• Bulletin of the Korean Chemical Society
• /
• 제23권2호
• /
• pp.221-224
• /
• 2002

Nucleophilic addition reactions of benzylamines (BA; $XC_6H_4CH_2NH_2$) to ethyl-${\alpha}$-cyanocinnamates (ECC;$YC_6H_4CH$=C(CN)COOEt) have been investigated in acetonitrile at $30.0^{\circ}C$. The rate is first order with respect to BA and ECC. The rate is slower than that expected from the additive effect of ${\sigma}^-$ or $R^-$ for the activating groups (CN and COOEt). Natural. bond orbital ${\pi}^{\ast}_{c=c}$ calculations show that the contribution of COOEt group may not be fully effective despite the coplanar molecular structure. The selectivity parameters including the cross-interaction constant (${\rho}_{xy}$ = -0.22) indicate that the addition occurs in a single step. The kinetic isotope effects ($k_H/k_D$=2.5-2.8) involving deuterated BA ($XC_6H_4CH_2ND_2$) nucleophiles and activation parameters (${\Delta}H^{\neq}=4{\sim}6\;kcal\;mol^{-1};{\Delta}S^{\neq}=-45{\sim}-52\;e.u.$) suggest a cyclic transition state in which N-$C_{\alpha}$ and H-$C_{\beta}$ bonds are formed concurrently.

• Macromolecular Research
• /
• 제12권2호
• /
• pp.219-224
• /
• 2004

In this work, we prepared hydrogels for wound dressing from a mixture of poly(vinyl alcohol) (PVA) and alginate using the $\^$60/Co ${\gamma}$-ray irradiation technique. We examined the physical properties of these hydrogels, including gelation, water absorptivity, and gel strength, to evaluate the applicability of these hydrogels for wound dressings. The biocompatibility of these hydrogels was also evaluated in vitro, in cultures of mouse fibroblasts, and in vivo, by subcutaneous implantation studies in rats. The gel content and strength increased upon increasing the radiation dose and upon decreasing the concentration of alginate. The degree of swelling was inversely proportional to the gel content and strength. The degree of cytotoxicity of the ${\gamma}$-ray-treated hydrogels was ca. 60% compared to the (－) control (serum) after 1 day of incubation. When the incubations were prolonged up to 2 days, the toxicity of all the samples decreased remarkably and reached that of the control. Subcutaneous implantation studies in rats indicated that foreign body reactions occurring around the implanted hydrogels were moderate and became minimal upon increasing the implantation time.

• Bulletin of the Korean Chemical Society
• /
• 제24권2호
• /
• pp.193-196
• /
• 2003

Nucleophilic addition reactions of benzylamines $(XC_6H_4CH_2NH_2)$ to benzylidene Meldrum's acids (BMA; $YC_6H_4CH=C(COO)_2C(CH_3)_2$) have been investigated in acetonitrile at 20.0 ℃. The rates of addition are greatly enhanced due to the abnormally high acidity of Meldrum's acid. The magnitudes of the Hammett $({\rho}_X\;and\;{\rho}_Y)$ and Bronsted $({\rho}_X$)$ coefficients are rather small suggesting an early transition state. The sign and magnitude of the cross-interaction constant, ${\rho}_{XY}$ (= -0.33), and kinetic isotope effects $(k_H/k_D\;{\stackrel}{~}{=}\;1.5-1.7)$ involving deuterated benzylamine nucleophilies $(XC_6H_4CH_2ND_2)$ are indicative of hydrogen-bonded cyclic transition state. The activation parameters, ${\Delta}H^{\neq}\;{\stackrel}{~}{=}\;4\;kcal\;mol^{-1}\;and\;{\Delta}S^{\neq}\;{\stackrel}{~}{=}\;-37\;e.u.$, are also in line with the proposed mechanism.

• Bulletin of the Korean Chemical Society
• /
• 제29권4호
• /
• pp.851-855
• /
• 2008

The reactions of O,O-diphenyl Z-S-phenyl phosphorothiolates with X-pyridines have been studied kinetically in acetonitrile at $35.0{^{\circ}C}$. The Hammett plots for substituent (Z) variations in the leaving group (log $k_2$ vs. $\sigma$ Z) are biphasic concave downwards with breaks at Z = H. The large magnitudes of ${\rho}X(\rho_{nuc})$, ${\beta}X(\rho_{nuc})$, and the cross-interaction constant, $\rho$XZ, suggest frontside nucleophilic attack toward the leaving group. The sign reversal of $\rho$Z from positive in $\sigma$ Z $\leq$ 0 to negative in $\sigma$ Z $\geq$ 0 is interpreted as the change in mechanism from concerted to stepwise with rate-limiting expulsion of the leaving group. The anomalous negative sign of $\rho$ Z for leaving groups with electron-withdrawing substituents is interpreted as the intramolecular ligand exchange process of the leaving group from the equatorial position in the intermediate to the apical position in the TS.

• Bulletin of the Korean Chemical Society
• /
• 제23권10호
• /
• pp.1459-1462
• /
• 2002

The kinetics of the addition of X-substituted benzylamines (BA) to Y-substituted Benzylideneacetylacetones (BAA) have been investigated in acetonitrile at $25.0^{\circ}C$. The reaction is studied under pseudo-first-order conditions by keeping a large excess of BA over BAA. The addition of BA to BAA occurs in a single step in which the addition of BA to $C_\alpha$ of BAA and proton transfer from BA to $C_\beta$ of BAA take place concurrently with a four-membered cyclic transition state structure. The magnitude of the Hammett ($p_X$) and Bronsted ($\beta_x$) coefficients are rather small suggesting an early tansition state (TS). The sign and magnitude of the cross-interaction constant, $p_{XY}$ (= -0.49), is comparatible to those found in the normal bond formation processes in the $S_N2$ and addition reactions. The normal kinetic isotope effect ($K_H/K_D$ > 1.0) and relatively low $\Delta$H^{${\neq}$}$ and large negative $\Delta$S^{${\neq}$}$ values are also consistent with the mechanism proposed.

• Bulletin of the Korean Chemical Society
• /
• 제32권10호
• /
• pp.3587-3591
• /
• 2011

The reactions of O,O-diethyl Z-S-aryl phosphorothioates with X-benzylamines are kinetically investigated in dimethyl sulfoxide at $85.0^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}x$) and Br$\ddot{o}$nsted [log $k_2$ vs $pK_a$(X)] plots are biphasic concave downwards for substituent X variations in the nucleophiles with a break point at X = H. The signs of the cross-interaction constants (${\rho}xz$) are positive for both the strongly and weakly basic nucleophiles. Considerably great magnitude of ${\rho}xz$ (= 6.56) value is observed with the weakly basic nucleophiles, while ${\rho}xz$ = 0.91 with the strongly basic nucleophiles. Proposed reaction mechanism is a stepwise process with a rate-limiting leaving group expulsion from the intermediate involving a backside nucleophilic attack with the strongly basic nucleophiles and a frontside attack with the weakly basic nucleophiles. The kinetic results are compared with those of the benzylaminolysis of O,O-diphenyl Z-S-aryl phosphorothioates.

• Steel and Composite Structures
• /
• 제27권2호
• /
• pp.185-192
• /
• 2018

Fly ash can significantly improve concrete workability and performance, and recycling fly ash in concrete can contribute to a cleaner environment. Since fly ash influences pozzolanic reactions in concrete, mechanical behaviors of concrete containing fly ash differ from traditional concrete. Creep behaviors of fly ash concrete filled steel tube arch were experimentally investigated for 10% and 30% fly ash replacement. The axes of two arches are designed as circular arc with 2.1 m computed span, 0.24 m arch rise, and their cross-sections are all in circular section. Time dependent deflection and strain of loading and mid-span steel tube were measured, and long term deflection of the model arch with 10% fly ash replacement was significantly larger than with 30% replacement. Considering the steel tube strain, compressive zone height, cross section curvature, and internal force borne by the steel tube, the compressive zone height and structural internal forces increased gradually over time due to concrete creep. Increased fly ash content resulted in more significant neutral axis shift. Mechanisms for internal force effects on neutral axis height were analyzed and verified experimentally.

• Nuclear Engineering and Technology
• /
• 제50권3호
• /
• pp.389-395
• /
• 2018

The present work aims to report the consequences of Darcy-Forchheimer medium in flow of Cross fluid model toward a stretched surface. Flow in porous space is categorized by Darcy-Forchheimer medium. Further heat transfer characteristics are examined via thermal radiation and heat generation/absorption. Transformation procedure is used. The arising system of nonlinear ordinary differential equations is solved numerically by means of shooting method. The effects of different flow variables on velocity, temperature, concentration, skin friction, and heat transfer rate are discussed. The obtained outcomes show that velocity was enhanced with the increase in the Weissenberg number but decays with increase in the porosity parameter and Hartman number. Temperature field is boosted by thermal radiation and heat generation; however, it decays with the increase in the Prandtl number.

• 한국철도학회:학술대회논문집
• /
• 한국철도학회 2007년도 춘계학술대회 논문집
• /
• pp.1097-1106
• /
• 2007

Rail provides running tract for train and broadly and widely conveys the weight of the train exerted from the train wheels that the rail directly supports onto the cross tie and roadbed, and supports the cross-sectional pressure exerted by centrifugal force at curvatures. That is, stationary rail provides surface on which dynamic train runs and guarantees cross-sectional resistance to enable the vertical snake motion of the train wheels as well as to maintain lateral force at curvatures. Rail provides running surface on which train wheels can run smoothly, and secures vertical and lateral force. However, it undergoes continuous destructive reactions (wearing and damages) and abrasion of the cladding by the train wheels. It is obvious that wearing will result when two metal parts act against each other. However, occurrence of abnormal wearing such as rapid wearing of the rail side due to complex generation of various mechanisms at the contact surface between the rail and train wheel flange. It is not easy to simply examine the causes of occurrence of abnormal wearing of rail and train wheel flange. Although countless number of academicians and specialists are conducting researches on abnormal wearing of rail and vertical wearing of train wheels, I believe it is too early to argue on pros and cons due to insufficiency of officially verified information on the issue. This review will be focusing on the examples of repairs that reduced the generation of abnormal wearing of rail by reviewing and improving characteristics of wearing and slack, speed of the train and cant as well as status of lubricator by choosing the compound curves present in the section between the $Anguk{\sim}Jongno3-ga$ Stations of the Route No. 3 among the compound curve tracks of the Seoul Metro Routes No. 3 & 4 at which abnormal wearing is generated continuously.

• 한국멀티미디어학회논문지
• /
• 제20권7호
• /
• pp.979-985
• /
• 2017

This paper, which covers a fluorescence microscopy image of brain tumor cells, looks at drug reactions by treating different types and concentrations of drugs on a plate of $24{\times}16$ wells. Due to the limitation of the field of view, a well was taken into 9 field images, and each has an overlapping area with its neighboring fields. To analyze more precisely, image stitching is needed. The basic method is finding a similar area using normalized cross-correlation (NCC). The problem is that some overlapping areas may not have any duplicated cells that help to find the matching point. In addition, the cell objects have similar sizes and shapes, which makes distinguishing them difficult. To avoid calculating similarity between blank areas and roughly distinguishing different cells, thresholding is added. The thresholding method classifies background and cell objects based on fixed thresholds and finds the location of the first seen cell. After getting its location, NCC is used to find the best correlation point. The results are compared with a simple boundary stitched image. Our proposed method stitches images that are connected in a grid form without collision, selecting the best correlation point among areas that contain overlapping cells and ones without it.