• Bulletin of the Korean Chemical Society
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• v.28 no.6
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• pp.936-940
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• 2007

The aminolyses of diphenyl phosphinic chloride (1) with substituted anilines in acetonitrile at 55.0 oC are investigated kinetically. Large Hammett ρ X (ρnuc = ?4.78) and Bronsted β X (βnuc = 1.69) values suggest extensive bond formation in the transition state. The primary normal kinetic isotope effects (kH/kD = 1.42-1.82) involving deuterated aniline (XC6H4ND2) nucleophiles indicate that hydrogen bonding results in partial deprotonation of the aniline nucleophile in the rate-limiting step. The faster rate of diphenyl phosphinic chloride (1) than diphenyl chlorophosphate (2) is rationalized by the large proportion of a frontside attack in the reaction of 1. These results are consistent with a concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state.

• Tribology and Lubricants
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• v.16 no.3
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• pp.166-172
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• 2000

The friction and wear characteristics of dental composite resins such as Charisma, Elitefil, TPH and Veridonfil were investigated. Furthermore, The surface characteristics examination, the analysis of contents of filler, Victors hardness and fracture toughness measurement of composite resins were preformed. The wear test applied ball to move reciprocationally on flat wear tester at room temperature. Microstructure of surfaces and worn surfaces were observed by SEM. Experimental results indicate that the friction coefficient of TPH was quite low, and the wear resistance of TPH was better than that of Charisma, Elitefil or Veridonfil at the same condition. The main wear mechanism was found to be plastic flow and abrasive wear by failure of filler's bond to the matrix.

• Proceedings of the Earthquake Engineering Society of Korea Conference
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• 2006.03a
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• pp.233-240
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• 2006

An experimental investigation on the behavior of reinforced concrete coupling beams is presented. The test variables are the span-to-depth ratio, the ratio of flexural reinforcement and the ratio of shear rebar. The distribution of arch action and truss action which compose the mechanism of shear resistance is discussed. This study proposes the deformation model for reinforced concrete coupling beams considering the bond slip of flexural reinforcement. The yielding of flexural reinforcements determines yielding states and the ultimate states of reinforced concrete coupling beam are defined as the ultimate compressive strain of struts and the degradation of compressive strength due to principal tensile strain of struts. It is expected that this model can be applied to displacement-based design methods.

• Bulletin of the Korean Chemical Society
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• v.18 no.4
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• pp.390-394
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• 1997

Nucleophilic substitution reactions of 2-thiopheneethyl benzenesulfonates (2-TEB) and 3-thiopheneethyl benzenesulfonates (3-TEB) with anilines and N,N-dimethylanilines (DMA) are investigated in acetonitrile at 60.0 ℃. The cross-interaction constants ρxz determined for the reactions with anilines are large negative (- 0.50) which are comparable to those for the similar predominantly frontside-attack SN2 reactions of 1-phenylethyl (1-PEB), 2-phenylethyl (2-PEB) and cumyl benzenesulfonates. A large negative ρxz value (- 0.4∼- 0.8) is considered to provide a mechanistic criterion for the frontside-attack SN2 mechanism with a four-center transition state. In agreement with this proposal the kinetic isotope effects, kH/kD, involving deuterated aniline nucleophiles are all greater than one reflecting partial N-H(D) bond cleavage in the transition state. The MO theoretical reactant structures of 1-PEB, 2-PEB and 2-TEB based on the PM3 calculation show that the benzene ring blocks the backside nucleophile approach to the reaction center carbon (Cα) enforcing the frontside-attack SN2 mechanism.

• Bulletin of the Korean Chemical Society
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• v.19 no.6
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• pp.642-645
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• 1998

The aminolysis reactions of phenylacetyl chlorides with anilines and N,N-dimethylanilines (DMAS) in acetonitrile at -15.0 ℃ are investigated. The magnitude of ρx (= -2.8 ∼ -2.9) and ρy (= 0.9 ∼ 1.3, after correcting for the fall-off), and the negative sign of ρxy (= -0.12) for the reactions with anilines suggest an associative SN2 mechanism. For the reactions with DMAs, the magnitude of these Hammett coefficients increases so that tighter bond making in the transition state (TS) is predicted. A nonlinear Hammett plots obtained for the DMAs with an electron acceptor substituent is interpreted to result from a more advanced degree of leaving group departure to assist closer approach of the bulky DMA in the TS. The normal secondary kinetic isotope effects $(k_H/k_D>1.0)$ involving deuterated anilines suggest partial deprotonation by hydrogen bonding to the departing chloride ion.

• Applied Chemistry for Engineering
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• v.7 no.2
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• pp.321-325
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• 1996

Quantum chemical calculations are used to characterize the decomposition of nitrogenmonoxide over $Cu^{n+}$-Y zeolite. The method of theoretical calculations, such as CNDO/2, have been applied to cluster models representing cation sites in zeolite to obtain total energies, LUMO energies, and Wiberg bond orders. The calculated total energies and bond orders of cluster models showed the reaction mechanism of NO decomposition over $Cu^{n+}$ site in zeolite framework. The suggested cluster models of varying Si/Al ratios studied with exchange cations in the $Cu^+$ and in the $Cu^{2+}$ states. And the calculated LUMO energies can predict L acidifies of cluster models. The results from these experiments showed the possibility of the mechanism of NO decomposition, progressing adsorption of NO, conversion to $N_2$ and $O_2$, desorption of $N_2$ and $O_2$ in sequence. The L acidity of $Cu^{2+}$ ion in cation site is more strong than $Cu^+$.

• Journal of the Korean Chemical Society
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• v.35 no.6
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• pp.673-679
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• 1991

The electrochemical reduction of N-tert-butylbenzothiazole-2-sulfenamide (TBBS; vulcanization accelerator) was investigated by direct current, differential pulse polarography, cyclic voltammetry and controlled potential coulometry. The electrode reduction of TBBS proceeded E-C-E-C reaction mechanism by four electrons transfer at irreversible one wave (-2.31 volts vs. Ag/0.1M AgN$O_3$ in AN). As the results of controlled potential electrolysis, mercaptobenzothiazole (MBT), benzothiazole disulfide (MBT dimer) and extricated sulfur were products which followed by cleavage of the sulfenamide (-S-N=) bond. Upon the basis of products analysis and polarogram interpretation with pH variable, electrochemical reaction mechanism was suggested.

• Journal of the Korean Chemical Society
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• v.35 no.6
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• pp.680-688
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• 1991

The electrochemical reduction of N-oxyldiethylenebenzothiazole-2-sulfenamide (ODBS; vulcanization accelerator) was investigated by direct current polarography, differential pulse polarography, cyclic voltammetry and controlled potential coulometry. The irreversible electrode reduction of ODBS proceeded E-C-E-C reaction mechanism by three electrons transfer with irreversible one wave (-1.86 volts vs. Ag/0.1 M AgN$O_3$ in AN). As the results of controlled potential electrolysis, mercaptobenzothiazole (MBT), benzothiazole disulfide (MBT dimer) and extricated sulfur were products which followed by cleavage of the sulfenamide (-S-N=) bond. Upo the basis of products analysis and polarogram interpretation witli pH variable, electrochemical reaction mechanism was suggested.

• Bulletin of the Korean Chemical Society
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• v.35 no.7
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• pp.2013-2018
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• 2014

The adsorption and decomposition of trimethylene oxide ($C_3H_6O$) molecule on the Al(111) surface were investigated by the generalized gradient approximation (GGA) of density functional theory (DFT). The calculations employed a supercell ($6{\times}6{\times}3$) slab model and three-dimensional periodic boundary conditions. The strong attractive forces between $C_3H_6O$ molecule and Al atoms induce the C-O bond breaking of the ring $C_3H_6O$ molecule. Subsequently, the dissociated radical fragments of $C_3H_6O$ molecule oxidize the Al surface. The largest adsorption energy is about -260.0 kJ/mol in V3, V4 and P2, resulting a ring break at the C-O bond. We also investigated the decomposition mechanism of $C_3H_6O$ molecules on the Al(111) surface. The activation energies ($E_a$) for the dissociations V3, V4 and P2 are 133.3, 166.8 and 174.0 kJ/mol, respectively. The hcp site is the most reactive position for $C_3H_6O$ decomposing.

• Bulletin of the Korean Chemical Society
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• v.25 no.6
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• pp.838-842
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• 2004

Amyloid peptide (A${\beta}$) is the major component of senile plaques found in the brain of patient of Alzheimer's disease. ${\beta}$-amyloid peptide (25-35) (A${\beta}$25-35) is biologically active fragment of A${\beta}$. The three-dimensional structure of A${\beta}$25-35 in aqueous solution with 50% (vol/vol) TFE determined by NMR spectroscopy previously adopts an ${\alpha}$-helical conformation from $Ala^{30}$ to $Met^{35}$. It has been proposed that A${\beta}$(25-35) exhibits pH- and concentration-dependent ${\alpha}-helix{\leftrightarrow}{\beta}$sheet transition. This conformational transition with concomitant peptide aggregation is a possible mechanism of plaque formation. Here, in order to gain more insight into the mechanism of ${\alpha}$-helix formation of A${\beta}$25-35 peptide by TFE, which particularly stabilizes ${\alpha}$-helical conformation, we studied the secondary-structural elements of A${\beta}$25-35 peptide by molecular dynamics simulations. Secondary structural elements determined from NMR spectroscopy in aqueous TFE solution are preserved during the MD simulation. TFE/water mixed solvent has reduced capacity for forming hydrogen bond to the peptide compared to pure water solvent. TFE allows A${\beta}$25-35 to form bifurcated hydrogen bonds to TFE as well as to residues in peptide itself. MD simulation in this study supports the notion that TFE can act as an ${\alpha}$-helical structure forming solvent.