• Title/Summary/Keyword: C-H insertion

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Theoretical Studies on the Alkylidene Silylenoid H2C = SiLiF and Its Insertion Reaction with R-H (R = F, OH, NH2)

  • Tan, Xiaojun;Wang, Weihua;Li, Ping;Li, Qingyan;Cheng, Lei;Wang, Shufen;Cai, Weiwang;Xing, Jinping
    • Bulletin of the Korean Chemical Society
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    • v.31 no.5
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    • pp.1349-1354
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    • 2010
  • The geometries and isomerization of the alkylidene silylenoid $H_2C$ = SiLiF as well as its insertion reactions with R-H (R = F, OH, $NH_2$) have been systematically investigated at the B3LYP/6-311+$G^*$ level of theory. The potential barriers of the three insertion reactions are 97.5, 103.3, and 126.1 kJ/mol, respectively. Here, all the mechanisms of the three reactions are identical to each other, i.e., an intermediate has been formed first during the insertion reaction. Then, the intermediate could dissociate into the substituted silylene ($H_2C$ = SiHR) and LiF with a barrier corresponding to their respective dissociation energies. Correspondingly, the reaction energies for the three reactions are -36.4, -24.3, and 3.7 kJ/mol, respectively. Compared with the insertion reaction of $H_2C$ = Si: and R-H (R = F, OH and $NH_2$), the introduction of LiF makes the insertion reaction occur more easily. Furthermore, the effects of halogen (F, Cl, Br) substitution and inorganic salts employed on the reaction activity have also been discussed. As a result, the relative reactivity among the three insertion reactions should be as follows: H-F > H-OH > H-$NH_2$.

Comparative assessment of the easiness and speed of insertion of three supraglottic airway devices - A manikin study - (3가지 성문위기도기(Supraglottic airway device)의 삽관 용이성과 삽관시간 비교 - 마네킨을 이용한 연구-)

  • Kim, Sang-Tae;Kang, Bo-Ra;Tak, Yang-Ju
    • The Korean Journal of Emergency Medical Services
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    • v.16 no.2
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    • pp.23-30
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    • 2012
  • Purpose : This study was designed to compare the easiness and speed of insertion of three supraglottic airway devices(SADs) in a manikin setting. Methods : Three different SADs - Laryngeal Mask Classic(cLMA), I-gel and Streamlined Liner of the Pharynx Airway(SLIPA) were applied. One hundred and nineteen paramedical students with(group H) or without (group L) previous airway experience were taught brief manikin training about the use of the cLMA, I-gel and SLIPA. The students inserted each device in a randomized order. Time to effective ventilation was recorded in seconds from holding the device to the first chest inflation. Success was determined as adequate chest wall movement. Results : The insertion attempts were lesser in I-gel($1.00{\pm}0.00$) and SLIPA($1.05{\pm}0.27$) than cLMA($1.16{\pm}0.41$, p<.05). The shortest time to insertion was recorded for I-gel($10.5{\pm}3.0sec$), followed by the SLIPA($12.9{\pm}4.5sec$) and cLMA($19.6{\pm}4.1sec$, p<.05). There were no significant differences in the insertion attempts and insertion time of I-gel between group L and group H. But in cLMA, longer insertion time and more insertion attempts were recorded in group L than group H. Conclusion : Both I-gel and SLIPA were superior to cLMA in the easiness and speed of insertion. Even in novice students, I-gel showed an excellent result in a manikin.

Dynamics of OH Production in the Reaction of O(1D2) with Cyclopropane

  • Jang, Sungwoo;Jin, Sung Il;Kim, Hong Lae;Kim, Hyung Min;Park, Chan Ryang
    • Bulletin of the Korean Chemical Society
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    • v.35 no.6
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    • pp.1706-1712
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    • 2014
  • The OH($X^2{\Pi}$, ${\upsilon}^{\prime\prime}=0,1$) internal state distribution following the reaction of electronically excited oxygen atom ($O(^1D_2)$) with cyclo-$C_3H_6$ has been measured using laser-induced fluorescence, and compared with that following the reaction of $O(^1D_2)$ with $C_3H_8$. The overall characteristics of the OH internal energy distributions for both reactions were qualitatively similar. The population propensity of the ${\Pi}(A^{\prime})$ ${\Lambda}$-doublet sub-level suggested that both reactions proceeded via an insertion/elimination mechanism. Bimodal rotational population distributions supported the existence of two parallel mechanisms for OH production, i.e., statistical insertion and nonstatistical insertion. However, detailed analysis revealed that, despite the higher exoergicity of the reaction, the rotational distribution of the OH following the reaction of $O(^1D_2)$ with $C_3H_8$ was significantly cooler than that with cyclo-$C_3H_6$, especially in the vibrational ground state. This observation was interpreted as the effect of the flexibility of the insertion complex and faster intramolecular vibrational relaxation (IVR).

Chemical Reactivity of Ti+ within Water, Dimethyl Ether, and Methanol Clusters

  • Koo, Young-Mi;An, Hyung-Joon;Yoo, Seoung-Kyo;Jung, Kwang-Woo
    • Bulletin of the Korean Chemical Society
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    • v.24 no.2
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    • pp.197-204
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    • 2003
  • The intracluster ion-molecule reactions of $Ti^+(H_2O)_n,\;Ti^+(CH_3OCH_3)_n,\;and\;Ti^+(CH_3OD)_n$ complexes produced by the mixing of the laser-vaporized plasma and the pulsed supersonic beam were studied using a reflectron time-of-flight mass spectrometer. The reactions of $Ti^+$ with water clusters were dominated by the dehydrogenation reaction, which produces $TiO^+(H_2O)_n$ clusters. The mass spectra resulting from the reactions of $Ti^+\;with\;CH_3OCH_3$ clusters exhibit a major sequence of $Ti^+(OCH_3)_m(CH_3OCH_3)_n$ cluster ions, which is attributed to the insertion of $Ti^+$ ion into C-O bond of $CH_3OCH_3$ followed by $CH_3$ elimination. The prevalence of $Ti^+(OCH_3)_m(CH_3OD)_n$ ions in the reaction of $Ti^+\;with\;CH_3OD$ clusters suggests that D elimination via O-D bond insertion is the preferred decomposition pathway. In addition, the results indicate that consecutive insertion reactions by the $Ti^+$ ion occur for up to three precursor molecules. Thus, examination of $Ti^+$ insertion into three different molecules establishes the reactivity order: O-H > C-O > C-H. The experiments additionally show that the chemical reactivity of heterocluster ions is greatly influenced by cluster size and argon stagnation pressure. The reaction energetics and formation mechanisms of the observed heterocluster ions are also discussed.

Insertion of Carbon Interlayer Into GaN Epitaxial Layer

  • Yu, H.S.;Park, S.H.;Kim, M.H.;Moon, D.Y.;Nanishi, Y.;Yoon, E.
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.02a
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    • pp.148-149
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    • 2012
  • This paper reports doping of carbon atoms in GaN layer, which based on dimethylhydrazine (DMHy) and growth temperature. It is well known that dislocations can act as non-radiative recombination center in light emitting diode (LED). Recently, many researchers have tried to reduce the dislocation density by using various techniques such as lateral epitaxial overgrowth (LEO) [1] and patterned sapphire substrate (PSS) [2], and etc. However, LEO and PSS techniques require additional complicated steps to make masks or patterns on the substrate. Some reports also showed insertion of carbon doped layer may have good effect on crystal quality of GaN layer [3]. Here we report the growth of GaN epitaxial layer by inserting carbon doped GaN layer into GaN epitaxial layer. GaN:C layer growth was performed in metal-organic chemical vapor deposition (MOCVD) reactor, and DMHy was used as a carbon doping source. We elucidated the role of DMHy in various GaN:C growth temperature. When growth temperature of GaN decreases, the concentration of carbon increases. Hence, we also checked the carbon concentration with DMHy depending on growth temperature. Carbon concentration of conventional GaN is $1.15{\times}1016$. Carbon concentration can be achieved up to $4.68{\times}1,018$. GaN epilayer quality measured by XRD rocking curve get better with GaN:C layer insertion. FWHM of (002) was decreased from 245 arcsec to 234 arcsec and FWHM of (102) decreased from 338 arcsec to 302 arcsec. By comparing the quality of GaN:C layer inserted GaN with conventional GaN, we confirmed that GaN:C interlayer can block dislocations.

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