• Bulletin of the Korean Chemical Society
• /
• 제31권5호
• /
• pp.1349-1354
• /
• 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-$NH_2$.

• Child Health Nursing Research
• /
• 제22권1호
• /
• pp.21-28
• /
• 2016

Purpose: The purpose of this study was to identify effects of EMLA (Eutectic Mixture of Local Anesthetics) cream application on pain perception and pain response during insertion of implanted venous access port needle in children with cancer. Methods: From December 2010 to August 2011, at U university hospital, 20 patients scheduled for implanted venous access port needle insertion were recruited, and randomly assigned to receive either EMLA or a placebo cream 1 hour before the implanted venous access port needle insertion. While conducting needle insertion, changes in pulse and oxygen saturation on the pulse oxymeter monitor were measured and pain behavior reaction was also measured during needle insertion in the treatment room. After conducting needle insertion, self-reported pain reaction, and mothers' perception of the children's pain reaction were measured. Collected data were statistically processed using SPSS version 17.0 for Windows, and analyzed using descriptive statistics, t-test. Results: Children's self-reported degree of pain, degree of pain as perceived by mothers and pain behavior reaction decreased significantly in the EMLA application group compared with the placebo group. Conclusion: Findings indicate that application of EMLA cream is effective in relieving pain in these children during implanted venous access port needle insertion.

• Bulletin of the Korean Chemical Society
• /
• 제23권5호
• /
• pp.779-782
• /
• 2002

• Bulletin of the Korean Chemical Society
• /
• 제35권6호
• /
• pp.1706-1712
• /
• 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).

• Journal of Photoscience
• /
• 제7권1호
• /
• pp.15-19
• /
• 2000

The photochemical reaction mechanism has been investigated for methanol insertion into the p-substituted phenylketo carbenes. The triplet spin state of phenyl koto carbene is stabilized by the neighbored carbonyl electrons. When the phenylketo carbene reacts with methanol, the ylied intermediate is formed, then moves to the activated transition state.

• Bulletin of the Korean Chemical Society
• /
• 제8권2호
• /
• pp.63-68
• /
• 1987

The photolysis and thermal reaction of hexafluorobenzene solution of icosahedral dicarba-closo-dodecaborane and various carbenes have been shown to lead to the formation of four isomeric insertion products to icosahedral molecules. The results showed the carbene insertion reaction to 1, 2-dicarba-closo-dodecaborane to occur at the positions of 4-, 5-, 7-, and 11-borons, 9-, and 12-borons 3-, and 6-borons and 8-, and 10-borons. The samples of 1, 7-, and 1, 12-dicarba-closo-dodecaborane with carbenes in hexafluorobenzene by photolysis showed no reaction. To find out the reactivities of carbenes to dicarba-closo-dodecaboranes, the total energies have been calculated and have been discussed the tendency for carbene insertion reactions to icosahedral carboranes.

• Bulletin of the Korean Chemical Society
• /
• 제24권2호
• /
• pp.197-204
• /
• 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.

• Bulletin of the Korean Chemical Society
• /
• 제34권5호
• /
• pp.1575-1578
• /
• 2013

• Bulletin of the Korean Chemical Society
• /
• 제23권1호
• /
• pp.86-92
• /
• 2002

A short synthesis of novel prostanoids, 12-epi-carbacyclins 3 and 24, has been accomplished using palladium chemistry as a key step. The silyl enol ether 10a prepared through organopalladium chemistry has been allowed to react with 1-octen-3-one in the presence of $Pd(OAc)_2$ to give compound 12 in a single step. The unusual chemo- and stereoselective reduction of the ${\alpha},{\beta}$-unsaturated ketone in 12 has been effected with (S)-BINALH. Subsequent desilylation and Wittig reaction have provided the Subsequent desilylation and Wittig reaction have provided the $PGI_2$ analogues 3 and 24.

• Bulletin of the Korean Chemical Society
• /
• 제16권10호
• /
• pp.994-997
• /
• 1995