• Title/Summary/Keyword: CD spectroscopy

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Biochemical and Biophysical Characterizations of the Interaction between Two PDZ Adapter Proteins NHERF and E3KARP in vitro

  • Hwang, Eun-Young;Jeong, Mi-Suk;Jang, Se-Bok
    • Bulletin of the Korean Chemical Society
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    • v.31 no.11
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    • pp.3241-3246
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    • 2010
  • NHERF ($Na^+/H^+$ exchanger regulatory factor) and E3KARP (NHE3 kinase A regulatory protein) play important roles in membrane targeting, trafficking and sorting of ion channels, transmembrane receptors and signaling proteins in many tissues. Each of these proteins contains two PDZ (PSD-95/Dlg-1/ZO-1) domains, which mediate the assembly of transmembrane and cytosolic proteins into functional signal transduction complexes. The interaction between NHERF and E3KARP was investigated by surface plasmon resonance spectroscopy (BIAcore), fluorescence measurement, His-tagged pull-down experiment, and size-exclusion column (SEC) chromatography. BIAcore experiments revealed that NHERF bound to E3KARP with an apparent $K_D$ of 7 nM. Fluorescence emission spectra of the NHERF-E3KARP complex suggested that the tight interaction between these proteins was accompanied by significant conformational changes in one or both. The CD spectra of NHERF and E3KARP show that the conformational changes of these proteins were dependent on pH and temperature. These results implicate that the NHERF-E3KARP complex allows intracellular signaling complexes to form through PDZ-PDZ interactions.

Preparation and Characterization of Half-Sandwich Cobalt(III) Complexes of Cp Ligands with a Rigid Thioanisole Side-Chain

  • S, Sujith;Lee, Bun-Yeoul;Han, Jin-Wook
    • Bulletin of the Korean Chemical Society
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    • v.28 no.8
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    • pp.1299-1304
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    • 2007
  • New sulfur functionalized cyclopentadiene ligands, 1-[2-(thioanisole)]-2,5-dimethylcyclopentadiene (3), 1-[2- (thioanisole)]-2,3,5-trimethylcyclopentadiene (4), and 1-[2-(thioanisole)]-2,3,4,5-tetramethylcyclopentadiene (5), were prepared. In these ligands, the S-donor atom is connected to a cyclopentadiene ring by a rigid phenylene spacer. CpCo(III)-diiodo half-sandwich complexes (6-8) were obtained from reaction the ligands (3- 5) with Co2(CO)8, followed by treatment of I2. Substitution reaction of CpCo(III)-diiodo complexes with MeLi yielded the corresponding CpCo(III)-dimethyl complexes (9-11). Further transformation to the corresponding cationic cobalt complexes (12-14) were achieved by reaction of the CpCo(III)-dimethyl complexes with HB(ArF)4·2Et2O and trapping with CD3CN. The new sulfur functionalized cyclopentadiene ligands having a rigid phenylene spacer and the corresponding cobalt complexes were characterized by 1H, 13C and 19F NMR spectroscopy. The diiodo Complex 6 was also characterized by a single crystal X-ray diffraction method.

Direction of Intercalation of a bis-Ru(II) Complex to DNA Probed by a Minor Groove Binding Molecule 4',6-Diamidino-2-phenylindole

  • Jang, Yoon Jung;Kim, Raeyeong;Chitrapriya, Nataraj;Han, Sung Wook;Kim, Seog K.;Bae, Inho
    • Bulletin of the Korean Chemical Society
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    • v.34 no.10
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    • pp.2895-2899
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    • 2013
  • Direction of intercalation to DNA of the planar dipyrido[3,2-a:2',3'-c]phenazine ligands (dppz) of a bis-Ru(II) complex namely, $[Ru(1,10-phenanthroline)_2dipyrido[3,2-a:2^{\prime},3^{\prime}-c]phenazine]^{2+}$ linkered by a 1,3-bis(4-pyridyl)propane, was investigated by probing the behavior of 4',6-diamidino-2-phenylindole (DAPI) that bound deep in the minor groove. Bis-intercalation of DPPZ resulted in a little blue shift and hyperchromism in DAPI absorption band, and a large decrease in DAPI fluorescence intensity which accompined by an increase in the dppz emission intensity. Diminishing the intenisty of the positive induced circular dichroism (CD) and linear dichroism (LD) were also observed. These spectral changes indicated that insertion of dppz ligand caused the change of the binding mode of DAPI, which probably moved to the exterior of DNA from the minor groove and interacted with the phospghate groups of DNA by electrostatic interaction. At the surface of DNA, DAPI binds at the phosphate groups of DNA by electrostatic attraction. Consequently, this observation indicated that the dppz ligand intercalated from the minor groove.

¹H NMR Study of the Effect of G-T Mismatches on Dynamics and Stability of d(GCGTGCGC)₂ and Its Berenil Complex

  • 허성호;홍석주;이조웅;정채준
    • Bulletin of the Korean Chemical Society
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    • v.17 no.11
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    • pp.1045-1052
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    • 1996
  • The effects of G-T mismatches on thermal stability, the base-pair lifetime and the global structure of a d(GCGTGCGC)2 duplex were studied by using 1H NMR, UV and CD spectroscopy. The existence of G-T mismatches was found to cause a noticeable change in the chemical environment of imino protons associated with significant decrease in the base-pair lifetime at the mismatched site as well as in thermal stability of the duplex itself. The melting transition of d(GCGTGCGC)2 was not cooperative at all at 100 mM or lower concentration of NaCl, but became cooperative at 500 mM or higher NaCl concentration. The melting temperature (Tm) of this duplex was 32℃ at 500 mM concentration of NaCl, which is much lower than that of d(GCGCGCGC)2 at the same NaCl concentration. This suggests that the decrease in stability may be ascribed to the decrease in the base-pair lifetime and the deviation from the normal structure due to the G-T mismatches. Adding berenil to d(GCGTGCGC)2 caused no observable change in the global structure but the large decrease in the base-pair lifetime and the stability of the duplex.

Heavy metal profiles of agricultural soils in Sakarya, Turkey

  • Isleyen, Mehmet;Akpinar, Aysegul;Eren, Beytullah;Ok, Gulsun
    • Environmental Engineering Research
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    • v.24 no.3
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    • pp.427-433
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    • 2019
  • Sakarya is famous for cucurbit productions in Turkey and cucurbits can grow as big as 560 kg of weight per fruit in its agricultural areas. There is no or limited information about contaminant levels and profiles of the agricultural fields in Sakarya. The purpose of this study is to investigate the levels of polycyclic aromatic hydrocarbons (PAHs) (naphthalene, phenanthrene, pyrene, and fluoranthene) and heavy metal (As, Cd, Cu, Cr, Ni, Pb, Zn) concentrations of the selected fields. Total 33 soil samples were collected from 12 counties of Sakarya where both cucurbits have been produced and organochlorine pesticides have been applied to the fields for more than 30 y during the historical plantation periods. Heavy metal and PAH contents in the soil samples were measured by an Inductively Coupled Plasma Emission Spectroscopy and a Gas Chromatography-Mass Spectrometry. The highest phenanthrene, pyrene, and fluoranthene concentrations were measured as 63.50 ng/g, 134.34 ng/g, 140.0 ng/g, respectively in the soil samples from Geyve County. Cu, Ni, and Cr concentrations were measured as 108.2 mg/kg, 219.9 mg/kg, and 173.1 mg/kg, respectively in Geyve's samples which were also the highest and 2-7 times more than the limit values given in the Turkish Soil Pollution Control Regulation. Precautions need to be taken for Sakarya's agricultural fields which are an important milestone of Turkey's cucurbit and fruit productions since the contaminants can be accumulated in the fruits and edible parts of the plants.

Effect of extraction conditions on chemical composition and antioxidant properties of mulberry fruit

  • Lee, Sora;Koo, Bonwoo;Ju, Wan-Taek;Kim, Hyun-Bok;Kweon, HaeYong;Lee, Ji Hae
    • International Journal of Industrial Entomology and Biomaterials
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    • v.42 no.2
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    • pp.25-32
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    • 2021
  • Mulberry fruit (Morus alba L.) contains phytochemicals, including 1-deoxynojirimycin, quercetin-glucoside, kaempferol-glucoside, and anthocyanins, which have antioxidant effects. In this study, mulberry fruit extract was prepared at various temperatures (25-100℃) and water/ethanol solvent concentrations (0%-100% ethanol). Fourier-transform infrared spectroscopy (FT-IR) and circular dichroism (CD) data indicated that the content of bioactive compounds such as polyphenols and flavonoids was lower in 100% ethanolic extracts than in 30%-50% ethanolic extracts. Radical scavenging activity determined using 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2'-azino-di-3-ethylbenzthiazoline sulfonic acid (ABTS) assays was highly correlated with polyphenol and flavonoid content. In conclusion, 30%-50% ethanolic extracts contained the highest contents of bioactive compounds and exhibited high levels of radical scavenging activity. These findings may inform the use of mulberry fruit extract as a functional food.

Leachability of lead, cadmium, and antimony in cement solidified waste in a silo-type radioactive waste disposal facility environment

  • Yulim Lee;Hyeongjin Byeon;Jaeyeong Park
    • Nuclear Engineering and Technology
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    • v.55 no.8
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    • pp.2889-2896
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    • 2023
  • The waste acceptance criteria for heavy metals in mixed waste should be developed by reflecting the leaching behaviors that could highly depend on the repository design and environment surrounding the waste. The current standards widely used to evaluate the leaching characteristics of heavy metals would not be appropriate for the silo-type repository since they are developed for landfills, which are more common than a silo-type repository. This research aimed to explore the leaching behaviors of cementitious waste with Pb, Cd, and Sb metallic and oxide powders in an environment simulating a silo-type radioactive waste repository. The Toxicity Characteristic Leaching Procedure (TCLP) and the ANS 16.1 standard were employed with standard and two modified solutions: concrete-saturated deionized and underground water. The compositions and elemental distribution of leachates and specimens were analyzed using an inductively coupled plasma optical emission spectrometer (ICP-OES) and energy-dispersive X-ray spectroscopy combined with scanning electron microscopy (SEM-EDS). Lead and antimony demonstrated high leaching levels in the modified leaching solutions, while cadmium exhibited minimal leaching behavior and remained mainly within the cement matrix. The results emphasize the significance of understanding heavy metals' leaching behavior in the repository's geochemical environment, which could accelerate or mitigate the reaction.

Microstructural Properties of the Insoluble Residue in a Simulated Spent Fuel

  • Kim, J.S.;Song, B.C.;Jee, K.Y.;Kim, J.G.;Chun, K.S.
    • Nuclear Engineering and Technology
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    • v.30 no.2
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    • pp.99-111
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    • 1998
  • Chemical composition of the insoluble residue in a simulated spent PWR fuel(SIMRJEL) were studied. SIMFUELS were prepared by adding calculated amount of FP(fission product) elements with a burnup of 3.6% FIMA(fission per initial metal atom) to uranium in nitrate solution, evaporating the mixed solution to dryness, calcining at 90$0^{\circ}C$ in a stream of 4% H$_2$ + 96% He, and heating the pellet at 140$0^{\circ}C$ under high and low oxygen potentials. Insoluble residue was obtained from the dissolution of the SIMFUEL with HNO$_3$(1 : 1). The chemical composition of the SIMFUELs and the insoluble residues was determined by EPMA(electron probe microanalysis), XPS(X-ray photoelectron spectroscopy) and by XRD (X-ray diffraction) measurements. All of the insoluble residues suspended and precipitated were composed mainly of Mo, Ru with a small amount of Zr, Rh, Pd and Cd. The amount of insoluble residue(<1 wt.%) and a Mo/Ru ratio decreased with increasing oxygen potential. Formation of the zirconium molybdate precipitate, ZrMo$_2$O$_{7}$(OH)$_2$($H_2O$)$_2$, was observed in the residues. The possible role of Mo on the phase formation was discussed in regard to oxygen potential.l.

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Sequence Dependent Binding Modes of the ΔΔ- and ΛΛ-binuclear Ru(II) Complexes to poly[d(G-C)2] and poly[d(A-T)2]

  • Chitrapriya, Nataraj;Kim, Raeyeong;Jang, Yoon Jung;Cho, Dae Won;Han, Sung Wook;Kim, Seog K.
    • Bulletin of the Korean Chemical Society
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    • v.34 no.7
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    • pp.2117-2124
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    • 2013
  • The binding properties and sequence selectivities of ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ (bip = 4,4'-biphenylene (imidazo [4,4-f][1,10]phenanthroline) complexes with $poly[d(A-T)_2]$ and $poly[d(G-C)_2]$ were investigated using conventional spectroscopic methods. When bound to $poly[d(A-T)_2]$, a large positive circular dichroism (CD) spectrum was induced in absorption region of the bridging moiety for both the ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complexes, which suggested that the bridging moiety sits in the minor groove of the polynucleotide. As luminescence intensity increased, decay times became longer and complexes were well-protected from the negatively charged iodide quencher compared to that in the absence of $poly[d(A-T)_2]$. These luminescence measurements indicated that Ru(II) enantiomers were in a less polar environment compared to that in water and supported by minor groove binding. An angle of $45^{\circ}$ between the molecular plane of the bridging moiety of the ${\Delta}{\Delta}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complex and the local DNA helix axis calculated from reduced linear dichroism ($LD^r$) spectrum further supported the minor groove binding mode. In the case of ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complex, this angle was $55^{\circ}$, suggesting a tilt of DNA stem near the binding site and bridging moiety sit in the minor groove of the $poly[d(A-T)_2]$. In contrast, neither ${\Delta}{\Delta}$-nor ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complex produced significant CD or $LD^r$ signal in the absorption region of the bridging moiety. Luminescence measurements revealed that both the ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complexes were partially accessible to the $I^-$ quencher. Furthermore, decay times became shorter when bis-Ru(II) complexes bound to $poly[d(G-C)_2]$. These observations suggest that both the ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complexes bind at the surface of $poly[d(G-C)_2]$, probably electrostatically to phosphate group. The results indicate that ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ are able to discriminate between AT and GC base pairs.

Electronic Structure and Elemental Composition of the Lead Sulfide Colloidal Quantum Dots Depending on the Types of Ligand and Post-Treatment (리간드 종류와 후처리 공정에 따른 황화납 콜로이드 양자점 박막의 전자 구조 및 원소 조성 분석)

  • Kim, Tae Gun;Choi, Hyekyoung;Jeong, Sohee;Kim, Jeong Won
    • Journal of the Korean Chemical Society
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    • v.60 no.6
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    • pp.402-409
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    • 2016
  • Thin films of lead sulfide colloidal quantum dots (CQDs) of 2.8 nm in diameter are fabricated and their surfaces are passivated by 3-mercaptopropionic acid (MPA) ligand or hybrid type ($MPA+CdCl_2$) ligand, respectively. The changes in valence band electronic structure and atomic composition of each PbS CQD film upon post-treatment such as air, N2 annealing or UV/Ozone have been studied by photoelectron spectroscopy. The air annealing makes the CQD fermi level to move toward the valence band leading to "p-type doping" regardless of ligand type. The UV/Ozone post-treatment generates $Pb(OH)_2$, $PbSO_x$ and PbO on both CQD surfaces. But the amount of the PbO has been reduced in hybrid type ligand case, especially. That is probably because the extra Pb cations in (111) surface are additionally passivated by $Cl_2$ ligand, which limits the reaction between the Pb cation and ozone.