• Title/Summary/Keyword: dimer formation

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Electropolymerization Mechanism for Poly(o-phenylenediamine) (PPD) and Its Electrocatalytic Behavior for $O_2$ Reduction

  • Jang, Dong Hun;Yu, Yong Seop;O, Seung Mo
    • Bulletin of the Korean Chemical Society
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    • v.16 no.5
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    • pp.392-397
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    • 1995
  • o-Phenylenediamine (o-PD) was electropolymerized on glassy carbon electrodes under a potential cycling condition. The resulting polymer films mediated electrons for the reduction of molecular oxygen at pH=1.0. It was found from the RDE, RRDE, and cyclic voltammetry experiments that the modified electrodes reduce oxygen to hydrogen peroxide at about 300 mV lower potential than the bare glassy carbon electrode. The polymer film consisted of more than two components. Among those, only one component was active in oxygen reduction, which was formed mainly in the earlier stage of the electropolymerization. 2,3-Diaminophenazine, a cyclic dimer of o-PD, was also active in the oxygen reduction reaction, from which it was suggested that the active polymeric component has a structural unit similar to the cyclic dimer. Finally, the electropolymerization mechanism for the formation of the active and inactive components has been proposed.

Increase of Spacer Sequence Yields Higher Dimer $(Fab-Spacer-Toxin)_{2}$ Formation

  • Yoo Mee-Hyeon;Won Jae-Seon;Lee Yong-Chan;Choe Mu-Hyeon
    • Journal of Microbiology and Biotechnology
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    • v.16 no.7
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    • pp.1097-1103
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    • 2006
  • The divalent antibody-toxins are expected to have increased binding avidities to target cells because of the two cell-binding domains. However, previous studies showed that the refolding yield of divalent antibody-toxin is very low, and it is assumed that homodimer formation of antibody-toxin is strongly interfered by the repulsion between the two large toxin domains that come close to each other during dimer formation. In this study, B3 antibody was used as a model antibody, and its Fab domain was used to construct three different kinds of Fab divalent molecules, $[B3(Fab)-toxin]_{2}$. The monomer Fab-toxin molecules were made by fusing the Fab domain of monoclonal antibody B3 to PE38, a truncated mutant form of Pseudomonas exotoxin (PE), and a connecting sequence that contained spacer amino acid sequence (G4S)n (n=l, 2, 3) was inserted between Fab and PE38. The prepared divalent molecules were $[Fab-S\;1,\;2,\;3-PE38]_{2}\;(=[Fab-SKPCIST-KAS(G_{4}S)nGGPE-PE38]_{2}\;(n=1,\;2,\;3))$, and they are derivatives of previously studied $[Fab-H2cys-PE38]_{2}\;(=[Fab-SKPCIST-KASGGPE-PE38]_{2})$. In $[Fab-Sl,\;2,\;3-PE38]_{2}$, two Fab-S1, 2, 3-PE38 monomers were covalently linked by the disulfide bond bridge made from cysteine in the -SKPCIST- sequence. The insertion of spacer amino acids after the disulfide bridge resulted in a 12-18 fold higher yield of dimer formation than previously constructed $[Fab-Hlcys-PZ38]_{2}[7]$, 3-4-fold higher than $[Fab-ext-PZ38]_{2}[25]$. These two molecules have less amino acid spacer sequence between the disulfide bridge and PE38 domain. The design of $[Fab-PE38]_{2}$ in this study gave molecules with a higher refolding yield. The results of cytotoxicity assay showed a higher cytotoxic effect of these divalent molecules than that of the monovalent scFv-PE38 molecule.

REACTION OF PAPER PULP AND ALKYL KETENE DIMER BY AGING TREATMENT DURING PAPERMAKIN PROCESS

  • Shin, Young-Doo;Seo, Won-Sung;Cho, Nam-Seok
    • Proceedings of the Korea Technical Association of the Pulp and Paper Industry Conference
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    • 2000.11a
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    • pp.83-83
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    • 2000
  • Alkylketene dimer was known as a cellulose reactive or alkaline size because it does not require to fix to the fiber as do the traditional rosin sizes. A proposed sizing mechanism of AKD was the formation of P -ketoester bond between AKD and cellulose which provides the permanent attachment and the orientation of the hydrophobic alkylchains outward. However, some questions about the reaction had arisen and thus, the sizing mechanism of AKD has been a subject of controversy for several decades. The major concern of the controversy is that AKD is really reactive with cellulose or not in the papermaking conditions. In this study, reaction between AKD and pulp fiber was investigated, in order to find out whether AKD forms P-ketoester with pulp fiber during aging under no catalyzed neutral condition with obvious spectroscopic evidence. In addition, effect of aging treatment on the sizing development was studied. It has been disclosed that, in absence of water, AKD reacted with cellulose to form P -ketoester linkage under no catalyzed neutral condition, while, in presence of water, most of AKD was hydrolyzed to a dialkyl ketone or P -ketoacid. In addition, during the aging treatment of AKD-sized paper, its typical IR spectra bands gradually were reduced, completely disappeared after 6hr aging, and formed new absorption bands at 1707cm-' and shoulder peak at 1700cm-' which refer to the typical dialkylketone absorption bands. Therefore, the formation of P -ketoester between AKD and pulp fiber is impossible in the practical papermaking process. It could be suggested that the sizing development of AKD-sized paper is obtained by next two mechanism: 1) formation of a thin-layer of AKD on the fiber surface through melting and spreading of AKD emulsion particles by heat and 2) the hydrolysis of AKD to dialkyl ketone which has higher melting point, during drying and storage of AKD sized papers.

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Dimerization of Fibril-forming Segments of α-Synuclein

  • Yoon, Je-Seong;Jang, Soon-Min;Lee, Kyung-Hee;Shin, Seok-Min
    • Bulletin of the Korean Chemical Society
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    • v.30 no.8
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    • pp.1845-1850
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    • 2009
  • We have performed replica-exchange molecular dynamics (REMD) simulations on the dimer formation of fibrilforming segments of $\alpha$-Synuclein (residues 71 - 82) using implicit solvation models with two kinds of force fields- AMBER parm99SB and parm96. We observed spontaneous formation of dimers from the extensive simulations, demonstrating the self-aggregating and fibril forming properties of the peptides. Secondary structure profile and clustering analysis showed that dimers with antiparallel $\beta$-sheet conformations, stabilized by well-defined hydrogen boding, are major species corresponding to global free energy minimum. Parallel dimers with partial $\beta$-sheets are found to be off-pathway intermediates. The relative instability of the parallel arrangements is due to the repulsive interactions between bulky and polar side chains as well as weaker backbone hydrogen bonds.

Computational Study on Oligomer Formation of Fibril-forming Peptide of α-Synuclein

  • Park, Seong-Byeong;Yoon, Je-Seong;Jang, Soon-Min;Lee, Kyung-Hee;Shin, Seok-Min
    • Bulletin of the Korean Chemical Society
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    • v.33 no.3
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    • pp.848-854
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    • 2012
  • We have studied the oligomerization of a fibril-forming segment of ${\alpha}$-Synulcein using a replica exchange molecular dynamics (REMD) simulation. The simulation was performed with trimers and tetramers of a 12 amino acid residue stretch (residues 71-82) of ${\alpha}$-Synulcein. From extensive REMD simulations, we observed the spontaneous formation of both trimer and tetramer, demonstrating the self-aggregating and fibril-forming properties of the peptides. Secondary structure profile and clustering analysis illustrated that antiparallel ${\beta}$-sheet structures are major species corresponding to the global free energy minimum. As the size of the oligomer increases from a dimer to a tetramer, conformational stability is increased. We examined the evolution of simple order parameters and their free energy profiles to identify the process of aggregation. It was found that the degree of aggregation increased as time passed. Tetramer formation was slower than trimer formation and a transition in order parameters was observed, indicating the full development of tetramer conformation which is more stable than that of the trimer. The shape of free energy surface and change of order parameter distributions indicate that the oligomer formation follows a dock-and-lock process.

THE EFFECT OF HYDROLYZED ALKYLKETENE DIMER ON SIZING DEVELOPMENT

  • Seo, Won-Sung;Shin, Jong-Ho;Cho, Nam-Seok
    • Proceedings of the Korea Technical Association of the Pulp and Paper Industry Conference
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    • 1999.11b
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    • pp.50-55
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    • 1999
  • Sizing development of AKD-sized paper by beta-ketoester formation has been debated until recent years because of absence of its obvious and direct spectroscopic evidence. In this study, reaction between AKD and cellulose was investigated to disclose the possibility of beta-ketoester formation between two components under no catalyzed neutral condition. In absence of water, AKD reacted with cellulose to form beta-ketoester linkage under no catalyzed neutral condition, while, in presence of water, most of AKD was hydrolyzed to a dialkyl ketone or beta-ketoacid. Therefore, the main mechanism of AKD sizing would not be the formation of beta-ketoester between AKD and cellulose in the papermaking process. It could be suggested that the sizing development of AKD-sized paper is obtained by next two mechanisms: 1) formation of a thin-layer of AKD on the fiber surface through melting and spreading of AKD emulsion particles by heat, and 2) the formation of ketone by the hydrolysis of AKD during drying and storage of AKD-sized papers.

Study on the Hydrogenation and Isomerization Reaction of Dimethylcyclopentadiene (디메틸시클로펜타디엔의 수소화 및 이성화반응 연구)

  • Jeong, Byung Hun;Han, Jeong Sik;Lee, Jeong Ho;Kim, Seong Bo;Lee, Bum Jae
    • Korean Chemical Engineering Research
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    • v.43 no.5
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    • pp.566-570
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    • 2005
  • The study on the hydrogenation and isomerization of unsaturated bicyclic hydrcarbon compounds using methylcyclopentadiene dimer (MCPD) was carried out. Exo compound was prepared through isomerization reaction after two hydrogenation reaction steps. In the first hydrogenation reaction which needs one mole of hydrogen, the formation rate of monomer was increased as dimer was decomposed at reaction temperature above $100^{\circ}C$. At first hydrogenation, DHDMCPD [dihydrodi(methylcyclopentadiene)] was formed and second hydrogenation was proceeded to produce THDMCPD [tetrahydrodi(methylcyclopentadiene)], the ratio of exo to endo THDMCPD was varied by the control of 2nd hydrogenation temperature. To improve the process, continuous 1st and 2nd hydrogenation conditions were established by using the 2nd stage heat controllable reactor. Also, catalytic activities were compared by the use of halogenized aluminum, metal halides and solid acids catalysts on the isomerization reaction from endo to exo THDMCPD.

The Electrocatalytic Reduction of Oxygen by Bis-Cobalt Phenylporphyrins in Various pH Solutions (여러 가지 pH 수용액에서 Bis-Cobalt Phenylporphyrin 유도체들에 의한 산소의 전극 촉매적 환원)

  • Yong-Kook Choi;Ki-Hyung Chjo;Jong-Ki Park
    • Journal of the Korean Chemical Society
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    • v.37 no.8
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    • pp.735-743
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    • 1993
  • The electrocatalytic reduction of oxygen is investigated by cyclic voltammetry and chronoamperometry at glassy carbon electrode and carbon microelectrode coated with a variety of cobalt phenylprophyrins in various pH solutions. Oxygen reduction catalyzed by the monomeric porphyrin Co(Ⅱ)-TPP mainly occurs through the 2e$^-$ reduction pathway resulting in the formation of hydrogen peroxide whereas electrocatalytic process carried out 4e$^-$ reduction pathway of oxygen to H$_2$O at the electrodes coated with cofacial bis-cobalt phenylporphyrins in acidic solution. The electrocatalytic reduction of oxygen is irreversible and diffusion controlled. The reduction potentials of oxygen in various pH solutions have a straight line from pH 4 to pH 13, but level off in strong acidic solution. The reduction potentials of oxygen shift to positive potential more 400 mV at the electrode coated with monomer Co-TPP compound than bare glassy carbon electrode while 750 mV at the electrode coated with dimer Co-TPP compound.

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Kinetic Studies of the Aggregation of 3,3'-Diethyl Oxacarbocyanine onto Polyacrylic Acid (폴리아크릴산 용액에서의 옥사카르보시안닌 색소분자의 회합현상에 대한 반응속도론적 연구)

  • Lee, Hong;Im, Eun Suk;Bae, Hyeon Ok
    • Journal of the Korean Chemical Society
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    • v.38 no.11
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    • pp.792-799
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    • 1994
  • The spectral changes of 3,3'-diethyl oxacarbocyanine(DOC) in the aqueous solution and in the presence of polyacrylic acid(PAA) were studied by means of absorption and fluorescence spectroscopy. The spectral change of DOC in the aqueous solution with concentration changes is attributed to the formation of dimer. In the presence of PAA, the characteristic changes of metachromatic band with changes of P/D (the ratio between available binding site and the dye concentration) are found and the discussions are made in terms of stacking theory. A kinetic study of the interaction between DOC and PAA was also investigated by the absorption and fluorescence stopped-flow spectroscopy. The observed relaxation effect in PAA-DOC system can be described quantitatively by assuming two relaxation processes occur.

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Quantitative Assay for the Binding of Jun-Fos Dimer and Activator Protein-1 Site

  • Lee, Sang-Kyou;Park, Se-Yeon;Jun, Gyo;Hahm, Eun-Ryeong;Lee, Dug-Keun;Yang, Chul-Hak
    • BMB Reports
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    • v.32 no.6
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    • pp.594-598
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    • 1999
  • The Jun and Fos families of eukaryotic transcription factors form heterodimers capable of binding to their cognate DNA enhancer elements. We are interested in searching for inhibitors or antagonists of the binding of the Jun-Fos heterodimer to the activator protein-1 (AP-1) site. The basic-region leucine zipper (bZIP) domain of c-Fos was expressed as a fusion protein with glutathione S-transferase, and allowed to form a heterodimer with the bZIP domain of c-Jun. The heterodimer was bound to glutathione-agarose, to which were added radiolabeled AP-1 nucleotides. After thorough washing, the gel-bound radioactivity was counted. The assay is faster than the coventional electrophoretic mobility shift assay because the gel electrophoresis step and the autoradiography step are eliminated. Moreover, the assay is very sensitive, allowing the detection of picomolar quantities of nucleotides, and is not affected by up to 50% dimethylsulfoxide, a solvent for hydrophobic inhibitors. Curcumin and dihydroguaiaretic acid, recently known inhibitors of Jun-Fos-DNA complex formation, were applied to this Jun-GST-fused Fos system and revealed to decrease the dimer-DNA binding.

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