• Bulletin of the Korean Chemical Society
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• v.35 no.2
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• pp.436-440
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• 2014

The ${\alpha}$-Effect; Ground state; Transition state; Intramolecular H-bonding; Yukawa-Tsuno plot; Second-order rate constants for aminolysis of 2-chloro-4-nitrophenyl X-substituted-benzoates (1a-h) have been measured spectrophotometrically in 80 mol % $H_2O/20$ mol % DMSO at $25.0^{\circ}C$. The Br${\emptyset}$nsted-type plot for the reactions of 2-chloro-4-nitrophenyl benzoate (1d) with a series of primary amines curves downward, which has been taken as evidence for a stepwise mechanism with a change in rate-determining step (RDS). The Hammett plots for the reactions of 1a-h with hydrazine and glycylglycine are nonlinear while the Yukawa-Tsuno plots exhibit excellent linearity with ${\rho}_X=1.22-1.35$ and ${\gamma}= 0.57-0.59$, indicating that the nonlinear Hammett plots are not due to a change in RDS but are caused by stabilization of substrates possessing an electron-donating group (EDG) through resonance interactions between the EDG and C=O bond of the substrates. The ${\alpha}$-effect exhibited by hydrazine increases as the substituent X changes from a strong EDG to a strong electron-withdrawing group (EWG). It has been concluded that destabilization of hydrazine through the electronic repulsion between the adjacent nonbonding electrons is not solely responsible for the substituent dependent ${\alpha}$-effect but stabilization of the transition state is also a plausible origin of the ${\alpha}$-effect.

• Bulletin of the Korean Chemical Society
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• v.34 no.8
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• pp.2251-2255
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• 2013

Second-order rate constants ($k_{HOO^-}$) for the nucleophilic substitution reactions of Y-substituted-phenyl diphenylphosphinates (4a-4i) with $HOO^-$ in $H_2O$ have been measured spectrophotometrically. The ${\alpha}$-nucleophile $HOO^-$ is 10-70 times more reactive than the reference nucleophile $OH^-$ although the former is ca. $4pK_a$ units less basic than the latter, indicating the ${\alpha}$-effect is operative. The Bronsted-type plot for the reactions of 4a-4i with $HOO^-$ is linear with ${\beta}_{lg}=-0.51$, a typical ${\beta}_{lg}$ value for reactions which were reported to proceed through a concerted mechanism. The Yukawa-Tsuno plot is also linear with ${\rho}=1.40$ and r = 0.47, indicating that a negative charge develops partially on the O atom of the leaving group, which can be delocalized to the substituent Y through resonance interactions. Thus, the reactions have been proposed to proceed through a concerted mechanism. The magnitude of the ${\alpha}$-effect (i.e., the $k_{HOO^-}/k_{HO^-}$ ratio) decreases linearly as the leaving-group basicity increases. It has been concluded that solvation effect is not solely responsible for the ${\alpha}$-effect found in this study but the transition-state stabilization through an intramolecular H-bonding interaction is also responsible for the ${\alpha}$-effect.

• Transactions of the Korean Society of Mechanical Engineers A
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• v.26 no.11
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• pp.2328-2335
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• 2002

A hybrid composite material has many potential usage due to the high specific strength and the resistance to fatigue, when compared to other composite materials such as fiber reinforced plastic(FRP) and metal matrix composite(MMC). However, the fracture mechanism of hybrid composite material is extremely complicated because of the bonding structure of metals and FRP. In this study, Al 7075 sheets and carbon epoxy preprags were used to fabricate the hybrid composite. Recently, nondestructive technique has been used to evaluate the fracture mechanism of these composite materials. AE technique was used to clarify the microscopic damage behavior and failure mechanism of A17075/CFRP hybrid composite. It was found that AE paralneters such as AE event, energy and amplitude were effective to evaluate the failure process of Al 7075/CFRP composite. In addition, the relationship between the AE signal and the characteristics of fracture surface using optical microscope was discussed.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.24 no.4
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• pp.266-270
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• 2011

We report on the formation mechanism of large Schottky barrier height (SBH) of nonalloyed Cr Schottky contacts on strained Al0.25Ga0.75N/GaN. Based on the current-voltage (I-V) and capacitance-voltage (C-V) data, the SBHs are determined to be 1.98 (${\pm}0.02$) and 2.07 (${\pm}0.02$) eV from the thermionic field emission and two-dimensional electron gas (2DEG) calculations, respectively. Possible formation mechanism of large SBH will be described in terms of the formation of Cr-O chemical bonding at the interface between Cr and AlGaN/GaN, low binding-energy shift to surface Fermi level, and the reduction of 2DEG electrons.

• Steel and Composite Structures
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• v.51 no.1
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• pp.53-61
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• 2024

Aluminum foams sandwich panel (AFSP) has been used in engineering field, where cyclic loading is used in most of the applications. In this paper, the fatigue life of AFSP prepared by the bonding method was investigated through a three-point bending test. The mathematical statistics method was used to analyze the influence of different plate thicknesses and core densities on the bending fatigue life. The macroscopic fatigue failure modes and damage mechanisms were observed by scanning electron microscopy (SEM). The results indicate that panel thickness and core layer density have a significant influence on the bending fatigue life of AFSP and their dispersion. The damage mechanism of fatigue failure to cells in aluminum foam is that the initial fatigue crack begins the cell wall, the thinnest position of the cell wall or the intersection of the cell wall and the cell ridge, where stress concentrations are more likely to occur. The fatigue failure of aluminum foam core usually starts from the semi-closed unit of the lower layer, and the fatigue crack propagates layer by layer along the direction of the maximum shear stress. The results can provide a reference for the practical engineering design and application of AFSP.

• Bulletin of the Korean Chemical Society
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• v.34 no.4
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• pp.1115-1119
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• 2013

A kinetic study is reported for nucleophilic substitution reactions of benzyl 2-pyridyl thionocarbonate (5b) and t-butyl 2-pyridyl thionocarbonate (6b) with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. General-base catalysis, which has often been reported to occur for aminolysis of esters possessing a C=S electrophilic center, is absent for the reactions of 5b and 6b. The Br${\o}$nsted-type plots for the reactions of 5b and 6b are linear with ${\beta}_{nuc}$ = 0.29 and 0.43, respectively, indicating that the reactions of 5b proceed through a stepwise mechanism with formation of a zwitterionic tetrahedral intermediate ($T^{\pm}$) being the rate-determining step while those of 6b proceed through a concerted mechanism. The reactivity of 5b and 6b is similar to that of their oxygen analogues (i.e., benzyl 2-pyridyl carbonate 5a and t-butyl 2-pyridyl carbonate 6a, respectively), indicating that the effect of modification of the electrophilic center from C=O to C=S (i.e., from 5a to 5b and from 6a to 6b) on reactivity is insignificant. In contrast, 6b is much less reactive than 5b, indicating that the replacement of the $PhCH_2$ in 5b by the t-Bu in 6b results in a significant decrease in reactivity as well as a change in the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway). It has been concluded that the contrasting reactivity and reaction mechanism for the reactions of 5b and 6b are not due to the electronic effects of $PhCH_2$ and t-Bu but are caused by the large steric hindrance exerted by the bulky t-Bu in 6b.

• Journal of Ocean Engineering and Technology
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• v.13 no.3 s.33
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• pp.77-82
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• 1999

The compleete joining method for dissimilar hot die punch materials and its real-time evaluation method are not available at present. Brazing method has been used for joining them, but it is known that the welded joint by the brazing has the lower bonding efficiency and reliability than the diffusion welding. The friction wleding with a diffusion mechanism in bonding was applied in this study. So, this work was carried out to determine the optimal friction welding conditions and to analyze mechanical properties of friction welded joints of hot die punch materials (STD61 for the blade part of hot die punch) to alloy steel (SCM440 for the shank park of hot die punch) such as plunger. In addition, acoustic emission test was carried out during friction welding to evaluate the weld quality.

• Steel and Composite Structures
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• v.37 no.4
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• pp.419-429
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• 2020

Composite structures are generally pressurized at both sides when repaired by the scarf repair method. But single-face vacuum bag curing (SVC) may be used in some practical scarf repair of penetration damage due to the low accessibility of composite structures, which can decrease bonding quality and may reduce structural mechanical properties. In this paper, experimental investigations were conducted on tensile and compressive properties of scarf-repaired composite laminates using SVC and double-face vacuum bag curing (DVC) in four hygrothermal environments. Finite element models of composite scarf joints with voids were established to further explore the failure mechanism of scarf-repaired laminates. Results show that the curing condition hardly affects tensile and compressive properties of the repaired laminates though it significantly affects the bonding quality with adhesive inner voids. Failure loads of scarf joints almost keep unchanged with adhesive voids increasing.

• Bulletin of the Korean Chemical Society
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• v.29 no.8
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• pp.1479-1484
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• 2008

Protein tyrosine phosphatase (PTP) 1B is the superfamily of PTPs and a negative regulator of multiple receptor tyrosine kinases (RTKs). Inhibition of protein tyrosine phosphatase 1B (PTP1B) has been proposed as a strategy for the treatment of type 2 diabetes and obesity. Recently, it has been reported that amentoflavone, a biflavonoid extracted from Selaginella tamariscina, inhibited PTP1B. In the present study, docking model between amentoflavone and PTP1B was determined using automated docking study. Based on this docking model and the interactions between the known inhibitors and PTP1B, we determined multiple pharmacophore maps which consisted of five features, two hydrogen bonding acceptors, two hydrogen bonding donors, and one lipophilic. Using receptor-oriented pharmacophore-based in silico screening, we searched the biflavonoid database including 40 naturally occurring biflavonoids. From these results, it can be proposed that two biflavonoids, sumaflavone and tetrahydroamentoflavone can be potent allosteric inhibitors, and the linkage at 5',8''-position of two flavones and a hydroxyl group at 4'-position are the critical factors for their allosteric inhibition. This study will be helpful to understand the mechanism of allosteric inhibition of PTP1B by biflavonoids and give insights to develop potent inhibitors of PTP1B.

• Bulletin of the Korean Chemical Society
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• v.32 no.4
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• pp.1258-1262
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• 2011

A new organogelator, L-Alanine dihydrazide derivative can self-assemble in various organic solvents and turned them into thermally reversible physical supramolecular organogels at extremely low concentrations (< 2 wt %). The gel-sol phase transition temperatures ($T_{GS}$) were determined as a function of gelator concentration and the corresponding enthalpies (${\Delta}H_g$) were extracted. Scanning electron microscopy (SEM) measurements revealed that the interspaces of fiber-like network structures were diminished with the increasing of the LMOG concentration. FT-IR spectroscopy studies revealed that hydrogen-bonding and hydrophobic interaction were the driving forces for the formation of the gels. Based on the data of XRD and molecular modeling, the possible packing modes for the formation of organogelator aggregates were proposed.