• Bulletin of the Korean Chemical Society
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• v.6 no.6
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• pp.362-366
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• 1985

The hydrogen atom transfer reaction between substituted methane, $CH_3X,$ and its radical, $CH_2X(X=H,F,CH_3,CN,OH\;and\;NH_2$ was studied by MINDO/3 method. The transition state(TS) structure and energy barriers were determined and variation of the transition state and of the reactivity due to the change of X were analyzed based on the potential energy surface characteristics. It was found that the greater the radical stabilization energy. the looser the TS becomes; the TS occurs at about 15% stretch of the C-H bond, which becomes longer as the radical stabilization energy of $CH_2X$ increasers. The intrinsic barrier, ${\Delta}E*_{x.x},$ of the reaction with X was found to increase in the order $H The degree of bond stretch of the C-H bond stretch of the C-H bond at the TS also had the same order indicating that the homolytic bond cleavage of the C-H bond is rate-determining. Orbital interactions at the TS between LUMO of the fragment $C{\ldots}H{\ldots}C$ and the symmetry adapted pair of nonbonding, $n{\pm}(=n_1{\pm}n_2),$ or pi orbitals of the two X atoms were shown to be the dominant contribution in determining tightness or looseness of the TS. The Marcus equation was shown to apply to the MINDO/3 barriers and energy changes of the reaction.

• Bulletin of the Korean Chemical Society
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• v.27 no.4
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• pp.495-502
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• 2006

Intramolecular energy flow and C-$H_{methyl}$ and C-$H_{ring}$ bond dissociations in vibrationally excited toluene in the collision with HF have been studied by use of classical trajectory procedures. The energy lost by the vibrationally excited toluene upon collision is not large and it increases slowly with increasing total vibrational energy content between 20,000 and 45,000 $cm ^{-1}$. Above the energy content of 45,000 $cm ^{-1}$, however, energy loss decreases. Furthermore, in the highly excited toluene, toluene gains energy from incident HF. The temperature dependence of energy loss is negligible between 200 and 400 K. Energy transfer to or from the excited methyl C-H bond occurs in strong collisions with HF transferring relatively large amount of its translational energy (>> $k_BT$) in a single step, whereas energy transfer to the ring C-H bond occurs in a series of small steps. When the total energy content $E_T$ of toluene is sufficiently high, either C-H bond can dissociate. The C-$H_{methyl}$ dissociation probability is higher than the C-$H_{ring}$ dissociation probability. The dissociation of the ring C-H bond is not the result of the intermolecular energy flow from the direct collision between the ring C-H and HF but the intramolecular flow of energy from the methyl group to the ring C-H stretch. The C-$H_{ring}$${\cdot}{\cdot}{\cdot}$HF interaction is not important in transferring energy and in turn bond dissociation.

• Journal of the Semiconductor & Display Technology
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• v.7 no.3
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• pp.1-4
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• 2008

The chemical shift of SiOC film was observed according to the flow rate ratio. SiOC film had the broad main band of $880\sim1190cm^{-1}$ and the sharp Si-$CH_3$ bond at $1252cm^{-1}$, and the peak position of the main bond in the infrared spectra moved to high frequency according to the increasing of an BTMSM flow rate. So the increment of the alkyl group induced the C-H bond condensation in the film, and shows the blueshift in the infrared spectra. In the case of P5000 system of Applied Materials Corporation, the strong bond of Si-CH3 bond in precursor does not enough to dissociated and ionized, because low plasma energy due to the capactive coupled CVD. Therefore, there was the sharp peak of Si-$CH_3$ bond at $1252cm^{-1}$.

• Journal of the Korean Chemical Society
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• v.38 no.10
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• pp.749-752
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• 1994

Two furanosesquiterpenes, (5'E)-5-(2',6'-dimethylocta-5',7'-dienyl) furan-3-carboxylic acid (1) and (1'E,5'E)-5-(2',6'-dimethylocta-l',5',7'-trienyl) furan-3-carboxylic acid (2), were isolated from soft coral Sinularia lochmodes collected from Palikir pass at Pohnpei Micronesia, June, 1990 in Hawaii. Their structures were elucidated by $^1H$, $^{13}C$ NMR, Homo-COSY, $^1H$-$^{13}C$ (1 bond) Heteronuclear Multiple Quantum Coherence Spectroscopy (HMQC), $^1H$-$^{13}C$ (2 and 3 bond) Heteronuclear Multiple Bond Coherence Spectroscopy (HMBC), Electron Impact Mass Spectroscopy (EI-ms), and Infrared Spectroscopy (IR).

• Journal of the Korean Chemical Society
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• v.32 no.4
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• pp.301-310
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• 1988

Reaction rates for mononuclear heterocyclic rearrangement of N-(5-phenyl-1,2,4-oxadiazol-3-yl)-N'-arylformamidines into 3-acylamino-1-aryl-1,2,4-triazoles were determined spectrophotometrically in dioxane/water (50 : 50, v/v). There are two different reaction paths according to pH. One is pH-independent path, the other is pH-dependent one. In pH-independent path, the result of substituent effect by IYT equation show that N-H bond breaking as well as new N-N bond formation controls the reaction rate. In pH-dependent path, concave-upward Hammett plot was observed. It can be concluded that new N-N bond formation is more advanced than N-H bond breaking in transition state for electron-donating substituents, but N-H bond breaking is more advanced than new N-N bond formation for electron-withdrawing substituents.

• Steel and Composite Structures
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• v.38 no.5
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• pp.563-582
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• 2021

The present study experimentally and analytically investigated the push-out behaviour of H-shaped steel section embedded in ultrahigh-performance fibre-reinforced concrete (UHPFRC). The effect of significant parameters such as the concrete types, fibre content, embedded steel length, transverse reinforcement ratio and concrete cover on the bond stress, development of bond stress along the embedded length and failure mechanism has been reported. The test results show that the bond slip behaviour of steel-UHPFRC is different from the bond slip behaviour of steel-normal concrete and steel-high strength concrete. The bond-slip curves of steel-normal concrete and steel-high strength concrete exhibit brittle behaviour, and the bond strength decreases rapidly after reaching the peak load, with a residual bond strength of approximately one-half of the peak bond strength. The bond-slip curves of steel-UHPFRC show an obvious ductility, which exhibits a unique displacement pseudoplastic effect. The residual bond strength can still reach from 80% to 90% of the peak bond strength. Compared to steel-normal concrete, the transverse confinement of stirrups has a limited effect on the bond strength in the steel-UHPFRC substrate, but a higher stirrup ratio can improve cracking resistance. The experimental campaign quantifies the local bond stress development and finds that the strain distribution in steel follows an exponential rule along the steel embedded length. Based on the theory of mean bond and local bond stress, the present study proposes empirical approaches to predict the ultimate and residual bond resistance with satisfactory precision. The research findings serve to explain the interface bond mechanism between UHPFRC and steel, which is significant for the design of steel-UHPFRC composite structures and verify the feasibility of eliminating longitudinal rebars and stirrups by using UHPFRC in composite columns.

• Proceedings of the IEEK Conference
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• 2008.06a
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• pp.487-488
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• 2008

SiOC films containing alkyl groups have a low dielectric constant because of the interaction between the C-H hydrogen bonds and the oxygen of high electro-negative atom. The Si-$CH_3$ in a void is broken by the $O_2$, therefore the strength of CH bond in Si-O-O-$CH_3$ bond increases. The Si-O-O-$CH_3$ bond is broken by nucleophilic attack due to Si atom, again. The elongation of C-H bond causes the red shift, and the compression of C-H bond causes the blue shift. Among these chemical shifts, the blue shift from $1000\;cm^{-1}$ to $1250\;cm^{-1}$ was related with the formation of pores. If the oxygen is deficient condition, the methylradicals of the electron-rich substitution group terminate easily the Si-O-Si cross-link, and the pore is originated from the cross-link breakdown due to much methyl radicals of Si-$CH_3$. The dielectric constant of the films decreases due to pore generation.

• Restorative Dentistry and Endodontics
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• v.39 no.4
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• pp.303-309
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• 2014

Objectives: Hydrogen peroxide ($H_2O_2$) surface treatment of fiber posts has been reported to increase bond strength of fiber posts to resin cements. However, residual oxygen radicals might jeopardize the bonding procedure. This study examined the effect of three antioxidant agents on the bond strength of fiber posts to conventional and self-adhesive resin cements. Materials and Methods: Post spaces were prepared in forty human maxillary second premolars. Posts were divided into five groups of 8 each: G1 (control), no pre-treatment; G2, 10% $H_2O_2$ pre-treatment; G3, G4 and G5. After $H_2O_2$ application, Hesperidin (HES), Sodium Ascorbate (SA) or Rosmarinic acid (RA) was applied on each group respectively. In each group four posts were cemented with Duo-Link conventional resin cement and the others with self-adhesive BisCem cement. Push-out test was performed and data were analyzed using 2-way ANOVA and tukey's post-hoc test (${\alpha}=0.05$). Results: There was a statistically significant interaction between the cement type and post surface treatment on push-out bond strength of fiber posts (p < 0.001, F = 16). Also it was shown that different posts' surface treatments significantly affect the push-out bond strength of fiber posts (p = 0.001). $H_2O_2$ treated posts (G2) and control posts (G1) cemented with Duo-link showed the highest ($15.96{\pm}5.07MPa$) and lowest bond strengths ($6.79{\pm}3.94$) respectively. Conclusions: It was concluded that $H_2O_2$ surface treatment might enhance the bond strength of fiber posts cemented with conventional resin cements. The effect of antioxidants as post's surface treatment agents depends on the characteristics of resin cements used for bonding procedure.

• Restorative Dentistry and Endodontics
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• v.48 no.2
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• pp.14.1-14.11
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• 2023

Objectives: This study investigated the effect of an aluminum chloride hemostatic agent on the shear bond strength (SBS) of a universal adhesive to dentin. Materials and Methods: Eighty extracted human molars were trimmed at the occlusal dentin surfaces and divided mesiodistally. According to hemostatic agent application, specimens were randomly allocated into control (C) and hemostatic agent (Traxodent; H) groups. Each group was divided into 4 subgroups according to the adhesive system (n = 20): Scotchbond Multi-Purpose (SBER), Clearfil SE Bond (CLSE), All-Bond Universal etch-and-rinse mode (ALER), and All-Bond Universal self-etch mode (ALSE). SBS was measured for half of the specimens at 24 hours, and the other half were thermocycled in water baths (group T). Fracture surfaces were examined to determine the failure mode. The SBS was measured, and data were analyzed using 1-way analysis of variance, the Student's t-test, and the Tukey honestly significant difference test (p = 0.05). Results: No significant differences in SBS were found between groups C and H for any adhesive system at 24 hours. After thermocycling, a statistically significant difference was observed between CT+ALSE and HT+ALSE (p < 0.05). When All-Bond Universal was applied to hemostatic agent-contaminated dentin, the SBS of H+ALSE was significantly lower than that of H+ALER (p < 0.05). The SBER subgroups showed no significant differences in SBS regardless of treatment and thermocycling. Conclusions: When exposed dentin was contaminated by an aluminum chloride hemostatic agent before dentin adhesive treatment, application of All-Bond Universal in etch-and-rinse mode was superior to self-etch mode.

• Bulletin of the Korean Chemical Society
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• v.23 no.12
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• pp.1811-1815
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• 2002

We have calculated energies and structures for the hydrogen bonded clusters between trimethyl phosphate and nitric acids. The hydrogen bond lengths between phosphoryl oxygen and the proton of nitric acid are short compared to normal hydrogen bonds, and the H-bond strengths are fairly strong. The hydrogen bond length becomes longer, and the strength becomes weaker, as more nitric acids are bound to the TMP. The average H-bond strengths for the $TMP-(HNO_3)_n$ complexes with n = 1, 2, and 3, are 9.6, 7.9 and 6.4kcal/mol at 300K respectively. Weak hydrogen bonds between nitrate oxygen and methyl proton might contribute to the stability of the clusters. Not only the BSSE but also the fragment relaxation energies should be considered to calculate hydrogen bond strengths for the complexes accurately.