• JSTS:Journal of Semiconductor Technology and Science
• /
• v.1 no.4
• /
• pp.197-201
• /
• 2001

The influence of argon, oxygen, and nitrogen admixtures on the dissociation of $Cl_2$ molecules in a glow discharge low-temperature plasma under the constant pressure conditions was investigated. For $Cl_2/Ar$ and $Cl_2/O_2$mixtures, the concentration of chlorine atoms was observed to be a practically constant at argon or oxygen concentrations up to 50%. This invariability is a most pro bably explained by relative increase in rate of $Cl_2$ direct electron impact dissociation due to the changes in electrophysical parameters of plasma such as EEDF, electron drift rate and mean energy. For all the considered mixtures, the contribution of stepwise dissociation involving active species from gas additives (metastable atoms and molecules, vibrationally excited molecules) was found to be negligible.

• Molecules and Cells
• /
• v.24 no.1
• /
• pp.119-124
• /
• 2007

TLR4 together with CD14 and MD-2 forms a pattern recognition receptor that plays an initiating role in the innate immune response to Gram-negative bacteria. Here, we employed the surface plasmon resonance technique to investigate the kinetics of binding of LPS to recombinant CD14, MD-2 and TLR4 proteins produced in insect cells. The dissociation constants ($K_D$) of LPS for immobilized CD14 and MD-2 were $8.7{\mu}m$, and $2.3{\mu}m$, respectively. The association rate constant ($K_{on}$) of LPS for MD-2 was $5.61{\times}10^3M^{-1}S^{-1}$, and the dissociation rate constant ($K_{off}$) was $1.28{\times}10^2S^{-1}$, revealing slow association and fast dissociation with an affinity constant $K_D$ of $2.33{\times}10^6M$ at $25^{\circ}C$. These affinities are consistent with the current view that CD14 conveys LPS to the TLR4/MD-2 complex.

• Bulletin of the Korean Chemical Society
• /
• v.32 no.7
• /
• pp.2301-2305
• /
• 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
• /
• v.24 no.6
• /
• pp.763-770
• /
• 2003

The $BH_5$ molecule, which is suggested as an intermediate of the acidolysis of $BH_4^-$, contains a weak two-electron-three-center bond and it requires extremely high-level of theories to calculate the energy and structure correctly. The structures and energies of $BH_5$ and the transition state for the hydrogen scrambling have been studied using recently developed multi-coefficient correlated quantum mechanical methods (MCCMs). The dissociation energies and the barrier heights agree very well with the previous results at the CCSD(T)/ TZ(3d1f1g, 2p1d) level. We have also calculated the potential energy curves for the dissociation of $BH_5$ to $BH_3$ and $H_2$. The lower levels of theory were unable to plot correct potential curves, whereas the MCCM methods give very good potential energy curves and requires much less computing resources than the CCSD(T)/ TZ(3d1f1g,2p1d) level. The potential energy of the $BH_5$ scrambling has been obtained by the multiconfiguration molecular mechanics algorithm (MCMM), and the rates are calculated using the variational transition state theory including multidimensional tunneling approximation. The rate constant at 300 K is 2.1 × $10^9s^{-1}$, and tunneling is very important.

• KSBB Journal
• /
• v.11 no.2
• /
• pp.225-237
• /
• 1996

Intrinsic binding kinetics of of 125I-bovine serum albumin (125I-BSA) and immobilized monoclonal anti-BSA (MAb 9.1) were studied. Small non-porous polystyrene beads (0.5${\mu}$m diameter) were used as a solid support to minimize the mass transfer interference on rate measurements. We demonstrated both theoretically and experimentally that the binding reaction is kinetically controlled. Rate measurements show that the association reaction is of second order and the dissociation reaction is of first order. Between 4 and $37^{\circ}C$ the measured equilibrium constant agrees well with the equilibrium constant calculated from the rate measurements. The temperature effects on association are much greater than on dissociation; the activation energy for association is about 9Kca1/mole, as compared to 2Kca1/mole for dissociation. The use of small non-porous beads as a solid support in binding studies essentially avoids mass transfer limitations; such a system makes it possible to determine the intrinsic binding characteristics of any immobilized antibody on a solid surface.

• Bulletin of the Korean Chemical Society
• /
• v.33 no.12
• /
• pp.4098-4102
• /
• 2012

The potential energy surface (PES) for the loss of HCN from the pyrimidine molecular ion has been explored using quantum chemical calculations. Possible reaction pathways to form five $C_3H_3N^{+{\bullet}}$ isomers have been obtained with Gaussian 4 model calculations. The rate constant for the HCN loss and the product branching ratio have been calculated using the Rice-Ramsperger-Kassel-Marcus theory on the basis of the obtained PES. The resultant rate constant agrees with the previous experimental result. By a kinetic analysis, it is proposed that the formation of $CH=CHC{\equiv}NH^{+{\bullet}}$ is favored near the dissociation threshold, while the formation of $CH=CHN{\equiv}CH^{+{\bullet}}$ is favored at high energies.

• YAKHAK HOEJI
• /
• v.32 no.2
• /
• pp.101-111
• /
• 1988

$[^3H]$ Quinuclidinyl benzilate(QNB) binding assays were performed in the dog ventricular sarcolemma fraction enriched approx. 32-fold in sarcolemma compared to the starting homogenate to elucidate the effect of antihistaminics on cardiac muscarinic receptor. Chlorpheniramine(CHP) inhibited specific binding of $[^3H]$QNB and delayed the equilibrium binding. The rate constants at $37^{\circ}C$ for formation and dissociation of the QNB receptor complex were $0.38{\times}10^9\;M^{-1}$ and $1.6{\times}10^{-2}\;min^{-1}$, respectively. The mean value for the dissociation constant from the pairs of the rate constants was 43. 2 pM and this value was similar to the value(44.8pM) determined from Scatchard analysis. CHP decreased association rate constant, indicating increase in $K_D$ value. Decrease in affinity without affecting the binding site concentration$(B_{max})$ for $[^3H]$QNB binding by CHP was also demonstrated by Scatchard analysis. $K_i$ values for $H_i$-blockers that inhibited specific $[^3H]$QNB binding were $0.02{\sim}4.8{\mu}M$. Cimetidine with $K_i$ value of $230{\mu}M$, however, was ineffective in displacing $[^3H]$QNB binding at concentration of $50{\mu}M$. The Hill coefficient for $H_1$-blockers were about one. The results indicate that $H_1$-antihistaminics inhibit $[^3H]$ QNB binding by interaction with myocardiac muscarinic cholinergic receptor and anticholinergic side effects of these drugs are mainly due to this receptor blocking mechanism.

• Journal of the Korean Chemical Society
• /
• v.24 no.1
• /
• pp.44-52
• /
• 1980

Ionic dissociation rates of $\alpha$-chlorobenzyl ethyl ether in each solvent of toluene-$d_8$ and carbon tetrachloride were measured by the method of dynamic NMR spectroscopy. The spin system of these 1H NMR spectra was $AB_3$. The theoretical spectrum was calculated by computer simulation of dynamic NMR spectra, which agreed very well with observed spectra. From this computer simulation, the ionic dissociation rate constant k was obtained, and by Eyring plot with it, slope and intercept length was gained, from which kinetic parameters were calculated.The easiness of ionic dissociation depended upon solvent polarity. Activation enthalpy was 4.7 kcal/mole in toluene-$d_8$, 10.7 kcal/mole in carbon tetrachloride, and activation entropy was -35. 8 e.u. in toluene-$d_8$, -14.4 e.u. in carbon tetrachloride. It was understood that though the ${\Delta}H^{neq}$ value was small, this ionic dissociation had an easier procession in nonpolar solvents with increasing temperatures. Considering that the ionic dissociation could be thought as the first step of $S_N1$ mechanism, attention might be paid to the results that the value of ${\Delta}S^{neq}$ had a large negative value in comparison with a small ${\Delta}H^{neq}$.

• BMB Reports
• /
• v.29 no.4
• /
• pp.286-293
• /
• 1996

Association of antigenic peptide with class I MHC is believed to be crucial for maintaining stable conformation of class I molecules. T2 cells that are defective in TAP gene function mainly express class I molecules with an unstable conformation due to little or no association with antigenic peptides, whereas T1 cells that are normal in TAP gene function mainly express the stable form of class I molecules. In this work, attempts were made to determine the molecular stability of stable and unstable class I molecules. Dissociation of HLA-A2 molecules on T1 and T2 cells was monitored by flow cytometry using anti-HLA-A2 antibody after the cells were treated with brefeldin A to shut down the transport of newly-assembled HLA-A2. Estimated dissociation rate constants for the stable and unstable forms of HLA-A2 were 0.076 $h^{-1}$ and 0.66 $h^{-1}$, respectively. It appeared that both T1 and T2 cells express stable and unstable class I complex, but with different ratios of the two forms. Furthermore, $interferon-{\gamma}$ treatment of T1 cells appeared to induce the expression of both the stable and unstable class I molecules. These results demonstrate that class I MHC molecules can be divided into two groups in terms of structural stability and that they exist on the cell surface in both forms in a certain ratio.

• Journal of the Korean Vacuum Society
• /
• v.7 no.s1
• /
• pp.20-24
• /
• 1998

Photploymer films are widely used in printing and electronic industries, and their usage is expanding to encompass holography, data storage and data processing, optical waveguides and compact disks, etc. One of widely used photoplymerization initiator, 20chloro-hexaarylbiimidazole (o-Cl-HABI), is studied by laser flash photolysis in dichloromethane solution in the absence and presence of the visible light photosensitizing dye, 2, 5-bis[(2, 3, 6, 7 -tetrahydro- 1H, 5H -benzo [i, j,] quinolizin -1-yl) methylene]-cyclopenta-none, (JAW). In the presence of JAW, an increase in triarylimidazolyl radicals L.formation is observed in relative to the absence of JAW. The mechanism of this photosensitizing dissociation is concluded as the dissociation of the o-Cl-HABI radical anion formed by the electron transfer from excited singlet state of JAW to o-Cl-HABI. The observed formation of L.radicals exhibits a linear dependence on o-Cl-HABI concentration. The rate constant of electron transfer obtained from this dependence is equal to (1.0$\pm$0.2) x $10^9 M^{-1}s^{-1}$. No reaction between the excited triplet state of JAW and o-Cl-HABI is found.