• Title/Summary/Keyword: Free ligand

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Highly Selective Fluorescent Signaling for Al3+ in Bispyrenyl Polyether

  • Kim, Hyun-Jung;Kim, Su-Ho;Quang, Duong Tuan;Kim, Ja-Hyung;Suh, Il-Hwan;Kim, Jong-Seung
    • Bulletin of the Korean Chemical Society
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    • v.28 no.5
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    • pp.811-815
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    • 2007
  • A series of bispyrenyl-polyether have been synthesized and investigated as a fluorescent chemosensor for metal ions. The results showed that bispyrenyl-polyether system is selective towards Al3+ ion over other ions tested. In free ligand, excited at 343 nm, it displays a strong excimer emission at around 475 nm with a weak monomer emission at 375 nm. A ratiometry of monomer (375 nm) increase and excimer (475 nm) quenching was shown only when Al3+ ion is bound to ligand, because two facing pyrene groups form a less efficient overlap of π?π stacking compared with that of free ligand.

NMR Study on the Internal Dynamics of Ketosteroid Isomerase

  • Lee, Hee-Cheon
    • Proceedings of the Korean Biophysical Society Conference
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    • 2003.06a
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    • pp.26-26
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    • 2003
  • The backbone dynamics of ketosteroid isomerase, a homodimeric enzyme with 125 amino acid residues per subunit, has been studied in the presence/absence of a steroid ligand and 5% trifluoroethanol (TFE) by $^{15}$ M relaxation measurements. The relaxation data were analyzed using the model-free formalism to extract the model-free parameters (S$^2$, $\tau$$_{e}$, and R$_{ex}$ ). The results show that a large number of the residues, particularly those involved in the dimer interaction, exhibit reduced order parameters (S$^2$) in the steroid-bound enzyme, indicating the increased high-frequency (pico- to nanosecond) motions in the interface region upon ligand binding. The results also show that that the presence of 5 % TFE in free enzyme causes little change or slight increase in the order parameters for a number of residues in the dimer interface region. However, the majority of the residues in free enzyme exhibit reduced order parameters in the presence of 5 % TFE, indicating that the increase in entropy is partially responsible for the increased stability of KSI by 5% TFE.E.E.

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$^1H$ NMR Study of Imidazole, L-Histidine, and Their Derivatives Coordinated to the Paramagnetic Undecatungstocobalto(II)silicate and -nickelo(II)silicate Anions

  • Moonhee Ko;Gyung Ihm Rhyu;Hyunsoo So
    • Bulletin of the Korean Chemical Society
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    • v.15 no.8
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    • pp.673-679
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    • 1994
  • $^1H$ NMR spectra of imidazole, 2-and 4(5)-methylimidazole, histamine, L-histidine, L-histidine methyl ester, N${\alpha}$-acetyl-L-histidine, and L-carnosine coordinated to the paramagnetic undecatungstocobalto(II)silicate ($SiW_{11}Co$) and undecatungstonickelo(II)silicate ($SiW_{11}Ni$) anions are reported. For these complexes the ligand exchange is slow on the NMR time scale and the pure resonance lines of the free ligand and the complexes have been observed separately at room temperature. Two different complexes are formed, depending upon which nitrogen atom of the imidazole ring is coordinated to the cobalt or nickel ion of $SiW_{11}M$. Thus the NMR spectrum of a $D_2O$ solution containing a ligand and $SiW_{11}M$ consists of three sets of lines originating from the free ligand and two complexes. All NMR lines of the $SiW_{11}Co$ complexes have been assigned unequivocally using the saturation transfer technique. The temperature dependence of some spectra are also reported. The NMR spectra of some complexes show that the internal rotation of the substituent on the imidazole ring is hampered by the heteropolyanion moiety even at room temperature.

Enantiomeric Separation of Free Amino Acids Using N-alkyl-L-proline Copper(Ⅱ) Complex as Chiral Mobile Phase Additive in Reversed Phase Liquid Chromatography

  • Lee Sun Haing;Oh Tae Sub;Lee Hae Woon
    • Bulletin of the Korean Chemical Society
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    • v.13 no.3
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    • pp.280-285
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    • 1992
  • Enantiomeric separation of free amino acids has been achieved by a reversed phase liquid chromatography with addition of a Cu(Ⅱ) complex of N-alkyl-L-proline (alkyl: propyl, pentyl or octyl) to the mobile phase. The amino acids eluted were detected by a postcolumn OPA system. N-alkyl-L-proline was prepared and used as a chiral ligand of Cu(Ⅱ) chelate for the enantiomeric separation. The concentration of the Cu(Ⅱ) chelate, the organic modifier and pH affect the enantiomeric separation of free amino acids. The retention behaviour, varied with change in pH and the concentration of the Cu(Ⅱ) chelate, was different compared with those of the derivatized amino acids. The elution orders between D- and L-forms were consistent except histidine showing that L-forms elute earlier than D-forms. The retention mechanism for the enantiomeric separation can be illustrated by the stereospecificity of the ligand exchange reaction and the hydrophobic interaction between the substituent of amino acids and reversed phase, $C_18$.

$^{15}$N NMR Relaxation Study of the Catalytic Residues in Y14F Mutant Ketosteroid Isomerase

  • Yoon, Ye-Jeong;Lee, Hyeong-Ju;Kim, Chul;Lee, Hee-Cheon
    • Journal of the Korean Magnetic Resonance Society
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    • v.8 no.2
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    • pp.77-85
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    • 2004
  • $^1$H-detected $^{15}$N NMR was employed to investigated the effect of mutation (Y14F) on the dynamic properties of catalytic residues in ${\Delta}^5$-3- ketosteroid isomerase (KSI) from Conamonas testosteroni. In particular, the backbone dynamics of the catalytic residues have been studied in free enzyme and its complex with a steroid ligand, 19-nortestosterone hemisuccinate, by $^{15}$N relaxation measurements. The relaxation data were analyzed using the model-free formalism to extract the model-free parameters (S$^2$, ${\tau}_e$, and R$_{ex}$). The results show that the mutation causes a significant decrease in the order parameter (S$^2$) for the catalytic residues of free Y14F KSI, presumably due to breakdown of the hydrogen bond network by mutation. In addition, the order parameters of Phe-14 and Asp-99 increased slightly upon ligand binding, indicating a slight restriction of the high-frequency (pico- to nanosecond) internal motions of the residues in the complexed Y14F KSI, while the order parameter of Tyr-55 decreased significantly upon ligand binding.

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Production and Characterization of DDT Antibodies and Its Application to Enzyme Immunoassay: Relation of Response and Affinity to Coating Ligand

  • Hong, Ji-Youn;Kim, Jong-Hyun;Park, Song-Ja;Lho, Dong-Seok;Choi, Myung-Ja
    • Bulletin of the Korean Chemical Society
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    • v.24 no.11
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    • pp.1605-1608
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    • 2003
  • To development an immunodetection method for DDT, 1,1,1-trichloro-2,2-bis(4-chorophenyl)ethane (p,p'-DDT) and its metabolites (p,p'-DDA, p,p'-DDE, p,p'-DDD), five derivatives of DDT haptens have been synthesised and characterized as coating ligands for antibody evaluation. The appropriate lengths of linkers were introduced to investigate a matching pair of coating ligand and antibody. Among these hapten derivatives, 2,2-bis(4-chlorophenyl)acetic acid (DDA), 5,5-bis(4-chlorophenyl)-5-hydroxypentanoic acid (DDHP) and 5,5-bis(4-chlorophenyl)-5-chloropentanoic acid (DDCP) were conjugated with keyhole limpet hemocyanin (KLH) for its use as an immunogen. The bovine serum albumin (BSA) conjugates of these derivatives were prepared as a coating ligand for monoclonal antibody screening. Fifteen monoclonal antibody clones were screened using these probes. 6,6-Bis(4-chlorophenyl)-6-hydroxyhexanoic acid (DDHH) and 3-[6,6-Bis(4-chlorophenyl)-6-hydroxyhexanoylamino]propanoic acid (DDHHAP), in addition to the above hapten derivatives, were conjugated to ovualbumin (OVA) and bovine serum albumin (BSA) for their use as coating ligands to measure the titration level of the antibody and the displacement of free analytes. The indirect competitive ELISA results indicate that the titration level and free analyte displacement were greatly influenced by the DDT derivatives and carrier proteins used. Three matching pairs of monoclonal antibodies and coating ligands were selected for the DDT immunoassay: antibody clone 1A3 and coating ligand DDA-OVA, 1A1 and DDHHAP-BSA, and 1A4 and DDHP-OVA.

Electrochemical Behavior of Mordant Red 19 and its Complexes with Light Lanthanides

  • Sang Kwon Lee;Taek Dong Chung;Song-Ju Lee;Ki-Hyung Chjo;Young Gu Ha;Ki-Won Cha;Hasuck Kim
    • Bulletin of the Korean Chemical Society
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    • v.14 no.5
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    • pp.567-574
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    • 1993
  • Mordant Red 19(MR19) is reduced at mercury electrode at -0.67 V vs. Ag/AgCl with two electrons per molecule in pH 9.2 buffer by differential pulse polarography and linear sweep voltammetry. The peak potential is dependent on the pH of solution. The exhaustive electrolysis, however, gives 4 electrons per molecule because of the disproportionation of the unstable hydrazo intermediate. The electrochemical reduction of lanthanide-MR19 complexes is observed at more cathodic potential than that of free ligand. The difference in peak potentials between complex and free ligand varies from 75 mV for $La^{3+}$ to 165 mV for $Tb^{3+}$ and increases with increasing the atomic number of lanthanide. The electrochemical reduction of lanthanide complexes with MR19 is due to the reduction of ligand itself, and it can be potentially useful as an indirect method for the determination of lanthanides. The shape of i-E curves and the scan rate dependence indicates the presence of adsorption and the adsorption was confirmed by potential double-step chronocoulometry and the effect of standing time. Also the surface excess of the adsorbed species and diffusion coefficients are determined. The composition of the complex is determined to be 1 : 2 by spectrophotometric and electrochemical methods.

Synthesis of 2-Substituted Benzofurans from o-Iodophenols and Terminal Alkynes with a Recyclable Palladium Catalyst Supported on Nano-sized Carbon Balls under Copper- and Ligand-Free Conditions

  • Yum, Eul Kgun;Yang, Ok-Kyung;Kim, Ji-Eun;Park, Hee Jung
    • Bulletin of the Korean Chemical Society
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    • v.34 no.9
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    • pp.2645-2649
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    • 2013
  • We have developed a one-step synthesis of benzofurans from o-iodophenol and various terminal alkynes, by using Pd catalyst supported on nano-sized carbon balls (NCB) under copper- and ligand free conditions. This recyclable catalyst could be reused more than 5 times in the same heteroannulation reaction. The results have demonstrated that diverse 2-substituted benzofurans with tolerant functional groups can be prepared simply and conveniently under these conditions.

Characterazation of Butyldithiodiacetic Acid, Benzmethyldithiodiacetic Acid and Cyclohexyldithiodiacetic Acid used Infrared Spectra in Aqueous Solution (수용액상에서 Infrared Spectra를 이용한 Butyldithiodiacetic Acid, Benzmethyldithiodiacetic Acid, Cyclohexyldithiodiacetic Acid의 특성에 관한 연구)

  • Doh, Kiel Myung;Kim, Ill Chool;Choi, Bo Yong
    • Journal of the Korean Chemical Society
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    • v.39 no.3
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    • pp.213-217
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    • 1995
  • Infrared Spectra of aqueous solution of BUDDA(Butyldithiodiacetic acid), BMDDA(Benzmethyldithiodiacetic acid), and CHDDA(Cyclohexyldithiodiacetic acid) are reported at various pH values. On the basis of the antisymmetric stretching bands of the ionized and un-ionized carboxyl group, the structures of the free-ligand are inferred. An approach to the study of these structures are compared with the results of potentiometric titration curve and IR Spectra studies.

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SNP (Single Nucleotide Polymorphism) Detection Using Indicator-free DNA (비수식화 DNA를 이용한 SNP의 검출)

  • Choi, Yong-Sung;Park, Dae-Hee;Kwon, Young-Soo
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2003.11a
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    • pp.224-226
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    • 2003
  • In this paper, we succeeded SNP discrimination of DNA hybridization on microarray using new electrochemical system. Using the electrochemical method with a label-free DNA has Performed DNA chip microarray. This method is based on redox of an electrochemical ligand. We developed scanning system with high performance.

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