground state dipole moment (${\mu}_g$) is estimated by using the modified Onsagar model and the excited state dipole moments (${\mu}_e$) were estimated by the method of solvatochromism as well as by utilizing the microscopic solvent polarity parameter ($E^N_T$). Further, the deviation of some of the points from the linearity of the $E^N_T$ versus Stokes shift indicates the existence of specific type of solute-solvent interaction. The excited state dipole moment of C 450 were found to be higher than those of the ground state and is interpreted in terms of the resonance structure of the molecule. A reasonable agreement has been observed between the values obtained by the method of solvatochromism and modified Onsagar model. It is observed that, corresponding to cyclohexane solution, the fluorescence maxima shift towards the red region with increasing the polarity of the solvents, hence the transition involved are of ${\pi}-{\pi}^*$ type.

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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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    • v.13 no.6
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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.

Design of Carrier Recovery Circuit for High-Order QAM - Part II : Performance Analysis and Design of the Gear-shift PLL with ATC(Automatic Transfer-mode Controller) and Average-mode-change Circuit (High-Order QAM에 적합한 반송파 동기회로 설계 - II부. 자동모드전환시점 검출기 및 평균모드전환회로를 적용한 Gear-Shift PLL 설계 및 성능평가)

  • Kim, Ki-Yun;Kim, Sin-Jae;Choi, Hyung-Jin
    • Journal of the Institute of Electronics Engineers of Korea TC
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    • v.38 no.4
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    • pp.18-26
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    • 2001
  • In this paper, we propose an ATC(Automatic Transfer mode Controller) algorithm and an average-mode-change method for use in Gear shift PLL which can automatically change loop gain. The proposed ATC algorithm accurately detects proper timing or the mode change and has a very simpler structure - than the conventional lock detector algorithm often used in QPSK. And the proposed average mode change method can obtain low errors of estimated frequency offset by averaging the loop filter output of frequency component in shift register. These algorithms are also useful in designing ASIC, since these algorithms occupy small circuit area and are adaptable for high speed digital processing. We also present phase tracking performance of proposed Gear-shift PLL, which is composed of polarity decision PD, ATC and average mode change circuit, and analyze the results by examining constellation at each mode.

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Degradation of Ferroelectric Properties of Pt/PZT/Pt Capacitors in Hydrogen-containing Environment

  • Kim, Dong-Chun;Lee, Won-Jong
    • Transactions on Electrical and Electronic Materials
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    • v.6 no.5
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    • pp.214-220
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    • 2005
  • The ferroelectric properties of the $Pt/PZT(Pb(Zr,Ti)O_3)/Pt$ capacitors are severely degraded when they are annealed in hydrogen-containing environment. Hydrogen atoms created by the catalytic reaction of Pt top electrode during annealing in hydrogen ambient penetrate into PZT films and generate oxygen vacancies by the reduction of the PZT films, which is likely to cause the degradation. The degree of hydrogen-induced degradation and the direction of voltage shift in P-E curves of the pre-poled PZT capacitors after annealing in hydrogen ambient is dependent on the polarity of the pre-poling voltage. This implies that oxygen vacancies causing hydrogen induced degradation are generated by hydrogen ions having a polarity. The degraded ferroelectricity of the PZT capacitors can be effectively recovered by the shift of oxygen vacancies toward the Pt top electrode interface during post-annealing in oxygen environment with applying negative unipolar stressing.

Effect of Deuterated Solvents on the Excited State Photophysical Properties of Curcumin

  • Barik, A.;Goel, N.K.;Priyadarsini, K.I.;Mohan, Hari
    • Journal of Photoscience
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    • v.11 no.3
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    • pp.95-99
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    • 2004
  • Optical absorption and emission studies have been carried out to understand the effect of deuterium on the solvent dependent photophysical properties of curcumin in deuterated solvents such as $CDCl_3,\;(CD_3)_2SO,\;(CD_3)_2CO,\;CD_3OD\;and\;CD_3CN$. Optical absorption spectral studies showed that there is no significant shift in absorption maxima compared to the non-deuterated solvent. The fluorescence maxima shows significant shift with polarity of solvent but not much affected by the deuteration. The fluorescence quantum yield of curcumin increased marginally in almost all the deuterated solvents, indicating reduction in the non-radiative pathways. The fluorescence decay was biexponential in all the solvents and the average fluorescence lifetime was not much affected with deuteration, but showed decrease with increasing solvent polarity. Based on these studies, it is concluded that intermolecular hydrogen transfer is only partially responsible for the excited state deactivation of curcumin.

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Solvent Dependence and Component of Linear Free Energy Relationship on the Chemical Shift of Methylene Proton in 1-(phenoxymethlyl)benzotriazole Derivatives (1-(phenoxymethyl)benzotriazole 유도체 중 methylene 양성자의 chemical shift 에 관한 자유에너지 관계의 조성과 용매 의존성)

  • Nack Do Sung
    • Journal of the Korean Chemical Society
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    • v.33 no.5
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    • pp.538-544
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    • 1989
  • The increase of B-type hydrogen bonding character between the hydrogen atom($H{\gamma}$) of methylene group in 1-(phenoxymethyl)benzotriazole (1) and 1-(thiophenoxymetyl)benzotriazole (2) derivatives, and solvents was caused by some factors such as;electron withdrawing strength (${\rho} > 0$) of X-substituent; local diamagnetic effect by Y atom (Y = O(1) > S(2)) with adjacent methylene group; and solvent polarity parameter ($E_T$ = Kcal/mol; acetone; 42.2 > chloroform; 39.0). From the basis on the findings, linear free energy relationship (LFER) components on the substituent chemical shift of methylene group ($CH_2-SCS$) in (1) exhibited a tendency that resonance(R)-effect was much larger than field(F) (or inductive(I))-effect in acetone and that the electrical effects were depend upon the solvent.

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The Dyeing Properties of Korean Knotweed Extract(Ⅱ) - The UV-visible Spectrophotometric Characteristics of Korean Knotweed Extracts - (호장근 추출액에 의한 염색성(Ⅱ) - 호장근 추출액의 자외 · 가시부 분광 특성 -)

  • Kim, Mi Suk;Choe, Seok Cheol
    • Textile Coloration and Finishing
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    • v.13 no.5
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    • pp.10-10
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    • 2001
  • The Purpose of this study was to investigate spectrophotometric characteristics of Korean knotweed extracts. The properties were evaluated by it′s extracting solvent, effect of metallic ion, variations of pH values and effect of light exposure. The results were as following; The highest absorbance was found in methanol extract of Korean knotweed, while the lowest absorbance was carbon tetrachloride extract. The UV-vis. spectra of Korean knotweed colors in several solvents showed hypsochromic shift of n-π/sup */ transition with the polarity of solvent. Absorbance and peak of UV-vis. spectra of Korean knotweed colors became lower and broader by addition of metallic ion. The light stability in irradiation with xenon ]amp of the color solution with Cu were higher than those of Al and Fe. The UV-vis. spectra of Korean knotweed extracts in various pH values showed bathochromic shift under alkaline condition, and their peaks disappeared after 5 hours exposure.

The Dyeing Properties of Korean Knotweed Extract( II ) - The UV-visible Spectrophotometric Characteristics of Korean Knotweed Extracts - (호장근 추출액에 의한 염색성(II) -호장근 추출액의 자외 . 가시부 분광 특성 -)

  • 김미숙;최석철
    • Textile Coloration and Finishing
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    • v.13 no.5
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    • pp.298-305
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    • 2001
  • The Purpose of this study was to investigate spectrophotometric characteristics of Korean knotweed extracts. The properties were evaluated by it's extracting solvent, effect of metallic ion, variations of pH values and effect of light exposure. The results were as following; The highest absorbance was found in methanol extract of Korean knotweed, while the lowest absorbance was carbon tetrachloride extract. The UV-vis. spectra of Korean knotweed colors in several solvents showed hypsochromic shift of $n->\pi^*$ transition with the polarity of solvent. Absorbance and peak of UV-vis. spectra of Korean knotweed colors became lower and broader by addition of metallic ion. The light stability in irradiation with xenon ]amp of the color solution with Cu were higher than those of Al and Fe. The UV-vis. spectra of Korean knotweed extracts in various pH values showed bathochromic shift under alkaline condition, and their Peaks disappeared after 5 hours exposure.

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