• Title/Summary/Keyword: Circular dichroism spectrum

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Induced Circular Dichroism Spectra and Chromatography by Interaction of Some Racemic Cobalt (III) Complexes and d-Tartrate$^2$- in Aqueous Solution (d-주석산이온과 라세미코발트(III) 착물과의 상호작용에 따른 유발원편광이색성 Spectra와 크로마토그래피)

  • Chang Eon Oh;Dae Ho Kang;Gab Choul Shin
    • Journal of the Korean Chemical Society
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    • v.25 no.5
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    • pp.306-310
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    • 1981
  • Induced circular dichroism spectra of racemic cobalt(III) complexes for $[Co(en)_3]^{3+},\;[Co(tn_)3]^{3+},\;cis-[Co(NH_3)(en)_2]^{3+},\;[Co({\beta}-ala)(en)2_]^{2+},\;[Co(gly)(en)_2]^{2+}\;and\;[Co(acac)(en)_2]^{2+}$ were measured when they were dissolved in aqueous d-tartrate2- solution at room temperature. Only a single negative CD spectrum was observed for all the complexes above in visible region(400∼500nm). It was interpreted that these CD bands were attributed to the difference in interaction between ${\Lambda}$-and ${\Delta}$-enantiomers with d-tartrate$^{2-}$. Namely, when d-tartrate$^{2-}$ was added to ${\Lambda}$-enantiomer and ${\Delta}$-enantiomer, it caused ${\Lambda}$-enantiomer to change greatly and ${\Delta}$-enantiomer to change only slightly; combined the results proved induced circular dichroism. The enantiomer for which the eluent has a stronger affinity should be eluted faster in ion-exchange column chromatography. It is possible to predict the elution order of chromatography from the sign of the induced CD if stronger interaction of chiral anion with the complex leads to greater change in the natural CD spectrum of the complex. The elution order was in complete agreement with the prediction from the sign of the induced CD spectrum for all the measured complexes.

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Absolute Configurations of (±)-Glabridin Enantiomers

  • Kim, Mi-Hyang;Kim, Soo-Un;Kim, Yong-Ung;Han, Jae-Hong
    • Bulletin of the Korean Chemical Society
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    • v.30 no.2
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    • pp.415-418
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    • 2009
  • Concerned with ambiguous stereochemistry assignment of natural (+)-glabridin, absolute configurations of (${\pm}$)-glabridin enantiomers were studied with synthetic glabridin. Synthetic glabridin enantiomers were separated by semi-preparative Sumi-chiral column chromatography, and characterized by UV-Vis and NMR spectroscopy. Three-dimensional molecular structure of glabridin was obtained as equatorial Ph-3 half chair chroman ring from semi-empirical PM3 calculation, and refined by coupling constants in $^1H$ NMR spectrum. Finally, absolute configurations of two enantiomers were determined by circular dichroism spectroscopy based on the empirical helicity rules. Absolute configuration of natural (+)-glabridin was confirmed as (R)-glabridin, as known.

Cu(II) Complexes Conjugated with 9-Aminoacridine Intercalator: Their Binding Modes to DNA and Activities as Chemical Nuclease

  • Kim, Jung-Hee;Youn, Mi-Ryung;Lee, Young-Ae;Kim, Jong-Moon;Kim, Seog-K.
    • Bulletin of the Korean Chemical Society
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    • v.28 no.2
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    • pp.263-270
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    • 2007
  • New mono- and bis-Cu(II)-triazacyclononane(tacn) complex that conjugated with 9-aminoacridine were synthesized, and their binding modes and DNA cleavage activity were investigated in this study. When the classic intercalator, 9-aminoacridine, was conjugated to mono- and bis-Cu(II)-tacn complexes, a significant red-shift and hypochromism in absorption spectrum was apparent in the acridine absorption region upon binding to DNA. Furthermore, the magnitude of the negative reduced linear dichroism signal in the substrate absorption region appeared to be larger than that in the DNA absorption region. These spectral observations indicated that the acridine moiety intercalated when the Cu(II)-tacn complex was conjugated. In contrast, from a close analysis of the circular and linear dichroism spectrum, the aminoacridine-free bis-Cu(II)-tacn complex was concluded to bind at the phosphate groups of DNA. The 9-aminoacridine-free-bis-Cu(II)-tacn complex produces the nicked and linear DNA. On the other hand, 9-aminoacridine conjugated mono-and bis-Cu(II)-tacn complexes showed unspecific binding with negligible DNA cleavage.

Circular Dichroism Spectra on the Counter Ions and the Solvent Dependence of trans-$[Co(R,R-chxn)_2Cl_2]^+$ Complex (trans-[Co(R,R-chxn)$_2Cl_2]^+$ 착물의 대이온 및 용매의존성 원편광이색성 스펙트라)

  • Chang Eon Oh;Yang Kim;Sung Yeul Park;Myung Ki Doh
    • Journal of the Korean Chemical Society
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    • v.35 no.5
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    • pp.493-499
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    • 1991
  • The circular dichroism (CD) spectrum of trans-[Co(R,R-chxn)$_2Cl_2]^+$ complex with different counter-ions have been measured in several organic solvents, where R,R-chxn is (1R,2R)-1,2-diaminocyclohexane. The observed variations in the CD spectrum of the complex exhibited remarkable solvent dependences. And it has been observed that the degree of the change of CD spectrum in the first absorption band region $(^1A_{2g})$ depends on the donor number (DN) of the solvents. From $^1H$ NMR spectrum, it is interpreted that these variations in the CD spectrum of trans-[Co(R,R-chxn)$_2Cl_2]^+$ complex are due to the favorable interaction between solvent molecules and the equatorial N-H protons of R,R-chxn ligands.

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NMR and Circular Dichroism Studies on Human CD99 Transmembrane Domain

  • Kim, Hai-Young;Shin, Joon;Shin, Young-Kee;Park, Seong-Hoe;Lee, Weon-Tae
    • Journal of the Korean Magnetic Resonance Society
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    • v.7 no.1
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    • pp.37-45
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    • 2003
  • Human CD99 is a ubiquitous 32-kDa transmembrane protein encoded by mic2 gene. Recently it has been reported that expression of a splice variant of CD99 transmembrane protein (Type I and Type II) increases invasive ability of human breast cancer cells. To understand structural basis for cellular functions of CD99 Type II, we have initiated studies on hCD99$\^$TMcytoI/ using circular dichroism (CD) and multi-dimensional NMR spectroscopy. CD spectrum of hCD99$\^$TMytoI/ in the presence of 200mM DPC and CHAPS displayed an existence ${\alpha}$-helical conformation, showing that it could form an ${\alpha}$-helix under membrane environments. In addition, we have found that the cytoplasmic domain of CD99 would form symmetric dimmer in the presence of transmembrane domain. Although it has been rarely figured out the correlation between structure and functional mechanism of hCD99$\^$TMcytoI/, the dimerization or oligomerization would play an important role in its biological function.

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Interaction of Ruthenium(II)[(1,10-phenanthroline)2benzodipyrido[3,2-a:2',3'-c]-phenazine]2+ with Single Stranded Poly(dA) and Poly(dT): Turning off the Light Switch

  • Lee, Jeong-Mi;Choi, Ji-Yoon;Kim, Jong-Moon;Lee, Sang-Yong;Lee, Hyo-Sun;Kim, Seog-K.;Cho, Tae-Sub
    • Bulletin of the Korean Chemical Society
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    • v.28 no.6
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    • pp.965-969
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    • 2007
  • The spectral properties, namely the circular dichroism, electric absorption and luminescence properties, of Λ- and Δ-[Ru(II)(1,10-phenanthroline)2benzodipyrido[b:3,2-h:2',3'-j]phenazine]2+ ([Ru(phen)2BDPPZ]2+) in the presence and absence of single stranded poly(dA) and poly(dT) were compared in this work. In the presence of single stranded DNAs, hypochromism in the absorption spectrum and significant changes in the circular dichroism spectrum in the ligand absorption band were apparent, indicating the strong interaction of the [Ru(phen)2BDPPZ]2+ complex with the single stranded DNAs. The luminescence intensity of the Ru(II) complex decreased stoichiometrically with increasing concentrations of the single stranded DNAs. All of these spectral changes were independent of the configuration of the Ru(II) complex and the nature of the DNA bases. Therefore, it is conceivable that both enantiomers of the [Ru(phen)2BDPPZ]2+ complex interact electrostatically with the negatively charged phosphate groups of DNA. However, the spectral properties of [Ru(II)(1,10-phenanthroline)3]2+ were not altered even in the presence of single stranded DNAs. Therefore, the size of the ligand involved in the interaction of the metal complex with the phosphate group of DNA may play an important role, even when the nature of the interaction is electrostatic.

Effect of Acetylation on Conformation of Glycinin (아세틸화가 Glycinin의 구조에 미치는 영향)

  • Kim, Kang-Sung;Rhee, Joon-Shick
    • Korean Journal of Food Science and Technology
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    • v.21 no.5
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    • pp.714-720
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    • 1989
  • Effects of acetylation on conformational changes of glycinin was studied using solvent perturbation, second derivative spectroscopy, near uv circular dichroism spectra and viscosity. Glycinin with purity of more than 93% was used for the experiment. Modification was carried out with acetic anhydride and glycinin with lysine residue modification of 0%, 28%, 65%, 85%, and 95% were used for the experiment. The result of solvent perturbation using some selected perturbants, such as glycerol, ethylene glycol, and dimethyl sulfoxide revealed that acetylation has caused increase In solvent accessibility of tyrosine residues from less than 40% in native protein to more than 70% for 95% acetylated glycinin. This was confirmed by second derivative spectroscopy. Near ultraviolet circular dichroism revealed that the spectra of native and acetylated glycinin were almost identical differing only in intensity and no other useful information could be derived from it. However, in the case of 95% acetylated glycinin the influence of tryptophan on the spectrum was more pronounced Specific viscosity of glycinin also increased by modification, the extent of which depended upon the degree of acetylation. These results supported that acetylation had caused globular conformation of glycinin to be expanded and denatured.

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Interaction of Cu(II)-meso-tetrakis(n-N-methylpyridiniumyl)porphyrin (n = 2,3,4) with Native and Synthetic Polynucleotides Probed by Polarized Spectroscopy

  • Lee, Mi-Jin;Lee, Gil-Jun;Lee, Dong-Jin;Kim, Seog-K.;Kim, Jong-Moon
    • Bulletin of the Korean Chemical Society
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    • v.26 no.11
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    • pp.1728-1734
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    • 2005
  • The interactions of Cu(II)-meso-Tetrakis(n-N-methylpyridiniumyl)porphyrin (n = 2,3,4), respectively referred to as o-, m- and p-CuTMPyP, and DNA, poly$[d(A-T)_2]$ and poly$[d(G-C)_2]$ were investigated by circular and linear dichroism (CD and LD). In the o-CuTMPyP case, in which the rotation of the pyridinium ring is prevented, the shape of the CD spectrum when associated to DNA and poly$[d(A-T)_2]$ resembles and is characterized by a positive band at a low drug to DNA concentration ratio (R ratio) and is bisignate at a high R ratio. The former CD spectrum shape has been attributed to porphyrin that is bound monomerically outside of DNA while the latter can be attributed to those that are stacked. When o-CuTMPyP is bound to poly$[d(G-C)_2]$, the excitonic CD appeared at a relatively high R ratio. In contrast, a characteristic negative CD band in the Soret region was apparent for both m- and p-CuTMPyP when bound to DNA and poly$[d(G-C)_2]$ at the low R ratios, indicating that the porphyrin molecule intercalates. However, the DNA is bent near the intercalation site and the plane of the porphyrin molecule tilts relative to the DNA helix axis, as judged by the magnitude of the reduced LD. Various stacking patterns were identified by the shape of the CD spectrum for m- and p-CuTMPyP when bound to poly$[d(A-T)_2]$. Three species for the former complex and two for the latter complex were found which may reflect the extent of the stacking.

XMCD and PES study of a compensated-ferrimagnetic half-metal Mn3Ga

  • Seong, Seungho;Lee, Eunsook;Kim, Hee Yeon;Kim, Younghak;Baik, Jaeyoon;Kang, J.S.
    • Current Applied Physics
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    • v.18 no.11
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    • pp.1190-1195
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    • 2018
  • By employing soft X-ray magnetic circular dichroism (XMCD), soft X-ray absorption spectroscopy (XAS), and photoemission spectroscopy (PES), we have investigated the electronic structure of the candidate zero-moment half-metallic $Mn_3Ga$. We have studied the ball-milled and annealed $Mn_3Ga$ powder samples that exhibit nearly zero magnetization. Mn 2p XAS revealed that Mn ions in $Mn_3Ga$ are nearly divalent for both of the Mn ions having the locally octahedral symmetry and those having the locally tetrahedral symmetry. The measured Mn 2p XMCD spectrum of $Mn_3Ga$ is very similar to that of ferrimagnetic $MnFe_2O_4$ having divalent Mn ions. The sum-rule analysis of the Mn 2p XMCD spectrum shows that both the spin and orbital magnetic moments of Mn ions in $Mn_3Ga$ are negligibly small, in agreement with the nearly compensated-ferrimagnetic ground state of $Mn_3Ga$. The valence-band PES spectrum of $Mn_3Ga$ agrees well with the calculated density of states, supporting the half-metallic electronic structure of $Mn_3Ga$.

Cyclic Oligopyrroles as Sensors for Absolute Configuration Determination of Carboxylic Acids

  • Lintuluoto Juha M.;Nakayama Kana;Setsune Jun-Ichiro
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.241-241
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    • 2006
  • Absolute configuration of carboxylic acids, including amino acids can be determined by circular dichroism (CD) exciton chirality method. This method employs cyclic oligopyrroles able to form stable complexes with carboxylic acids. Addition of carboxylic acids to the oligopyrroles induce CD spectrum at the macrocycle absorption region and in which the sign of the $1^{st}$ Cotton effect is determined solely by the absolute configuration of the carboxylic acid. The basicity of the pyrrole nitrogen can be controlled by macrocycle substitution thus yielding more sensitive chirality sensors.

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