• Title/Summary/Keyword: dimers

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Chemical Synthesis of Oligodeoxyribonucleotide ; Improvement of Deoxyribonucleoside Phosphorylation and Dideoxyribonucleotide Synthesis (Oligodeoxyribonucleotide의 화학적 합성 ; Deoxyribonucleoside의 인산화와 이량체 합성 방법의 개선)

  • Sang Jik Lee;Byung Soo Song;Jong Dae Kim
    • Journal of the Korean Chemical Society
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    • v.31 no.1
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    • pp.84-93
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    • 1987
  • The study was done with a focus on making the optimum condition on phosphorylation of deoxyribonucleoside with o-chlorophenylphosphoroditriazole as a phosphorylating agent. The result showed that the addition of 5 volume % pyridine to the dioxane solution accelerated the rate of reaction to a great extent and turned out to nearly quantitative yields on phosphorylation. On the basis of this improvement of optimum reaction conditions, a more efficient method to synthesize all-protected dideoxyribonucleotide from N, 5-O-blocked deoxyribonucleoside was developed. The dodecamer with a Hind Ⅲ recognition site was readily synthesized from five different dimers which were prepared through the newly improved method.

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Monooxo-bridged Binuclear Molybdenum (V) Complexes (IV) (한 개 산소 가교 이핵몰리브덴 (V) 착물 (제4보))

  • Sang Oh Oh;Jong Dal Rhee
    • Journal of the Korean Chemical Society
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    • v.26 no.2
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    • pp.81-87
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    • 1982
  • The monooxo-bridged binuclear molybdenum(V) complexes, $Mo_2O_3(NCS)_4(Bipy)_2\;(Bipy = bipyridine),\;Mo_2O_3(NCS)-4(Phen)-2$ (Phen = 1,10-phenanthroline), and $Mo_2O_3(NCS)_4(Ox)_2(OxH)_2$ (Ox = oxinato and OxH = oxine) have been prepared. Their electronic and IR spectra, electric conductivity, and magnetic susceptibility were measured. From the results all of th complexes turned out to be electroneutral dimers with about 0.5 BM, and in the oxine complex, $Mo_2O_3(NCS)_2(Ox)_2(OxH)_2$, the oxine seems to bind partly as monodentate and partly as bidentate molecule.

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Dynamics of CO Rebinding to Protoheme in Viscous Solutions

  • Lee, Tae-Gon;Park, Jae-Heung;Kim, Joo-Young;Joo, Sang-Woo;Lim, Man-Ho
    • Bulletin of the Korean Chemical Society
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    • v.30 no.1
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    • pp.177-182
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    • 2009
  • We present the geminate rebinding kinetics measurements of CO to 2-methylimidazole (2-MeIm) bound ferrous protoporphyrin- IX (FePPIX) in alkaline glycerol/water mixtures at 293 K after photolysis. The kinetics was probed by monitoring the CO stretching mode using femtosecond vibrational spectroscopy. When 2-MeIm is used in excess, heme dimers that typically form in low viscosity solutions disappear as the viscosity of the solvent increases. Heme aggregates formed in low viscosity solutions turn monomeric as more 2-MeIm is added, suggesting that 6-coordinated heme, including a strong proximal histidine tends to be in the monomeric form. The vibrational band of CO in the 2-MeIM-FePPIX-CO is well described by a single Gaussian function centered at 1958 $cm^-1$ and 28 $cm^-1$ full width at half maximum. The efficiency and rate of the geminate rebinding of CO to the heme increase with viscosity of the solvent, suggesting that retention of the dissociated CO near the heme, for a longer period by the viscous solvent media, accelerates rebinding.

Dynamics of Hydrogen on Si (100)

  • Boland, John J.
    • Proceedings of the Korean Vacuum Society Conference
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    • 2000.02a
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    • pp.25-25
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    • 2000
  • In this talk we discuss the dynamics of hydrogen on the Si(100)-2xl surface. At room temperature the sticking coefficient for molecular hydrogen on this surface is less than 10sup-12. However, hydrogen molecules desorbing from the surface do not have an excess of energy, suggesting at best a small barrier on the exit channel. These observations have led to speculation about the validity of detailed balance in this system. Here we show that this discrepancy can be explained by considering both the surface-molecule co-ordinate and that associated with the Si-Si dimer bond tiltangle. By preparing the surface dimers with a specific tiltangle we demonstrate that the barrier to adsorption is a function of this angle and that the sticking coefficient dramatically increase for certain angles. The adsorption-desopption dynamics can then be described in terms of a common potential energy hypersurface involving both of these co-ordinates. The implications of these observations are also discussed. The dynamics of adsorbed hydrogen atoms on the Si(100) surface is also described. Paired dangling bonds produced following recombinative hydrogen desorption are mobile at elevated temperatures. Pairs of dangling bonds are observed to dissociate, diffuse, and ultimately recombine. At sufficiently elevated temperatures dangling bond exchange reactions are observed. These data are analyzed in terms of an attractive zone and an effective binding interaction between dangling bonds. Insights that this provides into the nature of surface defects and the localized chemistry that occurs on this surface, are also discussed.

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Crystal Structure of β-Carbonic Anhydrase CafA from the Fungal Pathogen Aspergillus fumigatus

  • Kim, Subin;Yeon, Jungyoon;Sung, Jongmin;Jin, Mi Sun
    • Molecules and Cells
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    • v.43 no.9
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    • pp.831-840
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    • 2020
  • The β-class of carbonic anhydrases (β-CAs) are zinc metalloenzymes widely distributed in the fungal kingdom that play essential roles in growth, survival, differentiation, and virulence by catalyzing the reversible interconversion of carbon dioxide (CO2) and bicarbonate (HCO3-). Herein, we report the biochemical and crystallographic characterization of the β-CA CafA from the fungal pathogen Aspergillus fumigatus, the main causative agent of invasive aspergillosis. CafA exhibited apparent in vitro CO2 hydration activity in neutral to weak alkaline conditions, but little activity at acidic pH. The high-resolution crystal structure of CafA revealed a tetramer comprising a dimer of dimers, in which the catalytic zinc ion is tetrahedrally coordinated by three conserved residues (C119, H175, C178) and an acetate anion presumably acquired from the crystallization solution, indicating a freely accessible "open" conformation. Furthermore, knowledge of the structure of CafA in complex with the potent inhibitor acetazolamide, together with its functional intolerance of nitrate (NO3-) ions, could be exploited to develop new antifungal agents for the treatment of invasive aspergillosis.

Oxidative Inactivation of Peroxiredoxin Isoforms by H2O2 in Pulmonary Epithelial, Macrophage, and other Cell Lines with their Subsequent Regeneration (폐포상피세포, 대식세포를 비롯한 각종 세포주에서 H2O2에 의한 Peroxiredoxin 동위효소들의 산화에 따른 불활성화와 재생)

  • Oh, Yoon Jung;Kim, Young Sun;Choi, Young In;Shin, Seung Soo;Park, Joo Hun;Choi, Young Hwa;Park, Kwang Joo;Park, Rae Woong;Hwang, Sung Chul
    • Tuberculosis and Respiratory Diseases
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    • v.58 no.1
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    • pp.31-42
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    • 2005
  • Background : Peroxiredoxins (Prxs) are a relatively newly recognized, novel family of peroxidases that reduce $H_2O_2$ and alkylhydroperoxide into water and alcohol, respectively. There are 6 known isoforms of Prxs present in human cells. Normally, Prxs exist in a head-to-tail homodimeric state in a reduced form. However, in the presence of excess $H_2O_2$, it can be oxidized on its catalytically active cysteine site into inactive oxidized forms. This study surveyed the types of the Prx isoforms present in the pulmonary epithelial, macrophage, endothelial, and other cell lines and observed their response to oxidative stress. Methods : This study examined the effect of exogenous, excess $H_2O_2$ on the Prxs of established cell lines originating from the pulmonary epithelium, macrophages, and other cell lines, which are known to be exposed to high oxygen partial pressures or are believed to be subject to frequent oxidative stress, using non-reducing SDS polyacrylamide electrophoresis (PAGE) and 2 dimensional electrophoresis. Result : The addition of excess $H_2O_2$ to the culture media of the various cell-lines caused the immediate inactivation of Prxs, as evidenced by their inability to form dimers by a disulfide cross linkage. This was detected as a subsequent shift to its monomeric forms on the non-reducing SDS PAGE. These findings were further confirmed by 2 dimensional electrophoresis and immunoblot analysis by a shift toward a more acidic isoelectric point (pI). However, the subsequent reappearance of the dimeric Prxs with a comparable, corresponding decrease in the monomeric bands was noted on the non-reducing SDS PAGE as early as 30 minutes after the $H_2O_2$ treatment suggesting regeneration after oxidation. The regenerated dimers can again be converted to the inactivated form by a repeated $H_2O_2$ treatment, indicating that the protein is still catalytically active. The recovery of Prxs to the original dimeric state was not inhibited by a pre-treatment with cycloheximide, nor by a pretreatment with inhibitors of protein synthesis, which suggests that the reappearance of dimers occurs via a regeneration process rather than via the de novo synthesis of the active protein. Conclusion : The cells, in general, appeared to be equipped with an established system for regenerating inactivated Prxs, and this system may function as a molecular "on-off switch" in various oxidative signal transduction processes. The same mechanisms might applicable other proteins associated with signal transduction where the active catalytic site cysteines exist.

Effect of Protonic Acids on the Reaction Rate in Chemical Polymerization of Polyaniline (폴리아닐린의 화학적 중합 시 반응속도에 미치는 양성자산의 영향)

  • Hong, Jang-Hoo;Jang, Beom Soon
    • Applied Chemistry for Engineering
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    • v.16 no.5
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    • pp.684-688
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    • 2005
  • Aniline was polymerized in various protonic acid (HF, HC1, HBr, HI, $H_2SO_4$) aqueous solutions with different acidity. During the reaction, the dimer formation and the reaction rate were examined as functions of acidity (pH) and the size of counter ions. Open-circuit potential measurements were carried out to investigate the effect of protonic acid on the reaction rate. The results showed that polymerization rate in HF aqueous solution was very slow and polymerization did not occur in HI aqueous solution. These results were explained in terms of acidity and power of oxidation. The ratio of formation of dimers varied with the kind of protonic acid, and the results were explained with the nucleophilicity, solvation effect, and mobility of counter ions.

Purification and Characterization of Repressor of Temperate S. aureus Phage Φ11

  • Das, Malabika;Ganguly, Tridib;Chattoraj, Partho;Chanda, Palas Kumar;Bandhu, Amitava;Lee, Chia Yen;Sau, Subrata
    • BMB Reports
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    • v.40 no.5
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    • pp.740-748
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    • 2007
  • To gain insight into the structure and function of repressor proteins of bacteriophages of gram-positive bacteria, repressor of temperate Staphylococcus aureus phage ${\phi}11$ was undertaken as a model system here and purified as an N-terminal histidine-tagged variant (His-CI) by affinity chromatography. A ~19 kDa protein copurified with intact His-CI (~ 30 kDa) at low level was resulted most possibly due to partial cleavage at its Ala-Gly site. At ~10 nM and higher concentrations, His-CI forms significant amount of dimers in solution. There are two repressor binding sites in ${\phi}11$ cI-cro intergenic region and binding to two sites occurs possibly by a cooperative manner. Two sites dissected by HincII digestion were designated operators $O_L$ and $O_R$, respectively. Equilibrium binding studies indicate that His-CI binds to $O_R$ with a little more strongly than $O_L$ and binding species is probably dimeric in nature. Interestingly His-CI binding affinity reduces drastically at elevated temperatures ($32-42^{\circ}C$). Both $O_L$ and $O_R$ harbor a nearly identical inverted repeat and studies show that ${\phi}11$ repressor binds to each repeat efficiently. Additional analyses indicate that ${\phi}11$ repressor, like $\lambda$ repressor, harbors an N-terminal domain and a C-terminal domain which are separated by a hinge region. Secondary structure of ${\phi}11$ CI even nearly resembles to that of $\lambda$ phage repressor though they differ at sequence level. The putative N-terminal HTH (helix-turn-helix) motif of ${\phi}11$ repressor belongs to the HTH -XRE-family of proteins and shows significant identity to the HTH motifs of some proteins of evolutionary distant organisms but not to HTH motifs of most S. aureus phage repressors.

Structure of $\alpha$,$\beta$-Diphenylsuccinic Acid ($\alpha$,$\beta$-Diphenylsuccinic Acid의 구조)

  • 서일환;윤민중
    • Korean Journal of Crystallography
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    • v.5 no.2
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    • pp.108-112
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    • 1994
  • C19H20O5, Mr=314.337, triclinic,PI, a=10.291(2)A, b=11.218(3)A, c=3.059(1)A, α=74.54(2)°, β=1148.84(1)°, r=109.84(2)°, V=883.283(2)A3, λ(Mo Kα)=0.71069A, μ=0.47 mm-1, F(000)=324, 296K, Z=2, Dx=1.18Mgm-3. Final R=0.0580 for 1637[F>3σ(F)]unique refledtions. α,β-diphenylsuccinic acid, C16H14O4, are connedted with the solvent actone by hydrogen bond O(4)-H˙˙˙O(5), forming a dimer related by related by centrosymmentry thorough intermolecualr carboxylic hydrogen bond O(1)-H˙˙˙O(2)(-x,-y,-z). The nearest distance 3.288A[O(2)˙˙˙O(2)(-x,-y,-z)] between the dimers shows that the packing of the dimer is govermed by van der Waals'force.

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Synthesis of Dimeric Lignin Model Compounds - Veratrylglycerol-β-vanillylalcohol ether compounds - (리그닌 이양체(二量體) 모델화합물(化合物)의 합성(合成) - Veratrylglycerol-β-vanillylalcohol ether 화합물(化合物) -)

  • Zhao, Julan;Hwang, Byung-Ho
    • Journal of Forest and Environmental Science
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    • v.12 no.1
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    • pp.37-44
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    • 1996
  • Two dilignols composed of ${\beta}$-O-4 structure, a important substructure compound in lignin, was synthesized in high yield in a series of the synthetic studies of lignin model compounds. The dimers were identified with $^1H$ and $^{13}C$-NMR and Mass spectroscopy. The important compound of among them, the final synthetic compound [IV].is called 1-(3,4-dimethoxyphenyl)-2-(2'-methoxy-4'-hydroxymethylphenoxy)-propanediol-l,3. This dimeric lignin model compounds should be usefull for the studies of lignin reactions such as pulping, bleaching, pyrolysis, hydrogenolysis, oxidation, reduction, biodegradation, and chemical utilization.

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