• 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.

• Bulletin of the Korean Chemical Society
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• v.27 no.10
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• pp.1641-1647
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• 2006

Vibrational relaxation and competitive C-$H_{methyl}$ and C-$H_{ring}$ bond dissociations in vibrationally excited methylpyrazine in the collision with HF have been studied by use of classical trajectory procedures. The energy lost by the vibrationally excited methylpyrazine 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. The temperature dependence of energy loss is negligible between 200 and 400 K, but above 45,000 $cm^{-1}$ the energy loss increases as the temperature is raised. Energy transfer to or from the excited methyl C-H bond occurs in strong collisions with HF, that is, relatively large amount of translational energy is transferred in a single step. On the other hand, energy transfer to the ring C-H bond occurs in a series of small steps. When the total energy content ET of methylpyrazine is sufficiently high, either or both C-H bonds 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 direct intermolecular energy flow from the direct collision between the ring C-H and HF but the result of the intramolecular flow of energy from the methyl group to the ring C-H stretch.

• Bulletin of the Korean Chemical Society
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• v.30 no.5
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• pp.1164-1166
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• 2009

Aromatic aldehydes are efficiently self-condensed into $\alpha$-hydroxy carbonyl compounds by polystyrene-supported ammonium cyanide as an excellent organocatalyst in C-C bond formation. The reaction proceeds in water under mild reaction conditions. The polymeric catalyst can be easily separated by filtration and reused several times without appreciable loss of activity.

• Bulletin of the Korean Chemical Society
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• v.17 no.9
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• pp.826-830
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• 1996

Fourier transform infrared (FTIR) temperature studies were performed to examine the microstructural changes that occur in annealing process of the thin films of 1,2-polybutadiene (1,2-PBu)/palladium chloride (PdCl2) complex. The disappearance of the infrared absorption intensities at 1640, 1418, 994 and 910 cm-1 signifies the consumption of 1,2-vinyl groups of 1,2-PBu. The progressive loss of unsaturation and production of methyl groups as a function of temperature were identified by the enhanced infrared absorption intensities at 1447 and 1375 cm-1. The loss of pendent carbon-carbon double bond is considered to involve both palladium-catalyzed addition reaction and thermally induced cyclization.

• Steel and Composite Structures
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• v.13 no.6
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• pp.571-586
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• 2012

The paper addresses some key issues related to the design of composite slabs with cold-formed profiled steel sheets. An experimental programme is first presented, involving six composite slab specimens tested with a view to evaluating Eurocode 4 (EC4) provisions on testing of composite slabs. In four specimens, the EC4-prescribed 5000 load cycles were applied using different load ranges resulting from alternative interpretations of the reference load $W_t$. Although the rationale of the application of cyclic loading is to induce loss of chemical bond between the concrete plate and the steel sheet, no such loss was noted in the tests for either interpretation of the range of load cycles. Using the recorded response of the specimens the values of factors m and k (related to interface shear transfer in the composite slab) were determined for the specific steel sheet used in the tests, on the basis of three alternative interpretations of the related EC4 provisions. The test results confirmed the need for a more unambiguous description of the m-k test and its interpretation in a future edition of the Code, as well as for an increase in the load amplitude range to be used in the cyclic loading tests, to make sure that the intended loss of bond between the concrete slab and the steel sheet is actually reached. The study also included the development of a special-purpose software that facilitates design of composite slabs; a parametric investigation of the importance of m-k values in slab design is presented in the last part of the paper.

• Bulletin of the Korean Chemical Society
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• v.32 no.7
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• pp.2301-2305
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• 2011

The potential energy surface (PES) for the loss of HCN or HNC from the pyrazine molecular ion was determined based on quantum chemical calculations using the G3//B3LYP method. Four possible dissociation pathways to form four $C_3H_3N^{+{{\bullet}}$ isomers were examined. A Rice-Ramsperger-Kassel-Marcus quasi-equilibrium theory model calculation was performed to predict the dissociation rate constant and the product branching ratio on the basis of the obtained PES. The resultant rate constant for the HCN loss agreed with the previous experimental result. The kinetic analysis predicted that the formation of $CH=CHN{\equiv}CH^{+{\bullet}}+HCN$ was predominant, which occurred by three consecutive steps, a C-C bond cleavage to form a linear intermediate, a rearrangement to form an H-bridged intermediate, and elimination of HCN.

• Bulletin of the Korean Chemical Society
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• v.31 no.9
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• pp.2588-2592
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• 2010

The potential energy surfaces (PESs) for the primary and secondary dissociations of the phenylarsane molecular ion (1a) were determined from the quantum chemical calculations using the G3(MP2)//B3LYP method. Several pathways for the loss of $H{\cdot}$ were determined and occurred though rearrangements as well as through direct bond cleavages. The kinetic analysis based on the PES for the primary dissociation showed that the loss of $H_2$ was more favored than the loss of $H{\cdot}$, but the $H{\cdot}$. loss competed with the $H_2$ loss at high energies. The bicyclic isomer, 7-arsa-norcaradiene radical cation, was formed through the 1,2 shift of an $\alpha$-H of 1a and played an important role as an intermediate for the further rearrangements in the loss of $H{\cdot}$ and the losses of $As{\cdot}$ and AsH. The reaction pathways for the formation of the major products in the secondary dissociations of $[M-H]^+$ and $[M-H_2]^{+\cdot}$. were examined. The theoretical prediction explained the previous experimental results for the dissociation at high energies but not the dissociation at low energies.

• Journal of the Korean Chemical Society
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• v.67 no.6
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• pp.407-414
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• 2023

The present study uses quasi-classical trajectory procedures to examine the vibrational relaxation and dissociation of the methyl and ring C-H bonds in excited methylpyrazine (MP) during collision with either N₂ or O₂. The energy-loss (-ΔE) of the excited MP is calculated as the total vibrational energy (E_T) of MP is increased in the range of 5,000 to 40,000cm^-1. The results indicate that the collision-induced vibrational relaxation of MP is not large, increasing gradually with increasing E_T between 5,000 and 30,000 cm^-1, but then decreasing with the further increase in E_T. In both N₂ and O₂ collisions, the vibrational relaxation of MP occurs mainly via the vibration-to-translation (V→T) and vibration-to-vibration (V→V) energy transfer pathways, while the vibration-to-rotation (V→R) energy transfer pathway is negligible. In both collision systems, the V→T transfer shows a similar pattern and amount of energy loss in the ET range of 5,000 to 40,000cm^-1, whereas the pattern and amount of energy transfer via the V→V pathway differs significantly between two collision systems. The collision-induced dissociation of the C-H_methyl or C-H_ring bond occurs when highly excited MP (65,000-72,000 cm^-1) interacts with the ground-state N₂ or O₂. Here, the dissociation probability is low (10^-4-10^-1), but increases exponentially with increasing vibrational excitation. This can be interpreted as the intermolecular interaction below E_T = 71,000 cm^-1. By contrast, the bond dissociation above E_T = 71,000 cm^-1 is due to the intramolecular energy flow between the excited C-H bonds. The probability of C-H_methyl dissociation is higher than that of C-H_ring dissociation.

• Bulletin of the Korean Chemical Society
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• v.26 no.11
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• pp.1711-1716
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• 2005

Fragmentations and ion-molecule reactions of ionized cyclohexane propionic acid and cyclohexane butyric acid were studied using FTMS and theoretical calculations. The difference in bond dissociation depending on the aliphatic chain length was investigated and mechanisms for the possible rearrangements depending on the aliphatic carbon length were suggested. The most abundant fragment ion of the ionized cyclohexane propionic acid was c-$C_6H_{11}CH_2\;^+$ formed from the molecular ion by the direct C-C bond cleavage, while that of the ionized cyclohexane butyric acid was c-$C_6H_9C(OH)=OH^+$ formed by rearrangement of the molecular ion from the acid to diol form and loss of propyl radical. Stabilities of the radical and distonic ions of $C_nH_{2n}O^{+\bullet}$ formed from the molecular ion were compared. Protonated molecules were dissociated into smaller ions by losing one or two water molecules. The $[nM + H]^+$, $[nM + H - H_2O]^+$, and $[nM + H - 2H_2O]^+$ with n = 2 and 3 were generated by solvation with the neutral molecules in the ICR cell at long ion trapping time.

• Food Science and Biotechnology
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• v.15 no.3
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• pp.441-446
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• 2006

The biological effects of heating and chemical treatment on castor meal were investigated in order to develop a procedure to inactivate its antigenic activity in a way that is suitable for industrial applications. A 1% solution of purified castor bean allergen (CB-1A) was heat-treated with or without exposure to NaOH and NaOCI (250 ppm each). CB-1A exhibited extreme stability when heat-treated alone. In the presence of NaOH and NaOCl, CB-1A showed a drastic decrease in antigenic activity as the temperature surpassed the critical level of $70^{\circ}C$. The gradual disappearance of disc gel electrophoresis bands presumably responsible for the allergenicity of CB-1A, along with the significant losses of the amino acids phenylalanine, methionine, arginine, histidine, and cysteine correlated with the loss of CB-1A activity. CB-1A showed a single symmetrical band in SDS acrylamide gel electrophoresis with an estimated molecular weight of 6,000 daltons. The chemical and heat treatments reduced the disulfide bond content of CB-1A by 9.1% with a coincident increase in sulfhydryl bonds.