• Title/Summary/Keyword: Bond mechanism

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An Experimental Study to Prevent Debonding Failure of RC Beams Strengthened by AFRP Sheet (아라미드섬유쉬트로 휨 보강된 RC보의 부착파괴 방지에 관한 실험적 연구)

  • Choi, Ki-Sun;You, Young-Chan;Kim, Keung-Hwan
    • Journal of the Korea institute for structural maintenance and inspection
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    • v.11 no.5
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    • pp.144-152
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    • 2007
  • This study investigated the failure mechanism of RC beams strengthened with AFRP sheets. Total 5 half-scale RC beams were constructed and tested to estimate the effectiveness of various methods to prevent the debonding failure of AFRP sheets. From the experimental results, it was found that increasing bonded length or end U-wrappings does not prevent debonding failure. On the other hand, the beams with center U-wrappings and shear-keys reached the ultimate state with their sufficient performance. The center U-wrappings tended to control debonding of the longitudinal AFRP sheets because the growth of the longitudinal cracks along the edges of the composites was delayed. In case of shear-keys, it was sufficient to eliminate debonding and the beams failed by AFRP sheets rupture due to the sufficient bond mechanism.

In vivo metabolism of carbofuran in resistant and susceptible brown planthoppers, Nilaparvata lugens $St{\aa}l$ (저항성 및 감수성 벼멸구 체내에서의 카보후란 대사)

  • Yoo, Jai-Ki;Ahn, Yong-Joon;Shono, Toshio;Lee, Si-Woo
    • The Korean Journal of Pesticide Science
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    • v.2 no.2
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    • pp.75-82
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    • 1998
  • This study was conducted to find out the biochemical or metabolic resistance mechanism of brown planthopper (BPH) to carbofuran. Differences between resistant ($LD_{50};\;20.3{\mu}g/g$) and susceptible strains($LD_{50};\;0.3{\mu}g/g$) were shown. The amounts of carbofuran metabolite, benzofuranol, and the origin, not developed by Thin Layer Chromatography, were much more in the susceptible strain. But the mother compound, carbofuran, was much more in the resistant strain. The tendencies of metabolism one and three hours after treatment were similar in both strains except for the amounts of metabolites described above. From the study, it is supposed that hydrolytic enzyme, esterase, changes its role from cleaving the esteric bond of carbofuran to making conjugates with carbofuran. This seems to be the main resistance mechanism of BPH to carbofuran. Oxidase and transferase may play little or no role in resistance mechanism. Oxidative and transferring enzymes gave no effects on the metabolism of carbofuran in the resistant strain compared with the susceptible strain.

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Kinetics and Mechanism for Aquation of cis-[Co(en)$_2$YCl]$^{r+}$ (Y = NH$_3^-$, NO$_2$, NCS$^-$, H$_2$O} in Hg$^{2+}$ Aqueous Solution ($Hg^{2+}$ 수용액 내에서 cis-[Co(en)$_2$YCl]$^{r+}$ (Y = $NH_3$, NO$_2^-$, NCS$^-$, $H_2O$)의 아쿠아 반응속도와 반응메카니즘)

  • Byung-Kak Park;Joo-Sang Lim
    • Journal of the Korean Chemical Society
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    • v.32 no.5
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    • pp.476-482
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    • 1988
  • Kinetic studies and theoretical investigations were made to illustrate the mechanism of the aquation of cis-[Co(en)$_2$YCl]$^{r+}$ (Y = NH$_3$, NO$_2^-$, NCS$^-$, $H_2O$) in $Hg^{2+}$ aqueous solution UV/vis-spectrophotometrically. The aquation of cis-[Co(en)$_2$YCl]$^{r+}$ have been found to be the second order for overall reaction as first order for each of substrate and Hg$^{2+}$+ catalyst. The reaction rate was increased in the order of Y=NH$_3$ < NCS$^-$- < $H_2O$ < $NO_2^-$, which are neighboring group of Cl. The step of bond formation was found to be the rate determining one, because the net charge of central metal ion run parallel with the observed rate constant. On the basis of rate determining step, kinetic data and the observed activation parameters, we have proposed the Id mechanism for the reaction system. The rate equation derived from the proposed mechanism has been in agreement with the observed rate equation.

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Significant Substituent Effects on Pyridinolysis of Aryl Ethyl Chlorophosphates in Acetonitrile

  • Adhikary, Keshab Kumar;Lee, Hai Whang
    • Bulletin of the Korean Chemical Society
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    • v.35 no.5
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    • pp.1460-1464
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    • 2014
  • The substituent effects on the pyridinolysis (XC5H4N) of Y-aryl ethyl chlorophosphates are investigated in acetonitrile at $35.0^{\circ}C$. The two strong ${\pi}$-acceptor substituents, X = 4-Ac and 4-CN in the X-pyridines, exhibit large positive deviations from the Hammett plots but little positive deviations from the Br$\ddot{o}$nsted plots. The substituent Y effects on the rates are really significant and the Hammett plots for substituent Y variations in the substrates invariably change from biphasic concave downwards via isokinetic at X = H to biphasic concave upwards with a break point at Y = 3-Me as the pyridine becomes less basic. These are interpreted to indicate a mechanistic change at the break point from a stepwise mechanism with a rate-limiting bond formation (${\rho}_{XY}$ = -6.26) for Y = (4-MeO, 4-Me, 3-Me) to with a rate-limiting leaving group expulsion from the intermediate (${\rho}_{XY}$ = +5.47) for Y = (4-Me, H, 3-MeO). The exceptionally large magnitudes of ${\rho}_{XY}$ values imply frontside nucleophilic attack transition state.

A Mechanistic Study on the Nucleophilic Addition Reactions of Benzylamines to the Activated Olefins

  • Oh, Hyuck-Keun
    • Bulletin of the Korean Chemical Society
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    • v.29 no.6
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    • pp.1195-1198
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    • 2008
  • Kinetic studies of the additions of benzylamines to a noncyclic dicarbonyl group activated olefin, methyl $\alpha$-acetyl-$\beta$ -phenylacrylates (MAP), in acetonitrile at 30.0 ${^{\circ}C}$ are reported. The rates are lower than those for the cyclic dicarbonyl group activated olefins. The addition occurs in a single step with concurrent formation of the $C_\alpha$ -N and $C_\beta$ -H bonds through a four-center hydrogen bonded transition state. The kinetic isotope effects ($k_H/k_D$ > 1.0) measured with deuterated benzylamines ($XC_6H_4CH_2ND_2$) increase with a stronger electron acceptor substituent ($\delta\sigma$ X > 0) which is the same trend as those found for other dicarbonyl group activated series (1-4). The sign and magnitude of the cross-interaction constant, ρXY, is comparable to those for the normal bond formation processes in the $S_N2$ and addition reactions. The relatively low ${\Delta}H^\neq$ and large negative ${\Delta}S^\neq$ values are also consistent with the mechanism proposed.

Kinetic and Mechanism of the Addition of Benzylamines to α-Phenyl-β-thiophenylacrylonitriles in Acetonitrile

  • Hwang, Jae-young;Yang, Ki-yull;Koo, In-Sun;Sung, Dae-Dong;Lee, Ik-choon
    • Bulletin of the Korean Chemical Society
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    • v.27 no.5
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    • pp.733-738
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    • 2006
  • Nucleophilic addition reactions of p-substitutedbenzylamines $(XC _6H_4CH _2NH _2)$ to $\alpha$-phenyl-$\beta$-thiophenyl-acrylonitriles ($YC _4SH _2CH=C(CN)C_6H_4$Y') have been studied in acetonitrile at 25.0, 30.0, and 35.0 ${^{\circ}C}$. The reactions take place in single step in which the $C_\beta$ -N bond formation and proton transfer to $C_\alpha$ of $\alpha$-phenyl-$\beta$-thiophenylacrylonitriles occur concurrently with four-membered cyclic transition structure. These mechanistic conclusions are drawn based on (i) the large negative $\rho$x and large positive $\rho$Y' values and also large magnitude of $\rho$X, (ii) the negative sign and large magnitude of the cross-interaction constants ($\rho$XY), (iii) the normal kinetic isotope effects ($k_H/k_D$ > 1.0), and (iv) relatively low $\Delta H ^\neq$ and large negative $\Delta S ^\neq$ values.

Kinetics and Mechanism of the Addition of Anilines to β-Nitrostilbenes in Acetonitrile

  • Sung, Dae-Dong;Kang, Sang-Soo;Lee, Jong-Pal;Jung, Dae-Il;Ryu, Zoon-Ha;Lee, Ik-Choon
    • Bulletin of the Korean Chemical Society
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    • v.28 no.10
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    • pp.1670-1674
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    • 2007
  • Addition reactions of anilines (XC6H4NH2) to β-nitrostilbene (YC6H4CH=C(NO2)C6H4Y') have been investigated in acetonitrile at 30.0 oC. The magnitude of βX values (=0.11-0.34) indicates relatively earlier transition state for additions with anilines than with benzylamines. The signs of ρY and ρY' are positive with Δρ = ρY?ρY' = 0.04, demonstrating a TS imbalance with a negative charge development on the Cβ in the TS. The signs of cross-interaction constants ρXY (<0), ρXY' (<0) and ρYY' (>0) are consistent with bond forming and breaking processes. The relatively weak normal kinetic isotope effects involving deutarated nucleophiles, kH/kD>1, suggest an early, hydrogen-bonded, 4-member cyclic TS.

Chemical Reaction of Pentacene Growth on Hybrid Type Insulator by Annealing Temperature (하이브리드 타입 절연막 위에서 열처리 온도에 따른 펜타센 생성과 관련된 화학반응)

  • Oh Teresa
    • Journal of the Institute of Electronics Engineers of Korea SD
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    • v.43 no.2 s.344
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    • pp.13-17
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    • 2006
  • Pentacene channel for organic thin film transistor was deposited on the SiOC film by thermal evaporation. The growth of pentacene is related with the Diels-Alder reaction and the nucleophilic reaction by the thermal induction. The surface is an important factor to control the recursive Diels-Alder reaction for growing of pentacene on SiOC far The terminal C=C double bond of pentacene molecule was broken easily as a result of attack of the nucleophilic reagents on the surface of SiOC film. The nucleophilic reaction can be accelerated by increasing temperature on surface, and it maks pentacene to grow hardly on the SiOC film with a flow rate ratio of $O_2/(BTMSM+O_2)=0.5$ due to its inorganic property. The nucleophlic reaction mechanism is $SN_2(bimolecular nucleophilic substitution)$ type.

Sliding Wear Behavior of Plasma Sprayed Zirconia Coatingagainst Silicon Carbide Ceramic Ball

  • Le Thuong Hien;Chae Young-Hun;Kim Seock Sam;Kim Bupmin;Yoon Sang-bo
    • Proceedings of the Korean Society of Tribologists and Lubrication Engineers Conference
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    • 2004.11a
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    • pp.66-74
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    • 2004
  • The sliding wear behavior of $ZrO_2-22wt\%MgO\;(MZ)\;and\;ZrO_2-8wt\%Y_2O_3\;(YZ)$ deposited on a casting aluminum alloy with bond layer (NiCrCoAlY) by plasma spray against an SiC ball was investigated under dry test conditions at room temperature. At all load conditions, the wear mechanisms of the MZ and the YZ coatings were almost the same. The wear mechanisms involved the forming of a smooth film by material transferred on the sliding surface and pullout. The wear rate of the MZ coating was less than that of the YZ coating. With an increase normal load the wear rate of the studied coatings increased. The SEM was used to examine the sliding surfaces and elucidate likely wear mechanisms. The EDX analysis of the worn surface indicated that material transfer was occurred from the SiC ball to the disk. It was suggested that the material transfer played an important role in the wear performance.

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Reaction and Characterization of Silylene and its Precusor (Silylene과 Silylene 전구체의 반응 특성 연구)

  • Kong, Young Kun;Ahn, Young Man
    • Analytical Science and Technology
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    • v.7 no.3
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    • pp.321-327
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    • 1994
  • The mild thermal decomposition of 7, 7-dimethyl-1, 2, 3, 4, 5-pentaphenyl-7-silanorbornadiene with excess methyl alcohol proceeds to give 1-methoxydimethylsilyl-1, 2, 3, 4, 6-pentaphenylcyclohexa-2, 5-diene which is colorless needle crystal. The cophotolysis of the solution of 7-silanorbornadiene in the excess ethyl alcohol proceeds with loss of silylenes to give ethoxydimethylsilane which is insertion reaction product of silylene with O-H bond of ethyl alcohol. According to above results, it is presumed that the mechanism of photochemical decomposition and that of mild thermochemical decomposition of 7-silanorbornadiene are different.

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