• Bulletin of the Korean Chemical Society
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• 제32권spc8호
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• pp.2955-2959
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• 2011

Second-order rate constants for nucleophilic substitution reactions of 2,4-dinitrophenyl benzenesulfonate 1a with a series of alicyclic secondary amines in MeCN have been measured spectrophotometrically and compared with those reported previously for the corresponding reactions performed in aqueous medium to investigate the effect of medium on reactivity and reaction mechanism. The amines employed in this study are found to be more reactive in the aprotic solvent than in $H_2O$. The reactions of 1a in MeCN result in a linear Br${\o}$nsted-type plot with ${\beta}_{nuc}$ = 0.58, which contrasts to the curved Br${\o}$nsted-type plot reported previously for the corresponding reactions performed in the aqueous medium (i.e., ${\beta}_2$ = 0.86 and ${\beta}_1$ = 0.38). Accordingly, it has been concluded that the reaction mechanism changes from a stepwise mechanism to a concerted pathway upon changing the medium from $H_2O$ to MeCN. Reactions of Y-substituted phenyl benzenesulfonates 1a-c with piperidine in MeCN result in a linear Br${\o}$nsted-type plot with ${\beta}_{lg}$ = -1.31, indicating that expulsion of the leaving group is significantly more advanced than bond formation in the transition state. The trigonal bipyramidal intermediate ($TBPy^{\pm}$) proposed previously for the reactions in $H_2O$ would be highly unstable in MeCN due to strong repulsion between the negative charge in $TBPy^{\pm}$ and the negative dipole end of MeCN. Thus, destabilization of $TBPy^{\pm}$ in MeCN has been concluded to change the reaction mechanism from a stepwise mechanism to a concerted pathway.

• Bulletin of the Korean Chemical Society
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• 제32권11호
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• pp.3973-3978
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• 2011

The reductive pinacol coupling reaction of aldehydes or ketones creating a new C-C bond has been a major tool to produce 1,2-diol compounds. The reaction mechanism is known to be composed of sequential three steps (activation, coupling, and dissociation). In this work, we studied the dissociation step of half-titanocene-based catalytic systems. Cp and $Cp^*$ derivatives of the pinacolato-bridged dinuclear complex were synthesized and evaluated as possible models for intermediates from the coupling step. We monitored $^1H$-NMR spectra of the reaction between the metalla-pinacol intermediates and $D_2O$. New reaction routes of the dissociation step including oxo- and pinacolato-dibridged dinuclear complexes and oxo-bridged multinuclear complexes have been suggested.

• Bulletin of the Korean Chemical Society
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• 제33권10호
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• pp.3274-3278
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• 2012

The kinetic studies on the reactions of phenyl N-phenyl phosphoramidochloridate (8) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) have been carried out in acetonitrile at $60.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are huge secondary inverse ($k_H/k_D$ = 0.52-0.69). A concerted mechanism is proposed with a backside attack transition state (TS) on the basis of the secondary inverse DKIEs and the variation trends of the $k_H/k_D$ values with X. The degree of bond formation in the TS is really extensive taking into account the very small values of the DKIEs. The steric effects of the two ligands on the rates are extensively discussed for the aminolyses of the chlorophosphate-type substrates on the basis of the Taft equation.

• 한국세라믹학회지
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• 제15권2호
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• pp.89-97
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• 1978

The basic mechanism of adherence in sintered high purity alumina ceramic-to-metal bonding was studied. Emphasis was placed on flux composition, porosity of the fired ceramics, and metallizing mixtures. The study was conducted on 95 and 99.5% alumina, using molydbenum-manganese, molybdenum-manganese-silicon dioxide metallizing compositions. Metallizing was performed in wet hydrogen (dew point, ＋17$^{\circ}C$) at 145$0^{\circ}C$ for 45min. This experiment indicated that adhernece mechanism of ultra high purity alumina ceramic was attributed to formation of $MnAl_2O_$4, and in the case of 95% alumina containing glass, the migration of glass from the interface into the void of the metal coating was the main role to the adhrence. It showed also that greater the bond-strength was resulted as porosity was increased.

• 대한기계학회:학술대회논문집
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• 대한기계학회 2004년도 추계학술대회
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• pp.410-415
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• 2004

Molecular dynamics simulations of nanoimprint lithography in which a stamp with patterns is pressed onto amorphous poly-(methylmethacrylate) (PMMA) surface are performed to study the deformation of polymer. Force fields including bond, angle, torsion, inversion, van der Waals and electrostatic potential are used to describe the intermolecular and intramolecular force of PMMA molecules and stamp. Periodic boundary condition is used in horizontal direction and $Nos\acute{e}$-Hoover thermostat is used to control the system temperature. As the simulation results, the adhesion forces between stamp and polymer are calculated and the mechanism of deformation are investigated. The effects of the adhesion force and friction force on the polymer deformation are also studied to analyze the pattern transfer in nanoimprint lithography. The mechanism of polymer deformation is investigated by means of inspecting the indentation process, molecular configurational properties, and molecular configurational energies.

• 대한기계학회논문집
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• 제17권12호
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• pp.3028-3044
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• 1993

A metallic bond of great strength for the same or dissimilar metals can be produced by the explosive welding. The formation of a metallic jet at the interface between the two impacting plates has been simulated using the numerical hydrocode DYNA2D. The mechanism of explosive welding for the wave formation is also analyzed by the computer simulation technique. The microscopic with the experimentally observed behaviour of the explosive welding. The computer simulations of the explosive welding process have proven especially useful for analyzing the mechanism of metallic bones.

• 한국응용과학기술학회지
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• 제9권2호
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• pp.119-126
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• 1992

The kinetics of the hydrolysis of indolylacrylophenone derivatives(IA) was investigated by ultraviolet spectrophotometry in 30% dioxane-$H_2O$ at 25$^{\circ}C$ Rate equations were obtained over a wide pH range. On the basis of rate equation, general base catalysis and Hammett's plot, the mechanism of hydrolysis to the (IA) were proposed: Below pH 3.0, the hydrolysis of (IA) was proportional to hydronium ion concentration, between pH 4.0${\sim}$9.0 neutral water molecule and hydroxide ion were added to carbon-carbon double bond and over pH 10.0 hydrolysis of (IA) was proportional to hydroxide ion concentration.

• 한국콘크리트학회:학술대회논문집
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• 한국콘크리트학회 1999년도 봄 학술발표회 논문집(I)
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• pp.750-755
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• 1999

When the RC frame structures subjected to the seismic load, brittle shear failure of vertical members induces brittle collapse of whole structures. Failure mechanism like this is not desirable. So shear strengthening method to avoid this failure mechanism is needed. Recently, strengthening method using continuous fiber sheet is studied and used widely which have high elastic and high strength characteristics. In this study, RC columns which is strengthened by carbon fiber sheet in the form of tape or whole sheet were tested under the cyclic load. The parameter of this test is the amount of strengthening. As the amount of strengthening increase, strength, ductility and energy capacity increase. The failure mode of test results are shear and bond-split failure.

• 한국콘크리트학회:학술대회논문집
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• 한국콘크리트학회 2006년도 춘계학술발표회 논문집(I)
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• pp.50-53
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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.

• Computers and Concrete
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• 제1권3호
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• pp.249-260
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• 2004

The stress transmission mechanism in pretensioned concrete beams, though very interesting from an economical point of view, is very complex, integrating various phenomenons such as sliding, bond, bursting. For long the complexity of this mechanism has led engineers to provide a massive rectangular anchorage zone at each end of the beam. The necessity of using such a concrete reinforcement is certainly unquestionable in post-tensioned beams. However in pretensioned elements the stresses induced in concrete in the anchorage zone are smaller than in post-tensioned elements. In this article the stress field in the end zone is calculated numerically and from this analysis the possible reduction of the cross-section of the anchorage block is examined.