• Title/Summary/Keyword: Charge transfer complexation

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Complexation Studies for Cadmium (II) with Quercetin and (+)-Catechin (Quercetin과 (+)-Catechin의 카드뮴(II)에 대한 착물반응)

  • Lee, Jeong-Ho;Shin, Sun-Woo;Baek, Seung-Hwa
    • YAKHAK HOEJI
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    • v.53 no.6
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    • pp.342-350
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    • 2009
  • The interaction of cadmium (II) ion with quercetin and (+)-catechin was investigated in aqueous solution at various pH. The flavonoid/cadmium stochiometries for cadmium (II) binding to quercetin and (+)-catechin have been determined by UV-vis spectroscopy. 1 : 1 Cd (II)-Flavonoid complex had a maximum absorbance and showed the bathochromic shift of the long-wavelength band of the UV-vis spectra in the alkaline pH, that occurs upon complexation, due to a ligandto-metal charge transfer. These results suggest that Cd (II)-flavonoid complex has the optimal condition of chelation in 0.2 M $NH_3$ - 0.2 M $NH_4Cl$ (pH 8.0) solution.

Charge-Transfer Complexing Properties of 1-Methyl Nicotinamide and Adenine in Relation to the Intramolecular Interaction in Nicotinamide Adenine Dinucleotide (NAD$^+$)

  • Park, Joon-woo;Paik, Young-Hee
    • Bulletin of the Korean Chemical Society
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    • v.6 no.1
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    • pp.23-29
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    • 1985
  • The charge-transfer complexing properties of 1-methyl nicotinamide (MNA), an acceptor, and adenine, a donor, were investigated in water and SDS micellar solutions in relation to the intramolecular interaction in nicotinamide adenine dinucleotide ($NAD^+$). The spectral and thermodynamic parameters of MNA-indole and methyl viologen-adenine complex formations were determined, and the data were utilized to evaluate the charge-transfer abilities of MNA and adenine. The electron affinity of nicotinamide was estimated to be 0.28 eV from charge-transfer energy $of{\sim}300$ nm for MNA-indole. The large enhancement of MNA-indole complexation in SDS solutions by entropy effect was attributed to hydrophobic nature of indole. The complex between adenine and methyl viologen showed an absorption band peaked near 360 nm. The ionization potential of adenine was evaluated to be 8.28 eV from this. The much smaller enhancement of charge-transfer interaction involving adenine than that of indole in SDS solutions was attributed to weaker hydrophobic nature of the donor. The charge-transfer energy of 4.41 eV (280 nm) was estimated for nicotinamide-adenine complex. The spectral behaviors of $NAD^+$ were accounted to the presence of intramolecular interaction in $NAD^+$, which is only slightly enhanced in SDS solutions. The replacement of nicotinamide-adenine interaction in $NAD^+$ by intermolecular nicotinamide-indole interaction in enzyme bound $NAD^+$, and guiding role of adenine moiety in $NAD^+$ were discussed.

Studies on the Cd(II)-Flavonoid Chelation Reactions (카드뮴(II)-플라보노이드 킬레이트 반응에 관한 연구)

  • Lee, Jeong-Ho;Shin, Sun-Woo;Baek, Seung-Hwa
    • YAKHAK HOEJI
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    • v.54 no.1
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    • pp.13-21
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    • 2010
  • The interaction of cadmium (II) ion with quercetin, qurecitrin and (+)-catechin was investigated in aqueous solution at various pH. The flavonoid/cadmium stochiometries for cadmium (II) binding to flavonoid have been determined by UV-visible spectroscopy. 1:1 Cd(II)-Flavonoid complex had a maximum absorbance and showed the bathochromic shift of the long-wavelength band of the UV-vis spectra in the alkaline pH, that occurs upon complexation, is due to a ligand-tometal charge transfer. The optimal concentration of Cd(II)-flavonoid complexes showed that complexation reaction could be classified in the following way: 55.27 ${\mu}M$ catechin > 54.72 ${\mu}M$ quercetin > 53.52 ${\mu}M$ quercitrin at the chelating site level. These results suggest that Cd(II)-flavonoid complex has the optimal condition of chelation in 0.2 M $NH_3$ - 0.2 M $NH_4Cl$ (pH 8.0) solution.

Spectrophotometric Determination of Nizatidine and Ranitidine Through Charge Transfer Complex Formation

  • Walash, M.;Din, M.-Sharaf-EI;Metwalli, M.E.S.;RedaShabana, M.
    • Archives of Pharmacal Research
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    • v.27 no.7
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    • pp.720-726
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    • 2004
  • Two Spectrophotometric procedures are presented for the determination of two commonly used H2-receptor antagonists, nizatidine (I) and ranitidine hydrochloride (II). The methods are based mainly on charge transfer complexation reaction of these drugs with either ${\rho}-chloranilic$ acid (${\rho}-CA$) or 2, 3 dichloro-5, 6-dicyanoquinone (DDQ). The produced colored products are quantified spectrophotometrically at 515 and 467 nm in chloranilic acid and 000 methods, respectively. The molar ratios for the reaction products and the optimum assay conditions were studied. The methods determine the cited drugs in concentration ranges of 20-200 and $20-160\;\mu\textrm{g}/mL$ for nizatidine and ranges of 20-240 and $20-140\;\mu\textrm{g}/mL$ for ranitidine with chloranilic acid and DDQ methods, respectively. A more detailed investigation of the complexes formed was made with respect to their composition, association constant, molar absorptivity and free energy change. The proposed procedures were successfully utilized in the determination of the drugs in pharmaceutical preparations. The standard addition method was applied by adding nizatidine and ranitidine to the previously analyzed tablets or capsules. The recovery of each drug was calculated by comparing the concentration obtained from the spiked mixtures with those of the pure drug. The results of analysis of commercial tablets and the recovery study (standard addition method) of the cited drugs suggested that there is no interference from any excipients, which are present in tablets or capsules. Statistical comparison of the results was performed with regard to accuracy and precision using student's t-test and F-ratio at 95% confidence level. There is no significant difference between the reported and proposed methods with regard to accuracy and precision.

The Physicochemical Properties on the Charge Transfer Complexes under High Pressure (고압하의 전하이동착물에 대한 물성론적 연구-사염화탄소 용액내에서 헥사메틸벤젠과 여러 전자받게들간의 전하이동착물 생성에 대한 압력과 온도의 영향)

  • Kwun Oh Cheun;Kim Myong Ja;Kim Se Kyung
    • Journal of the Korean Chemical Society
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    • v.35 no.4
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    • pp.335-342
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    • 1991
  • The effect of pressure and temperature on the stabilities of the charge transfer complexes of 1,3,5-trinitrobenzene, tetrachloro-p-benzoquinone and tetracyanoethylene with hexamethylbenzene in carbon tetrachloride has been investigated by spectrophotometric measurements. The equilibrium constants for the formation of the complexes were obtained at various temperature and pressure, and thermodynamic parameters for the formation of the charge transfer complexes are calculated from these values. The relative stabilities of charge transfer complexes with hexamethylbenzene increase in the order; 1,3,5-trinitrobenzene < tetrachloro-p-benzoquinone < tetracyanoethylene. This may be regarded as an order of relative acidity of these compounds in complexation with hexamethylbenzene and is explained in terms of the negative inductive effect of the ${\pi}$ acceptors. The red-shift at higher pressure, the blue-shift at higher temperature and the relation between pressure and oscillator strength are discussed on the basis of thermodynamic functions.

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EXCITED-STATE TWISTED INTRAMOLECLILAR CHARGE TRANSFER OF p-N,N-DIMETHYLAMINOBENZOIC ACID IN AQUEOUS CYCLODEXTRIN SOLUTIONS: TIME-RESOLVED FLUORESCENCE STUDY

  • Kim, Yong-Hee;Cho, Dae-Won;Yoon, Min-Joong
    • Journal of Photoscience
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    • v.3 no.3
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    • pp.153-158
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    • 1996
  • The effects of $\alpha$- and $\beta$-cyclodextrins (CD) on the twisted intramolecular charge transfer (TICT) behavior of p-N,N'-dimethylaminobenzoic acid (DMABA) in buffered aqueous solution have been investigated by examining formation and decay behaviors of the TICT-typical dual fluorescence. The ratio of the TICT emission to the normal emission (I$_a$/I$_b$) increases linearly $\alpha$-CD concentration increases, while in the presence of $\beta$-CD it shows nonlinear dependences on the CD concentration. The analysis of the CD-dependent changes of the I$_a$/I$_b$ and absorption spectra demonstrates formation of 1:1 inclusion complexes between DMABA and CDs. The decay time of the normal emission (ca. 700 ps) is little affected by the formation of $\alpha$-CD inclusion complex, whereas it increases upto ca. 1.6 ns upon formation of $\beta$-CD inclusion complex. The TICT emission for the $\beta$-CD inclusion complex exhibits two decay components while it shows a single component for the $\alpha$-CD inclusion complex, indicating formation of one or two types of inclusion complex in the presence of $\alpha$-CD or $\beta$-CD, respectively. These results are attributed to the CD cavity size dependence on patterns of complexation between CDs and DMABA. The CD size dependences of the TICT fluorescence properties with the orientation of the guest molecule demonstrate that the specific hydrogen bonding between the carboxylic acid group and water plays an important role in the excited-state TICT.

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Fluorescent Compounds Having the Spaced and Integrated Type Receptors

  • Choi, Chang-Shik
    • Rapid Communication in Photoscience
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    • v.5 no.1
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    • pp.1-7
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    • 2016
  • Fluorescent receptors have gained much attention because of their usefulness in analysis and clarification of the roles of biomolecules in living systems. Molecular structures of the integrated type including that the receptor itself is fluorescent, and play an important role in having the functionality or selectivity of the fluorescent compounds. These spaced type fluorescent receptors are required to have special molecular design in order to transmit the information of molecular recognition to the fluorescent unit through the spacer unit. Compared with the spaced type fluorescent receptors, number of the integrated type receptors is limited due to the difficult molecular design and synthesis. Modification of alteration of the fluorophore frequently caused deterioration of the fluorescent property. Various spaced type and integrated type fluorescent receptors including switch on-off receptors are introduced in this article.

Spectrophotometric Determination of Ephedrine Alkaloids by Charge-Transfer Complexation (전하이동 착물형성에 의한 Ephedrine Alkaloids의 분석화학적 연구)

  • 옥치완;백채선
    • YAKHAK HOEJI
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    • v.31 no.5
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    • pp.330-337
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    • 1987
  • The weak UV absorbing ephedrine alkaloids such as ephedrine, pseudoephedrine, methylephedrine and norephedrine could be analyzed by charge-transfer spectrophotometric method. The results obtained are summarized as follows: (1) It was possible to determine a weak UV absorbing ephedrine alkaloids using the intense charge-transfer UV bands in chloroform. (2) This method was suitable for the spectrophotometric determination of ephedrine alkaloids in mixed pharmaceutical preparation. (3) Linear relationship was found between absorbance and concentration in the range of 1.0$\times$$10^{-5}M$~5$\times$$10^{-5}M$ of ephedrine ($\varepsilon$= 2.72$\times$$10^{4}LM^{-1}cm^{-1}$ and pseudoephedrine ($\varepsilon$=2.84$\times$$10^{4]LM^{-1}cm^{-1}$), 1.0$\times$$10^{-5}M$~5$\times$$10^{-5}$M of methylephdrine ($\varepsilon$=1.68$\times$$10^{4}LM^{-1}cm^{-1}$) and 1/3$\times$$10^{-4}M$~4/3$\times$$10^{-4}M$ of norephedrine ($\varepsilon$=0.74$\times$$10^{4}LM^{-1}cm^{-1}$. (4) CT- complex of ephedrine, pseudoephedrine and methylephedrine has absorption maxima at 293nm and norephedrine have absorption maximum at 253nm. (5) CT-complexes were formed in a 1:1 ratio between ephedrine alkaloids and iodine in chloroform. (6) By UV, IR, and $^1H$-NMR spectra, it could be inferred that CT-complexes were formed by interaction between the basic nitrogen of ephedrine alkaloids as electron (n) donor and iodine as electron ($\sigma$) acceptor.

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Synthesis, Characterization, and Crystal Structures of Iron(Ⅱ) and Manganese(II) Complexes with 4,7-bis(2-pyridylmethyl)-1-thia-4,7-diazacyclononane

  • Delong Zhang;Daryle H. Busch;Nathaniel W. Alcock
    • Bulletin of the Korean Chemical Society
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    • v.19 no.9
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    • pp.897-906
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    • 1998
  • A new synthesis has been developed for 1-thia-4,7-diazacyclononane and the complexation behavior of a particular derivative has been explored. The pentadentate ligand 4,7-bis(2-pyridylmethyl)-l-thia-4,7-diazacyclononane ([9]$N_2SPY_2$) and its iron(Ⅱ) and manganese(Ⅱ) complexes were prepared and characterized. Magnetic moments of 5.17 and 5.90 μB respectively, indicate that the iron(Ⅱ) and manganese(Ⅱ) complexes are high spin. Charge transfer transitions (d-π*) occur for [Fe(Ⅱ)([9]$N_2SPY_2)(X)]^{n+}$at 27027, 25000, and 24390 cm-1 for X=$H_2O$, Cl-, and OH-, respectively. In acetonitrile solution, the cyclic voltammogram of the manganese(Ⅱ) complex exhibits a redox couple at 0.92 V vs. NHE while the redox potentials for [Fe(Il)([9]$N_2SPY_2)(X)]^{n+}$ are 0.70, 0.66, and 0.37 V vs. NHE for X=$H_2O$, Cl-, and OH-, respectively. The d-π* charge transfer energy and Fe(Ⅱ)/Fe(Ⅲ) redox potential for [Fe(Ⅱ)([9]$N_2SPY_2)(X)]^{n+}$ increase in the same order: $H_2O>Cl^- >OH^-$. The crystal structures of the iron(Ⅱ) and manganese(Ⅱ) complexes reveal that the metal ions are sixcoordinate, binding to four nitrogen atoms and a sulfur atom from the pentadentate ligand, as well as a chloride anion, with the chloride and sulfur atoms in cis positions. The two metals have similar coordination geometries, which are closer to trigonal prismatic than octahedral. In both iron and manganese complexes, the M-N($sp_3$) trans to Cl- is 0.07 Å longer than the one cis to Cl- , and M-N($sp^2$) trans to S is 0.05 longer than the one cis to S atom.