• Bulletin of the Korean Chemical Society
• /
• v.1 no.3
• /
• pp.105-109
• /
• 1980

A general spectroscopic method is described for studies on the complex formation between metal ions and ligands, and is applied to $Cu^{2+}$ and $Ca^{2+}$binding to glycosaminoglycans. The order of binding constants for both ions is heparin >dermatan sulfate >chondroitin sulfate. The electrostatic forces are shown to be the predominant factor in the interaction. The 2- to 3-fold higher affinity for $Cu^{2+}$ than for $Ca^{2+}$ is obtained for heparin and dermatan sulfate, but little difference for chondroitin sulfate. These results are explained as chelation of both carboxyl and sulfate groups to $Cu^{2+}$ in former cases. The difference of binding constants among glycosaminoglycans is related to proposed various biological functions of the biopolymers.

• Bulletin of the Korean Chemical Society
• /
• v.18 no.9
• /
• pp.1010-1013
• /
• 1997

Nucleophilic substitution reactions of (Z)-phenylethyl (X)-benzenesulfonates with (Y)-pyridines were investigated in acetonitrile at 60 ℃ under respective pressures. The magnitudes of the Hammett reaction constants, ρX, ρY and ρZ indicate that a stronger nucleophile leads to a greater degree of bond formation of C-N and a better leaving group is accompanied by a less degree of bond breaking. The magnitude of correlation interaction term, ρij can be used to determine the structure of the transition state (TS) for the SN reaction. As the pressure is increased, the Hammett reaction constants, ρX and |ρY|, are decreased, but correlation interaction coefficient, ρXZ and |ρYZ|, are increased. The results indicate that the reaction of (Z)-phenylethyl (X)-benzenesulfonates with (Y)-pyridines probably moves from a dissociative SN2 to early-type concerted SN2 mechanism by increasing pressure. This result shows that the correlation interaction term ρij can be useful tool to determine the structure of TS, and also the sign of the product ρXZ·ρYZ can be predict the movement of the TS.

• Bulletin of the Korean Chemical Society
• /
• v.18 no.11
• /
• pp.1179-1182
• /
• 1997

The rates for the reaction of (Z)-phenacyl (X)-benzenesulfonates with (Y)-pyridines in acetone were measured by an electrical conductivity method at 1-2000 bars and 45 ℃. The magnitudes of the Hammett reaction constants, ρX, ρY and ρZ, represent the degree of Nu-C bond formation and that of C-L bond breaking. The magnitude of correlation interaction term ρij can be used to determine the structure of the transition state (TS) for the SN reaction. As the pressure is increased, the Hammett reaction constants, ρX, |ρY| and ρZ are increased, but correlation interaction coefficient, |ρXZ| and ρYZ, are decreased. The results indicate that the reaction of (Z)-phenacyl (X)-benzenesulfonates with (Y)-pyridines probably moves from an associative SN2 to late-type SN2 mechanism by increasing pressure.

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

• Transactions of the Korean Society of Mechanical Engineers B
• /
• v.33 no.6
• /
• pp.411-417
• /
• 2009

The transient shear stress response of an electrorheological fluid is investigated experimentally. The characteristic time constants of an electrorheological fluid sheared between two concentric cylinders were obtained under various electric field strengths and shear rates. Also, two experimental modes are adopted to investigate the effect of the shear flow on the dynamic behavior of the fluid; one is that the electric field is induced before shearing, and the other is the electric field is induced after shearing. From the difference in the response time between two modes, the cluster formation time were obtained. The response times were decreased with the increase of the shear rate, irrelatively of the electric field strength. The cluster formation time were monotonically increased with increase of shear rate, and thereafter, were converged with a certain value.

• Journal of the Korean Society of Food Science and Nutrition
• /
• v.13 no.1
• /
• pp.51-56
• /
• 1984

A red pigment was formed when heating dehydroascorbic acid in the presence of ${\alpha}-amino$ acids and thought to be an intermediate amino-reductone in the Strecker degradation. The reaction of pigment formation can be kinetically expressed as two-step consecutive first-order in the presence of excess of ${\alpha}-amino$ acids. The reaction rate constants were successfully determined by employing various amino acids (L-His., L-Gly., L-Thr., L-Ser. ) at different pH. The results suggested the formation of the red pigment was most favorable at the pH 5.0.

• Journal of Institute of Control, Robotics and Systems
• /
• v.16 no.1
• /
• pp.5-11
• /
• 2010

An adaptive formation control approach is proposed for nonhonolomic multiple mobile robots considering unknown slipping and skidding. It is assumed that unknown slipping and skidding effects are bounded by unknown constants. Under this assumption, the adaptive technique is employed to estimate the bounds of unknown slipping and skidding effects of each mobile robot. To deal with the skidding effect included in kinematics, the dynamic surface design approach is applied to design a local controller for each mobile robot. Using Lyapunov stability theorem, the adaptation laws for tuning bounds of slipping and skidding are induced and it is proved that all signals of the closed-loop system are bounded and the tracking errors and the synchronization errors of the path parameters converge to an adjustable neighborhood of the origin. Finally, simulation results are provided to verify the effectiveness of the proposed approach.

• Journal of the Korean Chemical Society
• /
• v.30 no.5
• /
• pp.456-464
• /
• 1986

The complex formation of branched poly(ethylene imine) (BPEI) with bivalent transition metal ions, such as Fe(II), Co(II), Ni(II) and Cu(II), have been investigated in terms of visible absorption and pH titration methods in an aqueous solution in 0.1M KCl at 30${\circ}$. The stability constants for M(II)-BPEI complexes was calculated with the modified Bjerrum method. The formation curves of M(II)-BPEI complexes showed that Fe(II), Co(II), Ni(II) and Cu(II) ions formed coordination compounds with four, two, two, and two ethylene imine group, respectively. In the case of Cu(II)-BPEI complex at pH 3.4 ∼ 3.8, ${\lambda}_{max}$ was shifted to the red region with a decrease in the acidity. The overall stability constants (log $K_2$) increased as the following order, Co(II) < Cu(II) < Ni(II) < Fe(II).

• Applied Chemistry for Engineering
• /
• v.2 no.1
• /
• pp.70-76
• /
• 1991

Water soluble poly(sulfonated styrene-co-acrylic acid) was polymerized with sulfonated styrene and acrylic acid in the presence of silver sulfate at $99^{\circ}C$ for 4 hrs. The complex formation of poly(sulfonated styrene-co-acrylic acid) with Cu(II) was carried out. The maximum absorption wavelength of the poly(sulfonated styrene-co-acrylic)-Cu(II) system at different pH values was observed at 274 nm and 295 nm. The reduced viscosity of the poly(sulfonated styrene-co-acrylic acid)-Cu(II) complex were measured in the various pH ranges. The formation constants and stability constants of poly(sulfonated styrene-co-acrylic acid)-Cu(II) complex were calculated from Bjerrum method. The changes of enthalpy, free energy and entropy in the above reaction were determined by Ringbom method.

• Journal of Nuclear Fuel Cycle and Waste Technology
• /
• v.1 no.1
• /
• pp.65-73
• /
• 2013

Temperature-dependent hydrolysis behaviors of aqueous U(VI) species were investigated with time-resolved laser fluorescence spectroscopy (TRLFS) in the temperature range from 15 to $75^{\circ}C$. The formation of four different U(VI) hydrolysis species was measured at pHs from 1 to 7. The predominant presence of $UO{_2}^{2+}$, $(UO_2)_2(OH){_2}^{2+}$, $(UO_2)_3(OH){_5}^+$, and $(UO_2)_3(OH){_7}^-$ species were identified based on the spectroscopic properties such as fluorescence wavelengths and fluorescence lifetimes. With an increasing temperature, a remarkable decrement in the fluorescence lifetime for all U(VI) hydrolysis species was observed, representing the dynamic quenching behavior. Furthermore, the increase in the fluorescence intensity of the further hydrolyzed U(VI) species was clearly observed at an elevated temperature, showing stronger hydrolysis reactions with increasing temperatures. The formation constants of the U(VI) hydrolysis species were calculated to be $log\;K{^0}_{2,2}=-4.0{\pm}0.6$ for $(UO_2)_2(OH){_2}^{2+}$, $log\;K{^0}_{3,5}=-15.0{\pm}0.3$ for $(UO_2)_3(OH){_5}^+$, and $log\;K{^0}_{3,7}=-27.7{\pm}0.7$ for $(UO_2)_3(OH){_7}^-$ at $25^{\circ}C$ and I = 0 M. The specific ion interaction theory (SIT) was applied for the extrapolation of the formation constants to infinitely diluted solution. The results of temperature-dependent hydrolysis behavior in terms of the U(VI) fluorescence were compared and validated with those obtained using computational methods (DQUANT and constant enthalpy equation). Both results matched well with each other. The reaction enthalpies and entropies that are vital for the computational methods were determined by a combination of the van't Hoff equation and the Gibbs free energy equation. The temperature-dependent hydrolysis reaction of the U(VI) species indicates the transition of a major U(VI) species by means of geothermal gradient and decay heat from the radioactive isotopes, representing the necessity of deeper consideration in the safety assessment of geologic repository.