• Title/Summary/Keyword: Solution NMR

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Rates and Mechanism of Fading Reaction of Magenta Azomethine Dye in Basic Solution (염기성 용액에서 마젠타 아조메틴 색소의 퇴색 반응속도와 메커니즘)

  • Lee Joong-Ho;Kim Jung-Sung;Kim Chang-Su
    • Journal of Environmental Science International
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    • v.14 no.7
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    • pp.711-717
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    • 2005
  • A magenta azomethine dye(D) was synthesized from the reaction of 3-methyl-1-phenyl-2-pyrazoline-5-one with N,N-diethyl-1,4-phenylenediamine. The magenta azomethine dye was identified on the basis of elemental analysis, $^{13}C-NMR$, infrared, and GC/MS studies. The magenta azomethine dye was decomposed in a basic solution. Rate constants of the fading reaction of magenta azomethine dye in ethanol-water solvent were measured spectrophoto­metrically at 540 nm. Reaction rate was increased with the increase of $[OH\^{-}]\;and\;[H\_{2}O]$ in the region of $[H_{2}O]=11\~40\;M$. The reaction was governed by the following rate law. -d[D]/dt = $\{k_o\;+\;k_{OH}[OH^-][H_{2O}]\}[D]$ A possible mechanism consistent with the empirical rate law has been proposed.

Topology effects on the LCST of end-capped poly(ethylene glycol)s

  • Kim, Jin Young;Moon, Hyo Jung;Ko, Du Young;Jeong, Byeongmoon
    • Biomaterials and Biomechanics in Bioengineering
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    • v.2 no.1
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    • pp.15-22
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    • 2015
  • Poly(ethylene glycol) end-capped with pentafluorophenyl group(s) in ABA (FP-PEG-FP) and AB (mPEG-FP) types were prepared. Even though they were similar in composition, the lower critical solution temperature (LCST) of FP-PEG-FP was observed at $23^{\circ}C$, whereas that of mPEG-FP was observed at $65^{\circ}C$. To understand the large difference in solution behaviour of the two polymers, UV-VIS spectroscopy, microcalorimetry, 1H-NMR spectroscopy, and dynamic light scattering were used. FP-PEG-FP has two hydrophobic pentafluorophenyl groups at the ends of hydrophilic PEG (1000 Daltons), whereas mPEG-PF has a highly dynamic PEG (550 Daltons) block that are anchored to a hydrophobic pentafluorophenyl group. PF-PEG-PF not only has a smaller conformational degree of freedom than mPEG-PF but also can form extensive intermolecular aggregates, therefore, PF-PEG-PF exhibits a significantly lower LCST than mPEG-PF. This paper suggests that topological control is very important in designing a temperature-sensitive polymer.

The Synthesis of Cellulose-graft-poly (L-lactide) by Ring-opening Polymerization and the Study of Its Degradability

  • Dai, Lin;Xiao, Shu;Shen, Yue;Qinshu, Baichuan;He, Jing
    • Bulletin of the Korean Chemical Society
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    • v.33 no.12
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    • pp.4122-4126
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    • 2012
  • Cellulose-graft-poly (L-lactide) (cellulose-g-PLLA) was successfully prepared via ring-opening polymerization (ROP) by using 4-dimethylaminopyridine (DMAP) as an organic catalyst in an ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl). The structure and morphology of the polymer was characterized by nuclear magnetic resonance (NMR) and transmission electron microscope (TEM). From wide-angle X-ray powder diffraction (WAXD) and degradation test (by acid, alkaline, PBS and enzyme solution), changes in the crystalline structure as a result of degradation was also investigated. The results indicated that materials which have low degree of crystallinity showing higher degradability, however, in acid liquor, enzyme solution, alkaline liquor and PBS system, the degradation rate of the polymer decreased by the above sequence. Moreover, with the further increase of graft degree of this material, its degradation degree decreased.

Synthesis and Characterization of Perylene-based Pyrrolopyrone Derivative for Organic Thin Film Transistor

  • Kim, Hyung-Sun;Jung, Sung-Ouk;Kim, Yun-Hi;Do, Lee-Mi;Kwon, Soon-Ki
    • Journal of Information Display
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    • v.6 no.4
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    • pp.1-5
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    • 2005
  • Perylene-based pyrrolopyrone derivative (PPD) was synthesized via condensation reaction with perylenetetracarboxylic dianhydride and 1,2-phenylenediarnine as n-type channel material. The structure of PPD was characterized by spectroscopic methods such FT-IR and $^1H$-NMR. PPD exhibited high thermal stability ($T_{d5wt%}: 560^{\circ}C$) and was found to be soluble only in protonic solvents with high acidity such as methane sulfonic acid and trifluoroacetic acid. The PPD solution showed maximum absorption and emission at 601 and 628 nm, respectively. Thin film transistors were fabricated by vacuum deposition and solution casting method. The electron mobilities of the devices were achieved as high as $0.17{\times}10^{-6}cm^2/Vs$ for vacuum deposited device and $0.4{\times}10^{-6}cm^2/Vs$ for spin coated device, respectively.

Conformation of L-Ascorbic Acid in solution. 1. Neutral L-Ascorbic Acid

  • Shin, Young A.;Kang, Young-Kee
    • Bulletin of the Korean Chemical Society
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    • v.12 no.1
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    • pp.61-67
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    • 1991
  • Conformational free energy calculations using an empirical potential function and the hydration shell model (a program CONBIO) were carried out on the neutral L-ascorbic acid (AA) in the unhydrated and hydrated states. The conformational energy was minimized from starting conformations which included possible conformations of six torsion angles in the molecule. The conformational entropy of each low energy conformation in both states was computed using a harmonic approximation. From the analysis of conformational free energies for AA in both states, intramolecular hydrogen bonds (HBs) are proved to be an essential factor in stabilizing the overall conformations, and cause the conformations in both states to be quite different from those in crystal. In the case of hydrated AA, there is a competition between HBs and hydration, and the hydration around the two hydroxyl groups attached to the acyclic side chain forces the molecule to form less stable HBs. The hydration affects strongly the conformational energy surfaces of AA. Several feasible conformations obtained in this work indicate that there exists an ensemble of several conformations in aqueous solution. The calculated probable conformations for the rotation about the C5-C6 bond of the acyclic side chain are trans and gauche +, which are in good agreement with results of NMR experiment.

Synthesis and Electrochemical Studies of Cu(II) and Ni(II) Complexes with Tetradentate Schiff Base Ligands

  • 조기형;정병구;김정희;전승원;임채평;최용국
    • Bulletin of the Korean Chemical Society
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    • v.18 no.8
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    • pp.850-856
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    • 1997
  • A series of tetradentate Schiff-base ligands; 1,3-bis(salicylideneimino) propane, 1,4-bis(salicylideneimino)butane, and 1,5-bis(salicylideneimino)pentane, and their Cu(Ⅱ) and Ni(Ⅱ) complexes have been synthesized. The properties of ligands and complexes have been characterized by elemental analysis, IR, NMR, UV-Vis spectra, molar conductance, and thermogravimetric anaylsis. The mole ratio of Schiff base to metal at complexes was found to be 1 : 1. All complexes were four-coordinated configuration and non-ionic compound. The electrochemical redox processes of the ligands and their complexes in DMF solution containing 0.1 M TEAP as supporting electrolyte have been investigated by cyclic voltammetry, chronoamperometry, differential pulse voltammetry at glassy carbon electrode, and by controlled potential coulometry at platinum gauze electrode. The redox process of the ligands was highly irreversible, whereas redox process of Cu(Ⅱ) and Ni(Ⅱ) complexes was observed as one electron transfer process of quasi-reversible and diffusion-controlled reaction. Also the electrochemical redox potentials of complexes were affected by chelate ring size of ligands. The diffusion coefficients of Cu(Ⅱ) and Ni(Ⅱ) complexes in DMF solution were determined to be 4.2-6.6×10-6 cm2/sec. Also the exchange rate constants were determined to be 3.6-9.7×10-2 cm/sec.

Ink-jet Printing for the Fabrication of a Flexible Electrochromic Device Based on the Water-Soluble Viologen-Functionalized Dendrimer

  • Yekefallah, Vahideh;Soleimani-Gorgani, Atasheh;Rouhani, Shohre;Najafi, Farhood
    • Journal of Electrochemical Science and Technology
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    • v.12 no.1
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    • pp.146-158
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    • 2021
  • This paper reports the preparation of an ink-jet printed flexible electrochromic device based on a water-soluble viologen-functionalized dendrimer. Polyamidoamine (PAMAM) dendrimers were modified with different concentrations of 1-1 bis(propylamine)-4,4'-bipyridylium dibromides to obtain solution-processable electrochromic materials (K1/2 and K1). FTIR, NMR, and elemental analyses are used to characterize synthesized viologens. Moreover, their electrochemical properties were investigated using cyclic voltammetry in an electrolyte solution consisting of 0.1 M HCl to find the optimum viologens. The low-cost ink-jet printer was used to print the prepared water-soluble electrochromic inks onto the ITO coated PET substrate to form desired transparent patterns. The electrolyte was applied on the printed electrochromic ink to make a sandwich with another ITO coated PET to prepare the electrochromic devices (ECD). By applying an electrical potential (0 to -2 V), the transparent ECD's color changed from colorless to blue. The color changes for the optimum ECD (K1), which had more viologen units on the dendrimer, was accompanied by an optical contrast of 47% and 311.5 ㎠C-1 coloration efficiency at 600 nm.

Synthesis and Electrochemical Studies of Ni(Ⅱ) Complexes with Tetradentate Schiff Base Ligands

  • 정병구;임채평;국성근;조기형;최용국
    • Bulletin of the Korean Chemical Society
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    • v.17 no.2
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    • pp.173-179
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    • 1996
  • A series of tetradentate Schiff base ligands; [1,2-bis(naphthylideneimino)ethane, 1,3-bis(naphthylideneimino)propane, 1,4-bis(naphthylideneimino)butane, and 1,5-bis(naphthylideneimino)pentane] and their Ni(Ⅱ) complexes have been synthesized. The properties of these ligands and their Ni(Ⅱ) complexes have been characterized by elemental analysis, IR, NMR, UV-vis spectra, molar conductance, and thermogravimetric analysis. The mole ratio of Schiff base to Ni(Ⅱ) metal was found to be 1:1. The electrochemical redox process of the ligands and their Ni(Ⅱ) complexes in DMF and DMSO solution containing 0.1 M tetraethyl ammonium perchlorate (TEAP) as a supporting electrolyte have been investigated by cyclic voltammetry, chronoamperometry, differential pulse voltammetry, and controlled potential coulometry at glassy carbon electrode. The redox process of the ligands was highly irreversible, whereas redox process of Ni(Ⅱ) complexes were observed as one electron transfer process in quasi-reversible and diffusion-controlled reaction. The electrochemical redox potentials of the Ni(Ⅱ) complexes were affected by the chelate ring size of ligands. The diffusion coefficients of Ni(Ⅱ) complexes containing 0.1 M TEAP in DMSO solution were determined to be 5.7-6.9 × 10-6 cm2/sec. Also the exchange rate constants were determined to be 1.8-9.5 × 10-2 cm2/sec. These values were affected by the chelate ring size of ligands.

Antimicrobial Activity of Lactobacillus reuteri Against Major Food-Borne Pathogens (Lactobacillus reuteri의 주요 식품 위해 미생물에 대한 항균 효과)

  • Kwon, Nam-Hoon;Kim, So-Hyun;Bae, W.K.;Kim, J.Y.;Lim, J.Y.;Noh, K.M.;Kim, J.M.;Ahn, J.S.;Hur, J.;Park, Y.H.
    • Journal of Food Hygiene and Safety
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    • v.16 no.4
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    • pp.264-273
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    • 2001
  • Antimicrobial activities of ave different probiotics (Lactobacillus reuteri, L. acidophillus, L. bulgaricus, L. casei and Bifidobacterium longum) against 8 bacterial pathogens were determined on the Mueller Hinton Agar containing supernatant of probiotics obtained from 3 different growth conditions (MRS without glycerol, MRS with 0.5 M glycerol or 0.25 M glycerol solution). Though antimicrobial activity of L. reuteri in the first two conditions was not better than the others', the activity was significantly higher than that of others in 0.25 M glycerol solution. This prominent effect might be attributable to reuterin, produced by L. reuteri using glycerol. We could detect the presence of reuterin in the supernatant of 0.25 M glycerol solution with 500 MHz Nuclear Magnetic Resonance (NMR). The result of minimum bactericidal concentration (dilution fold) has revealed that reuterin showed pan-bactericidal effects against 8 major food-borne pathogens. To examine any changes of antimicrobial activities of the probiotics, the probiotics were treated with different pH conditions, pepsin or trypsin digestion. Antimicrobial activity of reuterin was not entirely affected by any of these treatments, while the activities of the other probiotics were significantly decreased.

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Supramolecular Micelle from Amphiphilic Mn(III)-porphyrin Derivatives as a Potential MRI Contrast Agent

  • Choi, Kwang-Mo;Lee, Do-Hyung;Jang, Woo-Dong
    • Bulletin of the Korean Chemical Society
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    • v.31 no.3
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    • pp.639-644
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    • 2010
  • Amphiphilic porphyrin derivatives have been synthesized and characterized by $^1H$ NMR and MALDI-TOF-MS. All porphyrin derivatives showed very high solubility to aqueous medium as well as hydrophobic organic solvent. The UV-vis absorption of the porphyrin derivatives showed significant broadness and decrease of maximum intensity of absorption in aqueous solution. SEM experiment showed the formation of spherical micellar structure. The $T_1$ relaxation time of aqueous medium was drastically decreased in the presence of Mn(III)-porphyrin derivative, indicating that the supramolecular micelle has strong possibility to use as a $T_1$ contrast agent.