• Journal of the Korean Society of Safety
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• v.5 no.2
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• pp.17-23
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• 1990

This study was performed by experiments with ASTM's apparatus for determination of autoignition temperature to obtain autoignition characteristics of 1-Heptene, 2-Heptene and 3-Heptene, respectively. As results, minimum autoignition temperatures (MAIT) of 1-Heptene, 2-Heptene and 3-Heptene were 246$^{\circ}C$, 248$^{\circ}C$ and 254$^{\circ}C$, respectively and each dropping volume of these temperatures was 0.25$m\ell$, 0.20$m\ell$ and 0.20$m\ell$. Instantaneous ignition temperatures measured at each dropping volume of Heptene were 371$^{\circ}C$, 357$^{\circ}C$ and 342$^{\circ}C$, respectively. Relation ignition delay time with ignition temperature at minimum autoignition temperature agreed well with Semenov's equation, and the values of apparent activation energy from this equation were 47Kca1/mo1 for 1-Heptene, 35Kca1/mo1 for 2-Heptene and 29Kca1/mo1 for 3-Heptene. It was found that the values of apparent activation energy decreased as the position of double bond changed from end to center in C-C chain.

• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.221-224
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• 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.

• Bulletin of the Korean Chemical Society
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• v.9 no.3
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• pp.179-182
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• 1988

A simple correlation between cross interaction constants ${\rho}_{ij}$ and bond lengths in the transition state was obtained ; it has been shown that ${\rho}_{ij}$ corresponds to force constant of activation, which in turn is related to bond length by Badger's rule involving only universal constants. A satisfactory correlation between 4-31G ab initio calculated values of bond length and force constant for C-X streching in the transition state of the methyl transfer reaction, $X^-\;+\;CH_3X\;=\;XCH_3\;+\;X^-$, indicated that Badger's rule can be extended to bonds in the transition state. Independence of ${\rho}_{ij}$ values from the variable charge transmission of reaction centers has been demonstrated with nearly constant, experimentally determined I${\rho}$XYI values, and hence similar degree of bond formation, for various $S_N2$ reactions.

• Molecules and Cells
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• v.44 no.10
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• pp.758-769
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• 2021

Calcium homeostasis modulator 1 (CALHM1) is a membrane protein with four transmembrane helices that form an octameric ion channel with voltage-dependent activation. There are four conserved cysteine (Cys) residues in the extracellular domain that form two intramolecular disulfide bonds. We investigated the roles of C42-C127 and C44-C161 in human CALHM1 channel biogenesis and the ionic current (I_CALHM1). Replacing Cys with Ser or Ala abolished the membrane trafficking as well as I_CALHM1. Immunoblotting analysis revealed dithiothreitol-sensitive multimeric CALHM1, which was markedly reduced in C44S and C161S, but preserved in C42S and C127S. The mixed expression of C42S and wild-type did not show a dominant-negative effect. While the heteromeric assembly of CALHM1 and CALHM3 formed active ion channels, the co-expression of C42S and CALHM3 did not produce functional channels. Despite the critical structural role of the extracellular cysteine residues, a treatment with the membrane-impermeable reducing agent tris(2-carboxyethyl) phosphine (TCEP, 2 mM) did not affect I_CALHM1 for up to 30 min. Interestingly, incubation with TCEP (2 mM) for 2-6 h reduced both I_CALHM1 and the surface expression of CALHM1 in a time-dependent manner. We propose that the intramolecular disulfide bonds are essential for folding, oligomerization, trafficking and maintenance of CALHM1 in the plasma membrane, but dispensable for the voltage-dependent activation once expressed on the plasma membrane.

• Journal of Integrative Natural Science
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• v.10 no.4
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• pp.175-191
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• 2017

In organic chemistry amide synthesis is performed through condensation of a carboxylic acid and an amine with releasing one equivalent of water via the corresponding ammonium carboxylate salt. This method is suffering from tedious processes and poor atom-economy due to the adverse thermodynamics of the equilibrium and the high activation barrier for direct coupling of a carboxylic acid and an amine. Most of the chemical approaches to amides formations have been therefore being developed, they are mainly focused on secondary amides. Direct carbonylations of tertiary amines to amides have been an exotic field unresolved, in particular direct carbonylation of trimethylamine in lack of commercial need has been attracted much interests due to the versatile product of N,N-dimethylacetamide in chemical industries and the activation of robust N-C($sp^3$) bond in tertiary amine academically. This review is focused mainly on carbonylation of trimethylamine as one of the typical tertiary amines by transition metals of cobalt, rhodium, platinum, and palladium including the role of methyl iodide as a promoter, the intermediate formation of acyl iodide, the coordination ability of trimethylamine to transition metal catalysts, and any possibility of CO insertion into the bond of Me-N in trimethylamine. In addition reactions of acyl halides as an activated form of acetic acid with amines are reviewed in brief since acyl iodide is suggested as a critical intermediate in those carbonylations of trimethylamine.

• Journal of Radiopharmaceuticals and Molecular Probes
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• v.4 no.1
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• pp.16-21
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• 2018

Organoboron compounds and their derivatives are synthetically versatile building blocks because they are readily available, stable, and highly useful for potential organic transformations. Arylboronic esters are of particular interest due to their well-established synthetic methods: transition metal catalyzed borylations of aryl halides. However, the use of aryl halides as an electrophile has one serious disadvantage: formation of toxic halogenated byproducts. A promising alternative substrate to aryl halides would be phenol derivatives such as aryl ethers, esters, carbamates and sulfonates. The phenol derivatives involve several advantages: their abundance, relatively low toxicity and versatile synthetic application. However, utilization of the aryl methyl ether, which is one of the simplest phenol derivatives, remains as a challenge, as C-OMe bond activation requires high activation energy and methoxides are not good leaving groups. Nevertheless, there have been a significant recent progress on ipso-borylation of aryl methyl ether including Martin's nickel catalysis. Here, we review the current advance on the borylation of carbon-oxygen bonds of unactivated C-OMe bond in aromatic compounds.

• Bulletin of the Korean Chemical Society
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• v.34 no.11
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• pp.3218-3222
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• 2013

The aminolyses, anilinolysis and pyridinolysis, of bis(2-oxo-3-oxazolidinyl) phosphinic chloride (1) have been kinetically investigated in acetonitrile at 55.0 and $35.0^{\circ}C$, respectively. For the reactions of 1 with substituted anilines and deuterated anilines, a concerted SN2 mechanism is proposed based on the selectivity parameters and activation parameters. The deuterium kinetic isotope effects ($k_H/k_D$) invariably increase from secondary inverse to primary normal as the aniline becomes more basic, rationalized by the transition state variation from a backside to a frontside attack. For the pyridinolysis of 1, the authors propose a stepwise mechanism with a rate-limiting step change from bond breaking for more basic pyridines to bond formation for less basic pyridines based on the selectivity parameters and activation parameters. Biphasic concave upward free energy relationship with X is ascribed to a change in the attacking direction of the nucleophile from a frontside attack with more basic pyridines to a backside attack with less basic pyridines.

• The Journal of Advanced Prosthodontics
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• v.8 no.2
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• pp.94-100
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• 2016

PURPOSE. To evaluate the effects of hydrogen peroxide pretreatment and heat activation of silane on the shear bond strength of fiber-reinforced composite posts to resin cement. MATERIALS AND METHODS. The specimens were prepared to evaluate the bond strength of epoxy resin-based fiber posts (D.T. Light-Post) to dual-curing resin cement (RelyX U200). The specimens were divided into four groups (n=18) according to different surface treatments: group 1, no treatment; group 2, silanization; group 3, silanization after hydrogen peroxide etching; group 4, silanization with warm drying at $80^{\circ}C$ after hydrogen peroxide etching. After storage of the specimens in distilled water at $37^{\circ}C$ for 24 hours, the shear bond strength (in MPa) between the fiber post and resin cement was measured using a universal testing machine. The fractured surface of the fiber post was examined using scanning electron microscopy. Data were analyzed using one-way ANOVA and post-hoc analysis with Tukey's HSD test (${\alpha}=0.05$). RESULTS. Silanization of the fiber post (Group 2) significantly increased the bond strength in comparison with the non treated control (Group 1) (P<.05). Heat drying after silanization also significantly increased the bond strength (Group 3 and 4) (P<.05). However, no effect was determined for hydrogen peroxide etching before applying silane agent (Group 2 and 3) (P>.05). CONCLUSION. Fiber post silanization and subsequent heat treatment ($80^{\circ}C$) with warm air blower can be beneficial in clinical post cementation. However, hydrogen peroxide etching prior to silanization was not effective in this study.

• Korean Journal of Materials Research
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• v.10 no.9
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• pp.593-600
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• 2000

This paper investigated the conduction path and conduction mechanism in undoped polycrystalline diamond thin films deposited by microwave chemical vapor deposition. The resistances measured by ac impedance spectroscopy with different directions can not be explained by the previously-known surface conduction model. The electrodeposition of Cu and electroetching of Ag experiments showed that the conduction path is the grain boundaries within the diamond films. The electodeposition of Cu with an insulating surface layer further proved that the main conduction path in polycrystalline films in the grain boundaries. The film with high electrical conductivity has low activation energy of 45meV and higher dangling bond density. By considering the results and surface C chemical bonds, the H-C-C-H bonds at surface and in grain boundaries might be the origin of high conductivity in undoped diamond films.

• Bulletin of the Korean Chemical Society
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• v.31 no.4
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• pp.953-958
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• 2010

A laser ablation-molecular beam/reflectron time-of-flight mass spectrometric technique was used to investigate the ion-molecule reactions that proceed within $Ti^+(CH_3COCH_3)_n$ heterocluster ions. The reactions of $Ti^+$ with $CH_3COCH_3$ clusters were found to be dominated exclusively by an oxidation reaction, which produced $TiO^+(CH_3COCH_3)_n$ clusters. These ions were attributed to the insertion of a $Ti^+$ ion into the C=O bond of the acetone molecule within the heteroclusters, followed by $C_3H_6$ elimination. The mass spectra also indicated the formation of minor sequences of heterocluster ions with the formulas $Ti^+(C_3H_4O)(CH_3COCH_3)_n$ and $TiO^+(OH)(CH_3COCH_3)_n$, which could be attributed to C-H bond insertion followed by $H_2$ elimination and to the sequential OH abstraction by the $TiO^+$ ion, respectively. Density functional theory calculations were carried out to model the structures and binding energies of both the association complexes and the relevant reaction products. The reaction pathways and energetics of the $TiO^+\;+\;CH_2CHCH_3$ product channel are presented.