• Title/Summary/Keyword: zwitterion

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Kinetics and Mechanism of the Pyridinolysis of Aryl Cyclobutanecarboxylates in Acetonitrile

  • koh, Han-Joong;Han, Kwang-Lae;Lee, Hai-Whang;Lee, Ik-Choon
    • Bulletin of the Korean Chemical Society
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    • v.23 no.5
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    • pp.715-720
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    • 2002
  • Kinetic studies of the reaction of Z-aryl cyclobutanecarboxylates with X-pyridines in acetonitrile at $55.0^{\circ}C$ have been carried out. The reaction proceeds by a stepwise mechanism in which the rate-determining step is the breakdown of the zwitterion ic tetrahedral intermediate, T $\pm$ . These mechanistic conclusions are drawn based on (i) the large magnitude of ${\rho}X$ and $\rhoZ$, (ⅱ) the positive sign of ${\rho}XZ$ and the larger magnitude of $\rhoXZ$ than normal SN2 processes, (ⅲ) a small positive enthalpy of activation, ${\Delta}H{\neq}$, and a large negative, ${\Delta}S{\neq}$, and lastly (iv) adherence to the reactivity-selectivity principle (RSP) in all cases.

The Kinetic Study of Propylene Sulfide Polymerization Initiated by o-Sulfobenzoic Anhydride (Propylene Sulfide를 o-Sulfobenzoic Anhydride 개시제로 중합시킬 때 반응속도의 연구)

  • Man Jung Han
    • Journal of the Korean Chemical Society
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    • v.22 no.4
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    • pp.268-274
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    • 1978
  • The kinetics of the bulk polymerization of propylene sulfide initiated by o-sulfobenzoic anhydride were investigated, which proceeded by a zwitterionic mechanism.The instantaneous concentrations of monomer and initiator were determined by means of ir-and nmr-spectroscopy. The rate constant of propagation was found to be about three order of magnitude higher than that of initiation and this should be caused by a zwitterion mechanism.

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Well-Defined Thermoresponsive Copolymers with Tunable LCST and UCST in Water

  • Jung, Seo-Hyun;Lee, Hyung-Il
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.501-504
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    • 2014
  • A thermoresponsive polymer, poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA), was successfully synthesized by atom transfer radical polymerization (ATRP). Different amounts of 1,3-propanesultone were used as quaternization agent to transit the PDMAEMA into partially modified poly(zwitterions), resulting in p[DMAEMA-co-3-dimethyl(methacryloyloxyethyl)ammonium propanesulfonate] (PDMAEMA-co-PDMAPS). Molecular weight, molecular weight distribution, and degree of quarternization were determined by gel permeation chromatography (GPC) and 1H NMR spectroscopy. The transmission spectra of the 1.0 wt % aqueous solutions of the resulting polymers at 650 nm were measured as a function of temperature. Results showed that the lower critical solution temperature (LCST) and the upper critical solution temperature (UCST) could be easily controlled by the different composition of dimethylamino and zwitterion groups. The effect of partial quaternization on thermoresponsive properties was also studied by dynamic light scattering (DLS) with the same aqueous concentration (1.0 wt %) as employed for turbidimetry studies. The LCST and UCST values measured by DLS correlated well with those determined by turbidimetry.

The crystal and molecular structure of $\gamma$-hydroxy-.$\beta$-amino butyric acid

  • Kim, Yang-Bae
    • Archives of Pharmacal Research
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    • v.8 no.1
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    • pp.1-6
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    • 1985
  • The crystal structure or $\gamma$-hydroxy-$\betha$-aminobutyric acid was determined by MULTAN system with X-ray intensity data on a diffractometer and refined by the least-squares method to an R-value 0.034 for 711 reflections. The crystals were orthorhombic, space group $P2_{1}2_{1}2_{1}$, Z = 4, with a = 10.220, b = 8.257 and c = 6.556$\AA$. The molecule takes the zwitterionic form and skeletal conformation is trans-transform. The molecules are held together by intra-and intermolecular NH-O and OH--O hydrogen bonds.

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Excited State Proton Transfers and Subsequent Electron Rearrangement of Aqueous 6-Hydroxyquinoline

  • 유현웅;권혁진;장두전
    • Bulletin of the Korean Chemical Society
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    • v.18 no.2
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    • pp.156-161
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    • 1997
  • Aqueous 6-hydroxyquinoline in the first excited singlet state undergoes protonation to the imine group first in 15 ps, then in the time scale of 40 ps deprotonation from the enol group and finally, however, quickly as in 11 ps electron rearrangement to change into a resonance hybrid structure of quinoid-prevailing forms. Despite the fact that the decay time constant is smaller than the formation time constant, fluorescence from excited protropic zwitterion is observed to assign its maximum at 510 nm. The electron rearrangement is basically an intramolecular charge transfer from the deprotonated oxygen atom to the positively charged iminium ring without any notable change in nuclear geometry, producing a zwitterionic quinoid structure with much a smaller electric dipole moment than the zwitterionic protropic species. This photoproduct formed by consecutive excited state proton and electron transfers shows a smaller dipole moment in S1 than in S0 and a hypsochromic shift although its S1 state has (π, π*) character.

Surface Modification Using Spiropyran-Derivative and Its Analysis of Surface Potential Induced by UV (스파이로파이란에 의한 표면 개질 및 자외선에 의해 유도된 표면 전위에 대한 분석)

  • Lee, Bong-Soo;Han, Dong-Keun;Son, Tae-Il;Jung, Young-Hwan
    • Journal of the Korean Chemical Society
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    • v.55 no.3
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    • pp.478-485
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    • 2011
  • Merocyanine derivatives transformed from spiropyran-containing compounds by irradiating the light of ultraviolet (UV) include zwitterion of phenolate anion and amine cation. Complexation of this phenolate anion on merocyaninemodified surface and Ni ion among metal ions led to a change of surface charge and it was measured with kelvin prove force microscopy (KFM). We found that the resultant surface potential decreased linearly as UV-exposed time increased, and finally were saturated. Also it was analyzed through XPS the immobilized amount of Ni ions was increased according to increase of UV-exposed time. It is considered that these properties could be applied for detection and a quantitative control of different metal ions. Further research is to aim construct specific scaffold/matrix which enable high selective, high sensitive and, especially, a quantitative immobilization of metal ions-binding biomaterials such as proteins and cells.

Reaction Kinetics of Carbon Dioxide and Glycidyl Methacrylate using a Ionic Liquid Catalyst of Imidazole Immobilized on MCM41 (MCM41에 담지된 Imidazole 촉매에 의한 Glycidyl Methacrylate와 이산화탄소의 반응속도론)

  • Son, Young-Sik;Park, Moon-Ki;Kim, Gun-Woo;Park, Sang-Wook
    • Korean Chemical Engineering Research
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    • v.47 no.4
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    • pp.410-417
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    • 2009
  • Carbon dioxide was absorbed into GMA solution in a stirred flat cell using mesoporous catalyst Imidazole-CP-MS41, which was synthesized by CP-MCM41 with imidazole. Experiments were carried out at a batch-type absorber with different conditions, varying reaction temperature, concentration of GMA, solvent but maintaining 50 rpm of agitation speed and 2 g of catalyst. Absorption rate of $CO_2$ was used to obtain the kinetics based on the film theory using zwitterion mechanism with 2 elementary reaction and the kinetics were correlated with the solubility parameter of the solvents.

Obtaining the zwitterionic form of L-lysine from L-lysine monohydrochloride by electrodialysis

  • Aghajanyan, A.E.;Tsaturyan, A.O.;Hambardzumyan, A.A.;Saghyan, A.S.
    • Membrane and Water Treatment
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    • v.4 no.1
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    • pp.1-9
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    • 2013
  • The process of electromembrane transformation of L-lysine monohydrochlorides into their zwitterionic form in four- and two-chamber electrodialysis apparatus was investigated. The process of transformation at various concentrations of lysine monohydrochloride (0.1-0.6 mol.L-1) was studied and it was established that at the optimum density of current optimal concentrations of lysine hydrochloride during electrodyalisis was in the range of 0.2-0.4 mol.L-1. It was determined that the process of total transformation was accomplished when pH of the lysine solution achieved 10. Changes of concentrations of $Cl^-$ ions and lysine diffused into the neighboring chamber were determined depending on the time. The method developed by us allows adjusting the removal coefficient of $Cl^-$ ions during transformation to a maximal value, the losses of lysine diffused into the next chamber after its return to the technological cycle being less than 1.0 %. The specific energy consumption during the process of transformation in two- and four-chamber electrodialyzers was 0.19 and 0.205 A.h.kg-1 and the current efficiency was 75.9 and 73.1 %, correspondingly. Study of the process of electromembrane transformation allowed obtaining zwitterionic form of L-lysine from L-lysine monohydrochloride with minimal reagent and energy consumption.

Structure and Stability of γ-Aminobutyric acid-(H2O)n (n = 0-5) Clusters: Zwitterionic vs. Canonical forms

  • Kim, Ju-Young;Schermann, Jean Pierre;Lee, Sung-Yul
    • Bulletin of the Korean Chemical Society
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    • v.31 no.1
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    • pp.59-63
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    • 2010
  • Calculations are presented for the $\gamma$-aminobutyric acid-$(H_2O)_n$ (n = 0-5) clusters in both canonical and zwitterionic forms. We examine the effects of microsolvation on the structures and transformation between the canonical and zwitterionic forms. The canonical forms are predicted to be more stable for n = 0-4. With five microsolvating water molecules, the two forms of $\gamma$-aminobutyric acid become quasidegenerate, with the energies of zwitterionic forms slightly (by 1 - 3 kcal/mol) higher. The lowest energy zwitterionic conformer of $\gamma$-aminobutyric acid-$(H_2O)_5$ cluster is calculated to isomerize to canonical form through a barrier-less proton transfer process and is thus predicted to be kinetically unstable. Therefore, we predict that the canonical conformers of $\gamma$-aminobutyric acid should be observed predominantly in the gas phase at low temperature in presence of up to five water molecules.

Experimental study on the electrochemical properties of zwitterion and phosphate-based hybrid inhibitors in reinforced concrete (양쪽성 이온 및 인산염 기반 하이브리드 방청제의 전기화학적 특성에 관한 실험적 연구)

  • Tran, Duc Thanh;Jeong, Min-goo;Lee, Han-seung;Yang, Hyun-min;Singh, Jitendra Kumar
    • Proceedings of the Korean Institute of Building Construction Conference
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    • 2022.11a
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    • pp.37-38
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    • 2022
  • During the past decades, the corrosion of the steel rebar embedded in concrete structure surrounding marine environment is actually problematic and required the suitable preventive method. An eco-friendly corrosion inhibitor mix is investigated to stifle the active corrosion in comparison with other commercial corrosion inhibitors. The hybrid inhibitor enhances the corrosion resistance and the workability of concrete. However, it reduces the compressive strength slightly after 28-day-age. The electrochemical studies and mechanical studies are pointed out the corrosion resistance property, corrosion kinetics, and the mechanical properties of all concrete samples. H-3 is the optimum dose of hybrid inhbitor that meets the demand of both electrochemical property and mechanical property. It performs the noble features due to the formation of optimum amount of P-Zwitterions-(Cl)-Fe complex onto the steel rebar surface.

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