• Title/Summary/Keyword: Solution NMR

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Tailoring Molecular Precursors for Multicomponent Oxides

  • Hubert-Pfalzgraf, Liliane G.
    • The Korean Journal of Ceramics
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    • v.6 no.4
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    • pp.370-379
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    • 2000
  • Simple ways to build up mixed-metal molecules which can act as potential single-source precursors to multimetallic oxides are reviewed. Emphasis is given to Lewis acid-base reactions between metal alkoxides M(OR)/sub n/, and between metal alkoxides and more accessible oxide precursors, carboxylates M(O₂CR)/sub n/ and β-diketonates M(β-dik)/sub n/. Characterization of the precursors is achieved in the solid state (single crystal X-ray diffraction, FT-IR) and by multinuclear NMR in solution. The reactions proceed toward the formation of aggregates in which the different metals display their usual coordinations numbers, often six for transition metals, as shown. Strategies for fixing the stoichiometry between the metals are developed. The reactivity of the MM species (dissociation, effects of chemical modifiers, of other metallic species, hydrolytic or non-hydrolytic condensation, etc.) will be indicated. Transformations into oxides are illustrated on precursors for titanates or niobates.

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Purification and Structural Studies on Human Pro-ghrelin

  • Yun, Ji-Hye;Lee, Jee-Won;Lee, Weon-Tae
    • Journal of the Korean Magnetic Resonance Society
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    • v.12 no.1
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    • pp.40-50
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    • 2008
  • Ghrelin is a unique peptide hormone that releases growth factor and it stimulates appetite. It comes from pre pro-ghrelin by the post translational modification process and its innate functions are known as food up-take and the growth hormone regulation. Therefore, the structural information of ghrelin precursor is of importance in understanding it function. From our results, we found that the solution structure of ghrelin is mostly random coil conformation at neutral pH value and the structural population changes with pH environments. Data from circular dichroism in different TFE concentrations revealed that the secondary structure changes from random coil to a-helix and the isodichroic point is observed at 202nm, implying that two equilibrium states exist between random coil and helical structure.

Photochemistry and Thermochemistry of Picolyl Chlorides

  • Shim, Sang-Chul;Kim, Sung-Sik
    • Bulletin of the Korean Chemical Society
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    • v.3 no.3
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    • pp.110-115
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    • 1982
  • Thermochemistry and photochemistry of picolyl chlorides were studied. The thermal reaction of 2-picolyl chloride in benzene afforded intermolecular condensation product. In the case of 3-picolyl chloride, this type of the reaction did not occur, but polymers were obtained. A cyclic hexamer, suggested by a molecular model, was not formed because of the steric strain and low reactivity. The thermal reaction of 4-picolyl chloride gave a cyclic hexamer as well as a polymer. The cyclic hexamer, identified by NMR spectrum, showed ${\lambda}_{max}$ at 460 nm. The cyclic hexamer was cloven to the linear structure. Photolysis of 2-picolyl chloride at 253.7 nm gave a para-isomer followed by polymerization. When a methyl hydrogen of 2-methylpyridine is substituted by $CH_3O$, iso-PrO, and EtO group, the photoisomerization to the corresponding anilines or para-substituted pyridines did not occur within the range of the time used for 2-picolyl chloride. Thermolysis of picolyl chlorides in an acidic methanol solution did not afford any product.

$^{13}C$ and $^{51}V$ Nuclear Magnetic Resonance Studies of Vanadium(V) Complexes of Iminodiacetate Analogues

  • Lee, Man-Ho
    • Bulletin of the Korean Chemical Society
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    • v.13 no.1
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    • pp.22-26
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    • 1992
  • The solution structures of the vanadium(V) complexes of iminodiacetate analogues, such as iminodiacetate (IDA), methyliminodiacetate (MeIDA), ethyliminodiacetate (EtIDA), benzyliminodiacetate (BzIDA), pyridine-2,6-dicarboxylate (DPA), and 2-hydroxyethyliminodiacetate (HEIDA), have been studied by $^{13}C-$ and $^{51}V$-NMR spectroscopy. Assuming that the complexes have a $cis-VO_2$ core, IDA, MeIDA, EtIDA, and BzIDA act as facial tridentate ligands to form octahedral complexes, whereas DPA coordinates to $VO_2^+$ as a meridional tridentate. And one water molecule fulfills the remaining site to satisfy the coordination number of six. But HEIDA coordinates to $VO_2^+$ through one IDA moiety and one hydroxyl group, acting as a tetradenate.

Study of Oganophosphorus Compound (I). Synthesis of Heterocyclic Compounds Containing Phosphorus Atom

  • Dong-Young Oh;Byoung-Mog Kwon
    • Bulletin of the Korean Chemical Society
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    • v.1 no.2
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    • pp.54-57
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    • 1980
  • Trichloromethylphosphonyl dichloride was prepared by the aluminium chloride method. We synthesized several heterocyclic compounds containing phosphorus atom by the stepwise esterification of trichloromethylphosphonyl dichloride with ethylene glycol, 2-mercaptoethanol, ethylene diamine, and 2-aminoethanol and the resulting heterocyclic compounds are 2-trichloromethyl-1,3,2-dioxa-, 2-trichloromethyl-1,3,2-thioxa-, 2-trichloromethyl-1,3,2-diaza-, 2-trichloromethyl-1,3,2-diaza-, and 2-trichloromethyl-1,3,2-oxazaphospholane-2-oxide. The best results were obtained in the solution of triethylamine as hydrochloric acid trapping agent. The structure of five-membered heterocyclic phosphonates were characterized by their IR, NMR, and elementary analysis and the mass spectra of the compounds were analyzed.

Synthesis and Optical Properties of Poly[6'-(N-carbazolyl)hexyl-2-ethynylpyridinium bromide]

  • 갈영순;이상섭;배장순;김봉식;장상희;진성호
    • Bulletin of the Korean Chemical Society
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    • v.20 no.4
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    • pp.451-455
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    • 1999
  • The polymerization of 2-ethynylpyridine by alkyl bromide carrying carbazole moiety, 6-(N-carbazolyl)hexyl bromide, relatively proceed well to give the corresponding poly[6'-(N-carbazolyl)hexyl-2-ethynylpyridinium bromide) in high yields under DMF reflux conditions without any initiator or catalyst. This polymerization was influenced upon the initial monomer concentration. The polymer yields and inherent viscosities of the resulting polymers were in the range of 34-85% and 0.11-0.21 dL/g, respectively. Instrumental analyses using NMR, IR, and UV-visible spectroscopies and elemental analysis indicated that the resulting polymer has a conjugated polymer backbone system carrying pyridine and n-hexyl carbazole moiety. The polymers were mostly brown powders and completely soluble in DMF, DMSO, nitrobenzene, and formic acid. The photoluminescence spectrum of the dilute polymer solution with the excitation at 383 nm exhibited two sharp peaks at 495 and 540 nm.

Conformational Analysis and Molecular Dynamics Simulation of Lactose

  • 오재택;김양미;원영도
    • Bulletin of the Korean Chemical Society
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    • v.16 no.12
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    • pp.1153-1162
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    • 1995
  • The conformational details of β-lactose are investigated through molecular dynamics simulations in conjunction with the adiabatic potential energy map. The adiabatic energy map generated in vacuo contains five local minima. The lowest energy structure on the map does not correspond to the structure determined experimentally by NMR and the X-ray crystallography. When aqueous solvent effect is incorporated into the energy map calculation by increasing the dielectric constant, one of the local minima in the vacuum energy map becomes the global minimum in the resultant energy map. The lowest energy structure of the energy map generated in aquo is consistent with the one experimentally determined. Molecular dynamics simulations starting from those fivelocal minima on the vacuum energy map reveal that conformational transitions can take place among various conformations. Molecular dynamics simulations of the lactose and ricin B chain complex system in a stochastic boundary indicate that the most stable conformation in solution phase is bound to the binding site and that there are conformational changes in the exocyclic region of the lactose molecule upon binding.

$^{13}C\;and\;^{51}V $ Nuclear Magnetic Resonance Studies of Vanadium (Ⅴ)-$\alpha$-Hydroxycarboxylate Complexes

  • Man-Ho Lee;In-Whan Kim
    • Bulletin of the Korean Chemical Society
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    • v.14 no.5
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    • pp.557-561
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    • 1993
  • The interaction of vanadium(V) with various a-hydroxycarboxylate ligands in aqueous solution at pH 3.2 have been studied by $^{51}V$ and $^{13}C$ NMR spectroscopies. From the results it is supposed that vanadates mainly form the octahedral complexes with lactate, 2-hydroxybutyrate, glycerate, and malate. While, vanadates form the trigonal-bipyramidal complexes with glycolate, tartarate, and 2-hydroxy-3-methylbutyrate, and tetrahedral complexes with pyruvate(diol), 2-hydroxyisobutyrate, and 2-hydroxy-3-methylbutyrate. The bipyramidal products are formed as monomeric compounds. The octahedral products are formed as dimeric compounds with no evidence for a significant proportion of the monomeric derivatives. The complexes are mainly formed through the coordination at the carboxylate and the 2-hydroxyl groups of the ligands.

Biophysical study of bioactive-substance conformation and interaction with drugs in solution

  • Yu, Byung-Sul;Lee, Bong-Jin;Sohn, Dong-Hwan
    • Archives of Pharmacal Research
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    • v.8 no.3
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    • pp.109-117
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    • 1985
  • The interaction of salicylic acid (S. A.), salicylamide (S,M) with nucleic acid base derivatives such as 9-ethyl adenine (A), 1-cyclohexyl uracil (U), 2', 3'-benzylidine-5' trityl-cytidine (C), gaunosine-2', 3', 5'-isobutylate (G) has been spectroscopically investigated to determine the binding mechanism. NMR and IR spectra were measured in nonpolar solvents. The association constant K of the formation of complex was calculated from the IR spectra. Compounds S. A. and A form a 1:1 or 1:2 cyclic hydrogen-bonded complex depending on the sample concentration. Compounds S. A. and U form a 1:1 or 1:2 hydrogen-bonded complex on the sample concentration. Compounds S. A. and C form a 2:1 hydrogen-bonded complex at low concentration (0.0016M). Compound S. A. binds compound G, but its binding does not completely break the self-association of compound G, Compound S. M. binds compounds A. U. C. G. very weakly.

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Characterization by Solid-State $^51V$ NMRand X-ray Diffraction of Vanadium Oxide Supported on ZrO₂

  • 손종락;박만영;배영일
    • Bulletin of the Korean Chemical Society
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    • v.17 no.3
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    • pp.274-278
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    • 1996
  • Vanadium oxide-zirconia catalysts were prepared by dry impregnation of powdered Zr(OH)4 with aqueous solution of NH4VO3. The characterization of prepared catalysts was performed using 51V solid state NMR, XRD, and DSC. The addition of vanadium oxide up to 9 mol% to zirconia shifted the phase transitions of ZrO2 from amorphous to tetragonal toward higher temperatures due to the interaction between vanadium oxide and zirconia. On the basis of results of XRD and DSC, it is concluded that the content of V2O5 monolayer covering most of the available zirconia was 9 mol%. The crystalline V2O5 was observed only with the samples containing V2O5 content exceeding the formation of complete monolayer (9 mol%) on the surface of ZrO2.