• 제목/요약/키워드: spectroscopic titration

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Transition-Metal-Mediated Cytotoxicity of Quinolones to L1210 Cells

  • Ko, Tong-Sung;Kwon, Tae-Ik;Kim, Moon-Jip;Park Il-Hyeon;Ryu Hyeong-Won
    • Bulletin of the Korean Chemical Society
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    • 제15권6호
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    • pp.442-448
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    • 1994
  • Transition metals tested, $Cu^{2+}$, and $Ni^{2+}$, were found effective in the induction of the cytotoxicity of the quinolones tested, nalidixic acid, oxolinic acid, and pipemidic acid, against L1210 leukemia cells in vitro, whereas the alkaline earth metal, $Mg^{2+}$, was not. The differential effect of the metals on the quinolone cytotoxicity can be explained by their different mode of interaction with the quinolones. Our present difference spectroscopic titration data suggest that the transition metals can form DNA-intercalating agents, with the quinolones, which can cause the cytotoxicity.

An Eurpium(III) Hydrolytic Catalyst Favoring Anionic Phosphate Esters over Phosphate Triester'

  • 윤창원;오순진;전영진;최영서;손윤경;황보석;구자강;박준원
    • Bulletin of the Korean Chemical Society
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    • 제22권2호
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    • pp.199-204
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    • 2001
  • A Cryptate (221) having a short alcohol pendant (2) was metallated with europium(Ⅲ) in anhydrous condition, and its hydrolytic activity for phosphate esters at neutral pH was examined. While the activity for the phosphate diester and monoester is comparable to that of the parent metal complex [1Eu]3+, its hydrolytic activity towards a phosphate triester is significantly suppressed. Potentiometric titration and luminescence spectroscopic studies for the equilibrium behavior of the complex in solution suggest that a dimer formation through the metal hydroxides as well as the pendant alcohol is likely to happen. The low hydrolytic activity for the triester seems to be associated with the dimer formation.

NMR Spectroscopic Analysis on the Chiral Recognition of Noradrenaline by β-Cyclodextrin ( β-CD) and Carboxymethyl- β-cyclodextrin (CM- β-CD)

  • Lee, Sang-Hoo;Yi, Dong-Heui;Jung, Seung-Ho
    • Bulletin of the Korean Chemical Society
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    • 제25권2호
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    • pp.216-220
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    • 2004
  • ${\beta}$-CD and CM- ${\beta}$-CD as chiral NMR shift agents were used to resolve the enantiomers of noradrenaline (NA). The stoichiometry of each complex formed between the CDs and the enantiomers of NA was found to be 1 : 1 through the continuous variation plots. The binding constants (K) of the complexes were determined from $^1H$ NMR titration curves. This result indicated that both ${\beta}$-CD and CM- ${\beta}$-CD formed the complexes with the S(+)-NA more preferentially than its R(-)-enantiomer. The K values for the complexes with ${\beta}$-CD ($K_{S(+)}$ = 537 $M^{-1}$ and $K_{R(-)}$ = 516 $M^{-1}$ was larger than those with CM- ${\beta}$-CD ($K_{S(+)}$ = 435 $M^{-1}$ and $K_{R(-)}$ = 313 $M^{-1}$), however, enantioselectivity (${\alpha}$) of S(+)- and R(-)-NA to CM- ${\beta}$-CD ( ${\alpha}$ = 1.38) was larger than that to ${\beta}$-CD ( ${\alpha}$ = 1.04), indicating that CM- ${\beta}$-CD was the better chiral NMR solvating agents for the recognition of the enantiomers of NA. Two dimensional rotating frame nuclear Overhauser enhancement spectroscopy (ROESY) experiments were also performed to explain the binding properties in terms of spatial fitting of the NA molecule into the macrocyclic cavities.

Interaction Studies of a Novel, Water-Soluble and Anti-Cancer Palladim(II) Complex with Calf Thymus DNA

  • Mansouri-Torshizi, H.;Saeidifar, M.;Divsalar, A.;Saboury, A.A.;Shahraki, S.
    • Bulletin of the Korean Chemical Society
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    • 제31권2호
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    • pp.435-441
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    • 2010
  • We report the preparation and characterization of a new and water soluble complex of palladium(II) with 1,10- phenanthroline and butyldithiocarbamate ligands. This compound has been studied through spectroscopic techniques, $^1H$ NMR, IR, electronic spectra and elemental analysis and conductivity measurements. The complex shows 50% cytotoxic concentration ($Ic_{50}$) value against chronic myelogenous leukemia cell line, K562, much lower than that of cisplatin. Thus the mode of binding of this complex to calf thymus DNA have been extensively investigated by isothermal titration UV-visible spectrophotometry, fluorescence, gel filteration and other methods. UV-visible studies show that the complex exhibits cooperative binding with DNA and remarkably denatures the DNA at extremely low concentration ($~13\;{\mu}M$). Fluorescence studies indicate that the complex intercalate into DNA. Gel filtration studies suggest that the binding of Pd(II) complex with DNA is strong enough that it does not readily break. In these interaction studies, several thermodynamic and binding parameters are also determined which may reflect the mechanism of action of this type of compound with DNA.

Purification and Spectroscopic Characterization of the Human Protein Tyrosine Kinase-6 SH3 Domain

  • Koo, Bon-Kyung;Kim, Min-Hyung;Lee, Seung-Taek;Lee, Weon-Tae
    • BMB Reports
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    • 제35권3호
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    • pp.343-347
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    • 2002
  • The human protein tyrosine kinase-6 (PTK6) polypeptide that is deduced from the cDNA sequence contains a Src homology (SH) 3 domain, SH2 domain, and catalytic domain of tyrosine kinase. We initiated biochemical and NMR characterization of PTK6 SH3 domain in order to correlate the structural role of the PTK6 using circular dichroism and heteronuclear NMR techniques. The circular dichroism data suggested that the secondary structural elements of the SH3 domain are mainly composed of $\beta$-sheet conformations. It is most stable when the pH is neutral based on the pH titration data. In addition, a number of cross peaks at the low-field area of the proton chemical shift of the NMR spectra indicated that the PTK6 SH3 domain retains a unique and folded conformation at the neutral pH condition. For other pH conditions, the SH3 domain became unstable and aggregated during NMR measurements, indicating that the structural stability is very sensitive to pH environments. Both the NMR and circular dichroism data indicate that the PTK6 SH3 domain experiences a conformational instability, even in an aqueous solution.

Fluorescence Enhancement of 7-Diethylamino-4-methylcoumarin by Noncovalent Dipolar Interactions with Cucurbiturils

  • Park, Mee Ock;Moon, Myung Gu;Kang, T.J.
    • Bulletin of the Korean Chemical Society
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    • 제34권5호
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    • pp.1378-1382
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    • 2013
  • We have investigated the complex forming behavior of cucurbit[6]urils(CB6) and cucurbit[7]urils(CB7) with 7-diethylamino-4-methylcoumarin(C460) in water. The electronic absorption maximum of C460 shows bathochromic shift with the addition of CB7 and fluorescence intensity is greatly increased, while CB6 has no noticeable effects on the spectroscopic properties of C460. It is noted that CB7 interacts more strongly with C460 than CB6 does. Fluorescence lifetime also significantly increased for the CB7 complex, which is attributed to reduced polarity surrounding C460 and/or C460 being in a restricted environment. The stoichiometry for the complex formation determined from the fluorescence titration measurement indicates that 2:1 complex in which two CB7 molecules bind to C460 is formed. Thus, two step equilibrium processes are suggested for the complex formation and the binding constants are estimated. The semi-empirical electronic structures calculations indicate that C460 is not included in the CB7 cavity but interacts noncovalently with the portal carbonyls of CB7.

Structural and Magnetic Properties of the Brownmillerite $Ca_2Al_xFe_{2-x}O_5$ System

  • 김귀야;로권선;여철현
    • Bulletin of the Korean Chemical Society
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    • 제16권10호
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    • pp.934-938
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    • 1995
  • A series of solid solutions in the Ca2AlxFe2-xO5 (x=0.00, 0.50, 0.66, 1.00 and 1.34) system with brownmillerite structure has been synthesized at 1100 ℃ under an atmospheric air pressure. The solid solutions are analysed by powder x-ray diffraction analysis, Mohr salt titration, thermal analysis, and Mossbauer spectroscopic analysis. The x-ray diffraction analysis assigns the compositions of x=0.00 and 0.50 to the space group Pcmn and those of x=0.66, 1.00, and 1.34 to the Ibm2. Mo&ssbauer spectra have shown the coordination state and disordering of Al3+ and Fe3+ ions. The substituting preference of Al3+ ions for the tetrahedral site decreases with increasing x value. Magnetic susceptibility of the system has been measured in the temperature range of 5 K to 900 K. The solid solutions of the compositions of x=0.00, 0.50 and 0.66 have shown a thermal hysteresis and the thermoremanent magnetization gap decreases with increasing x value in the above systems. However the compositions of x=1.00 and 1.34 do not show the hysteresis. The exchange integral is calculated from Fe3+ ion occupancy ratio. The integral decreases with x value and thus the magnetic transition temperature decreases with the increasing x value.

$Cu^{2+}$-Anthraquinone Complexes : Formation, Interaction with DNA, and Biological Activity

  • Ko, Thong-Sung;Maeng, Hack-Young;Park, Mi-Kyeong;Park, Il-Hyun;Park, In-Sang;Kim, Byoung-Sun
    • Bulletin of the Korean Chemical Society
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    • 제15권5호
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    • pp.364-368
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    • 1994
  • Growth inhibition potency of the anthraquinones, anthraquinone-1,5-disulfonic acid and carminic acid, for Sarcoma 180 and L1210 leukemia cells in vivo and in vitro, was induced by the divalent transition metal ion, $Cu^{2+}$. On the other hand spectroscopic titration data show that the anthraquinone drugs form $Cu2^+$ chelate complexes (carminic acid : $Cu^{2+}$ = 1 : 6; anthraquinone-1,5-disulfonic acid : $Cu^{2+}$ = 1 : 3). Furthermore the $Cu^{2+}$-drug complexes associate with DNA to form the $Cu^{2+}$-anthraquinone-DNA ternary complexes. The formation of the complexes was further supported by the $H_2O_2-dependent$ DNA degradation, which can be inhibited by ethidium bromide, caused by the $Cu^{2+}$-drug complexes. It is likely that the $Cu^{2+}$-mediated cytotoxicity of the anthraquinone drugs is related with the $Cu^{2+}-mediated$ binding of the anthraquinone drugs to DNA and DNA degradation.

Cross-verified Measurement of Sulfide Concentration in Anaerobic Conditions Using Spectroscopic, Electrochemical, and Mass Spectrometric Methods

  • Nakkyu Chae;Samuel Park;Sungyeol Choi
    • 방사성폐기물학회지
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    • 제21권1호
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    • pp.43-53
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    • 2023
  • Sulfide concentrations critically affect worker safety and the integrities of underground facilities, such as deep geological repositories for spent nuclear fuel. Sulfide is highly sensitive to oxygen, which can oxidize sulfide to sulfate. This can hinder precise measurement of the sulfide concentration. Hence, a literature review was conducted, which revealed that two methods are commonly used: the methylene blue and sulfide ion-selective electrode (ISE) methods. Inductively coupled plasma optical emission spectroscopy (ICP-OES) was used for comparison with the two methods. The sulfide ISE method was found to be superior as it yielded results with a higher degree of accuracy and involved fewer procedures for quantification of the sulfide concentration in solution. ICP-OES results can be distorted significantly when sulfide is present in solution owing to the formation of H2S gas in the ICP-OES nebulizer. Therefore, the ICP-OES must be used with caution when quantifying underground water to prevent any distortion in the measured results. The results also suggest important measures to avoid problems when using ICP-OES for site selection. Furthermore, the sulfide ISE method is useful in determining sulfide concentrations in the field to predict the lifetime of disposal canisters of spent nuclear fuel in deep geological repositories and other industries.

페롭스카이트 $CaGa_{1-x}Fe_xO_{3-y}$계의 비화학량론과 물리적 성질 (Nonstoichiometry and Physical Properties of the Perovskite $CaGa_{1-x}Fe_xO_{3-y}$ System)

  • 노권선;류광현;장순호;여철현
    • 대한화학회지
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    • 제40권5호
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    • pp.295-301
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    • 1996
  • $CaGa_1-xFexO_3-y$계의 x=0.25, 0.50, 0.75 및 1.00에 해당하는 고용체를 $1150^{\circ}C$, 대기압하에서 제조하였다. X-선 회절분석, Mohr염 정정, Mossbauer 분광분석을 수행하여 합성된 고용체들의 구조, 비화학량론적 화학식 및 양이온들의 분포를 결정한 후 전기전도도와 자기측정을 수행하여 물성에 관한 논의를 하였다. X-선 회절분석으로부터 얻은 모든 조성의 결정계는 브라운밀러릿 사방정계이다. 환산 격자부피는 단위세포의 차원이 다른 X=0.25의 조성을 제외하고 x값이 증가함에 따라 직선성을 가지고 증가한다. Mohr염분석 결과 고용체들은 $Fe^{4+}$ 이온을 포함하지 않고 산소공위의 몰수인 y값은 0.50으로 고정된 값을 가진다. Mossbauer 분광분석으로부터 Fe 이온의 산화상태, 배위상태, 브라운밀러릿 구조 및 $Ga^{3+}$$Fe^{3+}$ 이온의 분포를 논의하였다. 전기전도도와 활성화에너지는 x값이 증가함에 따라 각각 증가와 감소하고 이들로부터 전자 전기전도 메커니즘을 제안한다. x=0.50~1.00의 조성을 냉각하면서 자기측정을 수행할 때 열적 자기 히스테리시스가 나타나며 이러한 현상을 공간군과 Dzyaloshinsky-Moriya 상호작용을 기초로 논의하였다.

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