• Title/Summary/Keyword: Bimolecular reaction

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LASER-Induced Vapour Phase Hetero-Epitaxy of A^{III}\;B^V$ Type Opto-Electronics (LASER 광려기 기상반응에 의한 III-V 족계 광전재기의 Hetero-Epitaxy 고찰)

  • 우희조;박승민
    • Korean Journal of Crystallography
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    • v.1 no.2
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    • pp.99-104
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    • 1990
  • The hetero-epitaxial growth of AmB v type onto-electronic material is attempted by means of the laser-induced chemical vapour deposition technique. The bimolecular gas phase reaction of trimethylgallium with ammonia on (001) alumina substrate for the epitaxy of gallium nitride is chosen as a model system. In this study, ArF exciter laser (193nm) is employed as a photon source. Marked difference is found in nucleation and in subsequent crystal incorporation between the doposits formed with and without the laser-irradiation. The surface coverage with isomorphically grown drystallites is pronounced upon "volume-excited" irradiation in comparison with the conventional thermal process. As to the crystal structure of the grown layers, the laser-induced deposits of GaN may be represented by either of the following two models: (001) plane of sapphire //y (001) plane of wurtzite-type GaN, OR (001) plane of sapphire//(001) plane of wurtzite-type-GaN (111) plane of twinned zinc blende-type GaN.

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Comparative Study of Emission Quenching of Tris(${\alpha},{\alpha}'$-diimine)-Ruthenium(II) Complexes in Homogeneous and Sodium Dodecyl Sulfate Micellar Solutions

  • Park, Joon-Woo;Nam, Eun-Jin;Ahn, Byung-Tae
    • Bulletin of the Korean Chemical Society
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    • v.12 no.6
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    • pp.686-691
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    • 1991
  • Emission quenching of photoexcited tris(${\alpha},{\alpha} '$-diimine)-ruthenium(II) complex cations, $RuL_3^{2+}$ (L: 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine; 4,4'-diphenyl-2,2'-bipyridine; 1,10-phenanthroline; 5-methyl-1,10-phenanthroline; 5,6-dimethyl-1,10-phenanthroline or 4,7-diphenyl-1,10-phenanthroline) by $Cu^{2+}$, dimethylviologen $(MV^{2+})$, nitrobenzene (NB), and oxygen was studied in aqueous homogeneous and sodium dodecyl sulfate (SDS) micellar solutions. The apparent bimolecular quenching rate constants $k_q$ were determined from the quenching data and life-times of $^{\ast}RuL_3^{2+}$. In homogeneous media, the quenching rate was considerably slower than that for the diffusion-controlled reaction. The decreasing order of quenching activity of quenchers was $NB>O_2>MV^{2+}>Cu^{2+}$. The rate with $Cu^{2+}$ was faster as the reducing power of $^{\ast}RuL_3^{2+}$ is greater. On the other hand, the rates with NB and $O_2$ were faster as the ligand is more hydrophobic. This was attributed to the stabilization of encounter pair by van der Waals force. The presence of SDS enhanced the rate of quenching reactions with $Cu^{2+}$ and $MV^{2+}$, whereas it attenuated the quenching activity of NB and $O_2$ toward $RuL_3^{2+}$. The binding affinity of quenchers to SDS micelle and binding sites of the quenchers and $RuL_3^{2+}$ in micelle appear to be important factors controlling the micellar effect on the quenching reactions.

(Photosensitive Polymers VII) Mechanism of Photosensitized Curing Reaction of Cinnamoylated Polymers ((感光性 高分子에 關한 硏究 VII) Cinnamoylated Polymers의 光增感 硬化反應機構)

  • Kim, Kwang-Sup;Shim, Jyong-Sup
    • Journal of the Korean Chemical Society
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    • v.10 no.4
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    • pp.166-174
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    • 1966
  • The multistep mechanism of photosensitized curing reaction cinnamoylated photosensitive polymer is proposed from the energy level diagram of cinnamic acid and sensitizer, and from the fact that excess of sensitizer brings the sensitivity to a limiting value etc. Various factors which have effects on the ability of sensitizer are also discussed. The mechanism involves following steps: activation to the first excited singlet states of cinnamoyl group(C) and sensitizer(S) by their absorption of photon, their intersystem crossing to the lowest triplet state, bimolecular internal quenching by formation of excimer of sensitizer, triplet excitation energy transfer and intermolecular addition between cinnamoyl group in ground state and that in triplet state. The rate equation derived from this mechanism is $-\frac{d[C]}{dt} = \frac{K_1[C]}{K_2 + [C]}[\frac{I^c_{abs}}{K_3 + [S]} + \frac{K_4[C]}{(K_5 + [C])(K_6 + [S])}(I^s_{abs} + \frac{K_7I^c_{abs}[S]}{K_8 + [S]})]$ where $I^c_{abs}\;and\;I^s_{abs}$: the rates of absorption of photon by cinnamoyl group and sensitizer $K_n$: Constants. It is proved with the cinnamate of poly(glyceryl phthalate)(PGC) in the absence of sensitizer using the infrared analytical method and successfully applied for the experimental data reported on the effects of the degree of cinnamoyl esterification and the concentration of sensitizer upon the sensitivity.

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Effect of Micelles on the Reaction of RuBPCase in Maize Leaf (옥수수 잎의 RuBPCase 반응에 미치는 미셀들의 영향)

  • 김의락;김현묵
    • KSBB Journal
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    • v.9 no.3
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    • pp.325-331
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    • 1994
  • PGA is formed in a route of CO2 fixation of RuBP catalyzed by RuBPCase, followed by reduction of the PGA by NADH to GAP This reduction is enhanced in an anionic micellar solution(SDS), in which NADH is distributed in the aqueous and the micellar pseudophases in a given ratio. This micellar bounded NADH reacts to PGA, and in higher micellar concentration than $1.25{\times}10^{-2}M$, most of NADH is oxidized to NAD+ by PGA. On the other hand, in the solutions of the positive ionic(CTABr), zwitter ionic(Chaps) and nonionic (Brij and Triton X-100) micelles, the reactions are also enhanced and the concentrations of NADH reach minima with micellar concentrations. Such minima are typical of micellar catalyzed bimolecular reactions, and the fall in concentrations of the reductant followed by a gradual increase is charataristic of reactions of hydrophobic substrates: that is, the reductions of PGA by NADH are sharply enhanced in a range of the lower micellar concentrations, and NADH amounts in ca. $1.25-2.50{\times}10^{-3}M$ micellar solutions are reached to minima, followed by gradual increases of the reductant concentration.

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