• Title/Summary/Keyword: $^{31}P$-NMR spectra

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Modulation of the Specific Interaction of Cardiolipin with Cytochrome c by Zwitterionic Phospholipids in Binary Mixed Bilayers: A $^2H$-and $^{31}P$-NMR Study

  • Kim, Andre;Jeong, In-Chul;Shim, Yoon-Bo;Kang, Shin-Won;Park, Jang-Su
    • BMB Reports
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    • v.34 no.5
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    • pp.446-451
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    • 2001
  • The interaction of cytochrome c with binary phospholipid mixtures was investigated by solid-state $^2H$- and $^{31}P$-NMR. To examine the effect of the interaction on the glycerol backbones, the glycerol moieties of phosphatidylcholine (PC), and cardioliph (CL) were specifically deuterated. On the binding of cytochrome c to the binary mixed bilayers, no changes in the quadrupole splittings of each of the components were observed for the PC/PG, PE/CL and PE/PG liposomes. In contrast, the splittings of CL decreased on binging of protein to the PC/CL liposomes, although those of PC did not change at all. This showed that cytochrome c specifically interacts with CL in PC/CL bilayers, and penetrates into the lipid bilayer to some extent so as to perturb the dynamic structure of the glycerol backbone. This is distinctly different from the mode of interaction of cytochrome c with other binary mixed bilayers. In the $^{31}P$-NMR spectra, line broadening and a decrease of the chemical shift anisotropy were observed on the binding of cytochrome c for all binary mixed bilayers that were examined. These changes were more significant for the PC/CL bilayers. Furthermore, the line broadening is more significant for PC than for CL in PC/CL bilayers. Therefore, it can be concluded that with the polar head groups, not only CL but also PC are involved in the interaction with cytochrome c.

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An NMR Study on the Phase Change of Lipid Membranes by an Antimicrobial Peptide, Protegrin-1

  • Kim, Chul
    • Bulletin of the Korean Chemical Society
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    • v.31 no.2
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    • pp.372-378
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    • 2010
  • Membrane disruption by an antimicrobial peptide, protegrin-1 (PG-1), was investigated by measuring the $^2H$ solid-state nuclear magnetic resonance (SSNMR) spectra of 1-palmitoyl-$d_{31}$-2-oleoyl-sn-glycero-3-phosphatidylcholine (POPC_$d_{31}$) in the mixture of PG-1 and POPC_$d_{31}$ lipids deposited on thin cover-glass plates. The experimental line shapes of anisotropic $^2H$ SSNMR spectra measured at various peptide-to-lipid (P/L) ratios were simulated reasonably by assuming the mosaic spread of bilayers containing pore structures or the coexistence of the mosaic spread of bilayers and a fast-tumbling isotropic phase. Within a few days of incubation in the hydration chamber, the pores were formed by the peptide in the POPC_$d_{31}$ and POPC_$d_{31}$/cholesterol membranes. However, the formation of the pores was not clear in the POPC_$d_{31}$/1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylglycerol (POPG) membrane. Over a hundred days after hydration, a rapidly rotating isotropic phase increased in the POPC_$d_{31}$ and the POPC_$d_{31}$/cholesterol membranes with the higher P/L ratios, but no isotropic phase appeared in the POPC_$d_{31}$/POPG membrane. Cholesterol added in the POPC bilayer acted as a stabilizer of the pore structure and suppressed the formation of a fast-tumbling isotropic phase.

Interactions of Membrane and PMAP-23 Studied by $^{31}P$ solid-state NMR Spectroscopy

  • Kim, Si-Won;Kim, Suhk-Mann
    • Journal of the Korean Magnetic Resonance Society
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    • v.11 no.2
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    • pp.110-114
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    • 2007
  • [ $^{31}P$ ] powder pattern spectra were measured to investigate the aspects of the interaction between the MLV (Multilamellar vesicle) and PMAP-23, a membrane of cathelicidin family and then CSAs(chemical shift anisotropy) were calculated to indentify the extent of perturbation of phospholipid mobility by the peptides. We found that acidic phospholipid interacts strongly with PMAP-23, and the analogues which modified to increase the amphipathic property showed that larger change of CSA. The analogue which introduced positive charge showed the same effects with amphipathic property.

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Conformations of Tetrahomodioxa-p0phenylcalix[4]arene Alkyl Ethers

  • No, Kwang-Hyun;Park, Young-Ja
    • Bulletin of the Korean Chemical Society
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    • v.23 no.11
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    • pp.1629-1634
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    • 2002
  • Reaction of tetrahomodioxa p-phenylcalix[4]arene with alkyl halide and NaH in DMF leads to the title tetra-alkylated derivatives, 7,13,21,27-tetra-phenyl-29,30,31,32-tetraalkyloxy-2,3,16,17-tetrahomo-3,17-dioxacalix [4]arenes, their preferred conformations were determined by NMR spectra as C-1,2-alternate. The molecular structure of allyl derivative has been solved by X-ray diffraction methods. The molecules have a conformation with pseudo center of symmetry. The benzene ring A is up, ring C is down, B and D rings are flat with respect to the plane of the macrocyclic ring.

The [M(cod)(PPh$_3)_2] PF_6$ (M = Rh, Ir; cod = 1,5-cyclooctadiene) Mediated Activiation of Aldehyde C-H Bond

  • Ko, Jae-Jung;Joo, Wan-Chul
    • Bulletin of the Korean Chemical Society
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    • v.8 no.5
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    • pp.372-376
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    • 1987
  • Acetone solution of quinoline-8-carbaldehyde reacts with $[Rh(cod)(PPh_3)_2] PF_6$and $[Ir(cod)(PPh_3)_2] PF_6$ to yield $[Rh(NC_9H_6CO)(H)(PPh_3)_2(CH_3COCH_3)] PF_6$ (1) and $[Ir(NC_9H_6CO)(H)(PPh_3)_2(CH_3COCH_3)] PF_6$ (2), respectively. The compound $[Ir(cod)(PPh_3)_2] PF_6$ also reacts with $Ph_2PC_6H_4-o-CHO$ in the acetone / $H_2O$ mixture to give $[Ir(Ph_2PC_6H_4-o-CO)(H)(PPh_3)_2(CH_3COCH_3)] PF_6$ (3). Compounds 1, 2, and 3 were characterized by infrared, $^1H$ NMR, $^{31}P$ NMR spectra and conductivity measurement. The $^1H$ NMR spectra of 1, 2, and 3 support the presence of a terminal hydride that is cis to the phosphine. The IR band of 3 at 2185 $cm^{-1}$, which is assigned to $\nu$(Ir-H), and the hydride cleavage reaction of 3 with $CCl_4$, provide evidence for the Ir-H bond.

Radical Addition Reaction of Phosphorous based Flame Retardant with End Groups of PET (1) - Reaction of Bisphenol A bis(diphenyl phosphate) - (PET 말단에 대한 인계난연제의 라디칼계 부가반응 (1) - 비스페놀에이비스다이페닐포스페이트의 반응 -)

  • Kim, Min-Kwan;Ghim, Han-Do
    • Textile Coloration and Finishing
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    • v.24 no.1
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    • pp.33-38
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    • 2012
  • In this study, to increase flame retardation of poly(ethylene terephthalate) (PET) in burning, bisphenol A bis(diphenyl phosphate) (BDP), a well known flame retardant containing phosphorous, was reacted on end groups of PET by radical pathway. End-capping mechanism of PET with BDP was suggested and confirmed by spectroscopic and thermal analysis. From 400 MHz $^{31}P$ solid state FT-NMR spectrum of end-capped PET (PET-BDP), phosphorus spectra peak in BDP was found at ca. -20 ppm. Furthermore, P-C bond stretching vibration peaks were found ca. $600cm^{-1}$ in FT-IR spectrums of PET-BDP. These results showed that BDP can be chemically added on end groups of PET by our method. Thermal characteristics of pure PET (pPET) and PET-BDP were measured and evaluated by TGA analysis. There was not significant changes in thermal characteristics of PET-BDP compared to that of pPET.

Radical Addition Reaction of Phosphorous based Flame Retardant with End Groups of PET (2) - Reaction of Resorcinol bis(diphenyl phosphate) - (PET 말단에 대한 인계난연제의 라디칼계 부가반응 (2) - 리소시놀비스다이페닐포스페이트의 반응 -)

  • Kim, Min-Kwan;Sohn, Kwang-Ho;Ghim, Han-Do
    • Textile Coloration and Finishing
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    • v.24 no.1
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    • pp.39-44
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    • 2012
  • To improve flame retardation of poly(ethylene terephthalate) (PET) against burning, resorcinol bis(diphenyl phosphate) (RDP), phosphorous containing flame retardant, was incorporated into PET backbone by radical reaction pathway. Radical endcapping of PET with RDP was confirmed by spectroscopic and thermal analysis. From 400 MHz $^{31}P$ solid state FT-NMR spectrum of PET with RDP (PET-RDP), phosphorus spectra peak in RDP was found at ca. -10 ppm. Furthermore, P-C bond stretching vibration peaks were found ca. $530cm^{-1}$ in FT-IR spectrums of PET-RDP. These results indicated that RDP can be chemically bound at the ends of PET by radical addition method. Thermal characteristics of pure PET (pPET) and PET-RDP were measured and evaluated by TGA thermal analysis. There was not significant changes in thermal characteristics of PET-RDP compared to that of pPET.

Synthesis Catalytic Application of Several$d^8Transition Metal Diphosphine Complexes, (MCl_2PP) (M = Ni^{2+}, Pd^{2+}, Pt^{2+}, Au^{3+} ; PP = diphosphines)$ (몇가지 $d^8$ 전이금속-디포스핀 착물 ($MCl_2PP$)의 합성과 촉매적 응용 (M = $Ni^{2+}$, $Pd^{2+}$, $Pt^{2+}$, $Au^{3+}$ ; PP = diphosphines))

  • Park Yu-Chul;Kim Kyung-Chae;Cho Young-Jae
    • Journal of the Korean Chemical Society
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    • v.36 no.5
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    • pp.685-691
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    • 1992
  • The $d^8$-transition metal complexes containing diphosphine, $MCl_2PP$ were prepared by using $K_nMCl_m$ as starting materials, wherein M were Ni(II), Pd(II), Pt(II) and Au(III) and PP were bis(diphenylphosphino)methane(dppm), bis(diphenylphosphino)ethane(dppe), bis(diphenylphosphino)propane (dppp) and bis(diphenylphosphino)ethylene(dppety). The complexes were characterized by the spectral property $(^H-NMR$, $^{31}P-NMR$ and UV-Visible spectra) together with elemental analysis. The complexes were tested for the catalytic activity on the formation reactions of 3(2H)-furanone and cyclic carbonate. The only Ni(II)- and Pd(II)-diphosphine complexes displayed a good catalytic effects in the production of 3(2H)-furanone from 2-methyl-3-butyn-2-ol [reaction (1)]. But all the diphosphine complexes as catalyst were almost inactive towards cyclic carbonate production preaction [reaction (2)].

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Cadmium Detoxification Mechanism in Klebsiella aerogenes ATCC 10031 (Klebsiella aerogenes ATCC 10031의 카드뮴 해독기작)

  • 이기성;유순애;곽인영;박영식;최영길
    • Korean Journal of Microbiology
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    • v.28 no.2
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    • pp.134-144
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    • 1990
  • In order to examine that what kind of system correlated with cadmium detoxification mechanism in Klebsiella aerogenes ATCC 10031, we tried to investigate the effect of phosphate upon the detoxification and also elucidate whether the cadmium phosphate and/or polymeric Cd-Pi complex is formed actually in cell or not. As the results, it was shown that growing pattern had long lag adaptive phase of 12 hr to 24 hr, at the concentrations of 0.02 mM and 0.08 mM cadmium, respectively. Cadmium was accumulated more highly in the fraction of cell wall and membrane than in those of cytoplasm. In case of phosphate starving cells added cadmium, inorganic polyphosphate system was primarily correlated with Cd-detoxification during the lag phase for the accommodation to cadmium, on the other hand, Cd:Sulfide complex system secondarily correlated it during the stationary phase. These results implied that polyphosphate system and Cd:sulfide complex system, these two systems were operated compensatively each other. Considering the results obsdrved with EM and examined tha changes of sulfide and polyphosphate amount, it was reflected that Cd:S complex was located at the cell surface. In the results of $in-vivo^{31}$P NMR spectra in the cells with cadmium pressure, several phosphate signals arose newly from the polyphosphate region with moving chemical shift of it. This phinomenon strongly implied the actual existence of Dd:Pi comples and /or Cd:poly-P complex in the cell and also the cellular compartmentalization of cadmium detoxifying mechanism.

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Cytotoxic Compounds from the Flowers of Paulownia coreana (오동나무꽃의 항암성분)

  • Oh, Joa-Sub;Zee, Ok-Pyo;Moon, Hyung-In
    • Korean Journal of Pharmacognosy
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    • v.31 no.4
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    • pp.449-454
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    • 2000
  • In search for plant-derived cytotoxic compounds, it was found that the $CHCl_3$ and EtOAC extracts obtained from the flowers of Paulownia coreana Uyeki (Scrophulariaceae) exhibited significant cytotoxic activity against human tumor cell lines, A549, SK-OV-3, SK-MEL-2, XF498, and HCT15. Activity-guided fractionation on the basis of the inhibitory activity against the growth of human tumor cell lines, in vitro, and repeated column chromatography afforded several cytotoxic compounds from P. coreana. The structures and stereochemistry of these compounds were established, on the basis of analysis of spectra including IR, UV, EI-MS, $^{1}H-NMR,\;^{13}C-NMR$ and some chemical transformations, as Compound PCCl $(2-hydroxy-4(15),11(13)-eudesmadien-8{\beta},12-olide)$, Compound $PCC2(2,3-dihydro-4-hydroxy-1(15),11(13)-xanthadien-8{\beta},12-olide)$, Compound PCE1 (chrysophanol), Compound PCE2 (emodin), Compound PCE3 (physcion). Cytotoxic activity of compounds obtained from P. coreana. on five tumor cells lines was evaluated by procedure of SRB methods.

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