• Journal of Pharmaceutical Investigation
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• v.19 no.2
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• pp.71-79
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• 1989

Complex formation of water-soluble polyparacyclophanes bearing two diphenylmethane or two diphenyl ether skeletons with l-anilinonaphthalene-8-sulfonate (ANS) and 2-p-toluidinylnaphthalene-6-sulfonate (TNS) was investigated quantitatively to develop useful host compounds comparing with ${\alpha}\;-\;and\;{\beta}-cyc1odextrins$$({\alpha}-\;and\;{\beta}-CyDs$) in aqueous solution. Benesi-Hildebrand type analysis of the fluorescent intensity showed that the dissociation constants (Kd) of paracyclophane-ANS complexes were $1.55\;{\times}\;10^{-4}M$ for 1,6,20,25-tetraaza[6.1.6.1]paracyclophane(CPM 44) and $1.23\;{\times}\;10^{-4}M$ for 1,7,21,27-tetraaza[7.1.7.1]paracyclophane (CPM 55), and those of paracyclophane-TNS complexes were $6.99\;{\times}\;10^{-6}M$ for CPM 44 and $6.23\;{\times}\;10^{-5}M$ for CPM 55, in 1:1 molar ratio. On the other hand, the Kd values of 1,7,21,27-tetraaza-14,34-dioxa[7.1.7.1]paracyclophane (CPE 55)-ANS, 1,8,22,29-tetraaza-15,36-dioxa[8.1.8.1]paracyclophane (CPE 66)-ANS, CPE 55-TNS, CPE 66-TNS complexes were $1.75\;{\times}\;10^{-3}M$, $3.07\;{\times}\;10^{-3}M$, $3.75\;{\times}\;10^{-3}M$ and $2.15\;{\times}\;10^{-3}M$, respectively. On the contrary, the Kd values of ${\alpha}-CyD-ANS$, ${\beta}-CyD-ANS$, ${\alpha}-CyD-TNS$ and ${\beta}-CyD-TNS$ complexes were found to be $3.98\;{\times}\;10^{-2}M$, $1.05\;{\times}\;10^{-2}M$, $1.38\;{\times}\;10^{-2}M$ and $3.52\;{\times}\;10^{-4}M$, respectively. These results mean that the complexation of CPMs with ANS or TNS is by 5.6-1,975 fold stronger than that for ${\alpha}-or\;{\beta}-CyDs$, and the complex formation of CPEs with ANS or TNS is nearly same as or somewhat stronger than that for ${\alpha}-or\;{\beta}-CyDs$. From the Kd values determined at different temperatures, thermodynamic parameters were calculated and the complexation was found to be a spontaneous exothermic reaction. The effects of pH on Kd values of CPM 44-ANS, and CPM 55-ANS complexes were negligible in the range of pH 1.2-1.8. However, the Kd values of these complexes increased significantly with increasing ionic strength.

• Journal of the Korean Chemical Society
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• v.33 no.1
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• pp.3-10
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• 1989

In order to obtain a clue in understanding enzymatic hydrolysis in which the His-Cys moieties of papain protease is involved, we prepared cationic peptide-sufactants bearing histidyl, cysteinyl, and both histydyl and cysteinyl residues. Their catalytic efficiency toward the hydrolysis of PNPL were investigated in comicellar phases formed with $N^{+}C_{2}CysC_{12}$, $N^{+}C_{2}HisC_{12}$, $N^{+}C_{2}HisCysC_{12}$ increased markedly in the same order compared with that of $N^{+}C_{2}AlaC_{12}$. The markedly increased catalytic effects are attributed to the imidazole groups of $N^{+}C_{2}HisC_{12}$ and the thiol groups of $N^{+}C_{2}CysC_{12}$, and the large catalytic efficiency of $N^{+}C_{2}HisCysC_{12}$, is considered due to the interaction of the imidazole and the thiol groups. In order to investigate catalytic activities, rate constants for the functional groups, km* and dissociation constants, pKa have been determined. The results showed that $k^{\ast}_m$ and pKa of the imidazole groups were $7.91{\times}10^{-4}S^{-1}$ and 6.49, and those of the thiol groups were $6.00{\times}10^{-4}S^{-1}$ and 10.50. The catalytic effects of comicellar systems on the hydrolysis of p-nitrophenyl esters has increased according to the increasing size of the alkyl carbon number. Therefore, the catalytic effects have been increasing by the interaction of micellar hydrophobic parts and substrates as well as action of the functional groups.

• Journal of Photoscience
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• v.9 no.2
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• pp.314-316
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• 2002

In halobacterial membrane, pharaonis phoborhodopsin (or pharaonis sensory rhdopsin II, psRII) forms a complex with its transducer pHtrII. Flash-photolyis of D75N mutant did not yield M-intermediate but an O-like intermediate is observed. We examined the interaction between D75N of ppR and t-Htr (truncated pHtrII). These formed a complex in the presence of n-dodecyl-$\beta$-D-maltoside, and the association accelerated the decay of the 0 of D75N from 15 to 56 s$\^$-1/. From the decay time constants under varying ratios of D75N and t-Htr, n, the molar ratio of D75N/t-Htr in the complex, and K$\_$D/, the dissociation constant, were estimated. The value of n was unity and K$\_$D/ was estimated to 146 nM. This K$\_$D/ value can be considered as the association between the photo-intermediate and t-Htr, which is deduced by the method of estimation. Previously we (Photochem. Photobiol. 74, 489-494 (2001)) reported K$\_$D/ of 15 $\mu$M for the interaction between the wild-type and t-Htr by means of the change of M-decay rates. Therefore, this value should be the K$\_$D/ value for the interaction between M of the wild-type and t-Htr.

• Journal of Microbiology and Biotechnology
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• v.6 no.4
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• pp.250-254
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• 1996

MR-387A [(2S, 3R)-2-hydroxy-3-amino-4-phenylbutanoyl-L-valyl-L-prolyl-(2, 4-trans)- L-4-hydroxy-proline] reversibly inhibits aminopeptidase N (BC 3.4.11.2) in a process that is remarkable for its unusual degree of time dependence. The time required to inactivate the enzyme by 50$%$ ($t_{1/2}$) for establishing steady-state levels of $EI^*$complex was approximately 5 minutes. This indicates that the inhibition is a slow-binding process. In dissociation experiments of $EI^*$ complex, enzymic activity was regained slowly in a quadratic equation, indicating that the inhibition of aminopeptidase N by MR-387A is tight-binding and reversible. Thus, the binding of MR-387A by aminopeptidase N is slow and tight, with $K_{i}$ (for initial collision complex, EI) and $K_i{^*}$ (for final tightened complex, $EI^*$) of $2.2\times10^{-8}$ M (from Lineweaver-Burk plot) and $4.4\times10^{-10}$ M (from rate constants), respectively. These data indicate that MR-387A and aminopeptidase N are bound approximately 200-fold more tightly in the final $EI^*$complex than in the initial collision EI complex.

• Applied Chemistry for Engineering
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• v.4 no.4
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• pp.672-682
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• 1993

2, 4-Heptadione(abbreviated to 24HTD) was synthesized from methylpropyl ketone and ethyl acetate with sodium amide, and the equilibrium and the kinetic characteristics of copper extraction by 24HTD-chloroform were investigated. Equilibrium constants such as the dissociation constant and the distribution coefficient of 24HTD and the stability constant of the 24HTD-Cu chelate were evaluated from the spectrophotometry, and the overall equilibrium constant of the extraction was also determined. The extracted species of the 24HTD-Cu chelate was found to be $CuR_2$ and the initial rate of the extraction of coupper by 24HTD in chloroform was expressed by $R_0=k[\bar{HR}]([Cu^{2+}]/[H^+])^{0.5}$.

• Journal of the Korean Chemical Society
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• v.26 no.5
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• pp.326-332
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• 1982

The structure of the complex extracted from an aqueous solution containing methylene blue and tetrafluoroborate with 1,2-dichloroethane has been investigated by comparing IR spectrum of the extract with those of pure components and appeared to be an 1 : 1 contact ion-pair between monovalent ions of opposite charge. The extraction constant obtained from the absorbance data measured at 658nm in 1,2-dichlorethane has a value of 1.1${\times}$at$10^4M{-1}$ 25$^{\circ}$C in the range from 1.43${\times}10^{-2}$ to 2.86${\times}10^{-1}$M HF. In the solvent extraction with nitrobenzene, the identical experiments show that extraction constants are increased with HF concentration possibly due to dissociation of the ion-pair in nitrobenzene.

• Journal of the Korean Chemical Society
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• v.38 no.10
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• pp.705-709
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• 1994

The kinetics of the oxidation reaction of malonic acid by ceric ion in 1 M sulfuric acid solution at $20^{\circ}C$ have been investigated by spectrophotometric method. The reaction rate at a large excess of malonic acid was found to be pseudo-first order. The observed pseudo-first order rate constants, $k_{obs}$, are dependent on the concentration of malonic acid, [MA], of which relationship has been found to be $k_{obs}$ = (0.592[MA])/(1+14.5[MA]$^2$). A mechanism for the reaction has been suggested on the basis of the above rate equation. The rate determining step may be the electron transfer reaction between enolate type malonate anion, which is formed by the acid dissociation reaction of malonic acid, and Ce(IV). The rate depression in the range of high concentration of MA has been explained by the formation of 1 : 2 chelate between Ce(IV) and malonate. According to the mechanism, the pH dependence of the rate, which was studied by Sengupta et al., has also been explained.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2002.07a
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• pp.281-287
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• 2002

The stochiometric composition of AgGaS$_2$ polycrystal source materials for the AgGaS$_2$/GaAs epilayer was prepared from horizontal furnace. From the extrapolation method of X-ray diffraction patterns it was found that the polycrystal AgGaS$_2$ has tetragonal structure of which lattice constant a$\sub$0/ and c$\sub$0/ were 5.756 ${\AA}$ and 10.305 ${\AA}$, respectively. AgGaS$_2$/GaAs epilayer was deposited on throughly etched GaAs(100) substrate from mixed crystal AgGaS$_2$ by the Hot Wall Epitaxy (100) system. The source and substrate temperature were 590$^{\circ}C$ and 440$^{\circ}C$ respectively. The crystallinity of the grown AgGaS$_2$/GaAs epilayer was investigated by the DCRC (double crystal X-ray diffraction rocking curve). The optical energy gaps were found to be 2.61 eV for AgGaS$_2$/GaAs epilayer at room temperature. The temperature dependence of the photocurrent peak energy is well explained by the Varshni equation, then the constants in the Varshni equation are given by ${\alpha}$ : 8.695${\times}$10$\^$-4/ eV/K, and ${\beta}$ = 332 K. From the photocurrent spectra by illumination of polarized light of the AgGaS$_2$/GaAs epilayer, we have found that crystal field splitting ΔCr was 0.28 eV at 20 K. From the PL spectra at 20 K, the peaks corresponding to free and bound excitons and a broad emission band due to D-A pain are identified. The binding energy of the free excitons are determined to be 0.2676 eV and 0.2430 eV and the dissociation energy of the bound excitons to be 0.4695 eV.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2004.04b
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• pp.56-59
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• 2004

The stochiometric composition of $AgGaS_2$ polycrystal source materials for the $AgGaS_2/GaAs$ epilayer was prepared from horizontal furnace. From the extrapolation method of X-ray diffraction patterns it was found that the polycrystal $AgGaS_2$ has tetragonal structure of which lattice constant $a_0$ and $c_0$ were 5.756 ${\AA}$ and 10.305 ${\AA}$, respectively. $AgGaS_2/GaAs$ epilayer was deposited on throughly etched GaAs (100) substrate from mixed crystal $AgGaS_2$ by the Hot Wall Epitaxy (HWE) system. The source and substrate temperature were $590^{\circ}C$ and $440^{\circ}C$ respectively. The crystallinity of the grown $AgGaS_2/GaAs$ epilayer was investigated by the DCRC (double crystal X-ray diffraction rocking curve). The optical energy gaps were found to be 2.61 eV for $AgGaS_2/GaAs$ epilayer at room temperature. The temperature dependence of the photocurrent peak energy is well explained by the Varshni equation, then the constants in the Varshni equation are given by ${\alpha}=8.695{\times}10^{-4}eV/K$, and $\beta$=332 K. From the photocurrent spectra by illumination of polarized light of the $AgGaS_2/GaAs$ epilayer, we have found that crystal field splitting $\Delta$ Cr was 0.28 eV at 20 K. From the PL spectra at 20 K, the peaks corresponding to free and bound excitons and a broad emission band due to D-A pairs are identified. The binding energy of the free excitons are determined to be 0.2676 eV and 0.2430 eV and the dissociation energy of the bound excitons to be 0.4695 eV.

• Journal of the Korean Chemical Society
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• v.27 no.3
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• pp.178-182
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• 1983

The conductances of sodium, potassium, ammonium, tetramethylammonium, and tetraethylammonium iodides, picrates(Pic) of sodium and potassium, and tetrabutylammonium tetraphenyl-boride have been measured in ethylene carbonate-acetone mixtures at $25{\circ}C$. The limiting equivalent conductances of the electolytes were computed by Fuoss-Kraus equation and the order was $(C_4H_9)_4NB(ph)_4 at any composition of the mixtures. The dissociation constants of the salts showed that the mixtures are good ionizing solvents for the salts. The order of limiting ionic equivalent conductance, $Na^+, is consistent with exactly the reverse order found for solvation number. Effective solvated radii calibrated by the Nightingale method showed that picrate ion seems to be unsolvated and that iodide ion seems to be solvated to some extent in the mixtures.