• Bulletin of the Korean Chemical Society
• /
• v.17 no.9
• /
• pp.820-826
• /
• 1996

The p2H dependence of the NMR chemical shifts of the proton signals of heme methyl groups and ionizable groups in the vicinity of the heme were investigated. The p2H titration of heme methyl signals in four macroscopic oxidation states by saturation tranfer method was performed in the range between p2H 5.2 and 9.0. While the p2H dependence of the heme methyl resonance in fully oxidized state was small, most resonances in the intermediate oxidation states showed certain shifts. Particularly, methyl resonances of heme 1 (sequential heme numbering) exhibited sharp p2H dependence in acidic range. β-CH2 of the propionate of hemes 1 and 4 were titrated in the range of p2H 4.5-9.0. Only the 6-propionate group of heme 1 was protonated in this p2H range and its titration curve was similar to those of methyl resonances of heme 1 in intermediate oxidation states. Analysis of the microscopic redox potentials showed that they change depending on p2H. The ionizable groups responsible for the p2H dependence of these potentials are 6-propionate of heme 1 in acidic range and His 67 in basic range.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
• /
• v.19 no.1
• /
• pp.1-7
• /
• 2021

The pH dependence of sorption distribution coefficient (Kd) of Np(IV) on MX-80 in Ca-Na-Cl type solution with the ionic strength of 0.3 M, which was similar to one of the reference groundwaters in crystalline rock, was experimentally investigated under the reducing conditions. The overall trend of Kd on MX-80 was independent of pH at 5 ≤ pH ≤ 10 but increased as pH increased at pH ≤ 5. The 2-site protolysis non-electrostatic surface complexation and cation exchange model was applied to the experimentally measured pH dependence of Kd and the optimized surface complexation constants of Np(IV) sorption on MX-80 were estimated. The values of surface complexation constants in this work agreed relatively well with those in the Na-Ca-Cl solution previously evaluated, suggesting that compared to Na+, the competition of Ca2+ with Np(IV) for surface complexation on MX-80 was not much strong in Ca-Na-Cl solution. The sorption model well predicted the pH dependence of Kd values but slightly overestimated the sorption at the low pH region.

• Journal of Sericultural and Entomological Science
• /
• v.39 no.2
• /
• pp.169-173
• /
• 1997

The behavior of tyrosine(Tyr.) residue of Bombyx mori silk fiber from yellow fluorescent cocoon has been examined for the dependence of pH in aqueous silk solution under the presence of orange II salt. Through the peak separation of angular dependence of spectral pattern of 15N-Tyr. and [1-13C]-Tyr. between the fiber axis and the molecular bond direction, N-H bond in fiber as well as the orientation distribution around the fiber axis were analyzed. Also, and sericin component was obtained from these angular dependence of oriented spectral pattern. The pH dependence of the 13C NMR chemical shift of B. mori silk fibroin was examined in aqueous solution in the presince of orange II are broad at pH$\geq$7.0. However, these become sharper at pH$\geq$8.0 and remain sharp at higher pH. In these higher pH range, a chemical shift change occurs due to the deprotonation of the Tyr. side group of fibroin. At higher pH. such a hydrophobic cluster is destroyed because of the electrostatic interaction according to the deprotonation of the Tyr-OH group.

• Bulletin of the Korean Chemical Society
• /
• v.9 no.1
• /
• pp.40-44
• /
• 1988

The pH dependence studies of Raman spectra are reported for water-soluble free-base, Zn, Co and Cu tetrakis (4-sulfonatophenyl) porphine in pH 4, pH 7 and pH 13.9 aqueous solution. For free base porphine, the substantial differences are found in absorption and Raman spectra between pH 4 and pH 7 or pH 10 aqueous solutions due to the protonation at low pH. For Zn and Co porphyrins, the hydrolysis equilibrium constants are obtained by spectrophotometric titration experiments. The consistent shifts in Raman frequencies are found at high pH due to the hydrolysis. For Cu porphyrins, instead of hydrolysis the aggregation effect is detected at high pH through the absorption and Raman studies.

• Bulletin of the Korean Chemical Society
• /
• v.7 no.2
• /
• pp.137-142
• /
• 1986

The luminescence spectra of $Ru(bpy)_3^{2+}$ in poly(methacrylic acid) (PMA) solutions varied sensitively with pH. At pH < 5.5, the emission intensity increased with pH up to 4 times, while it decreased with pH beyond the pH. The enhanced emission intensity was accompanied by blue-shift of the emission maxima as much as 15 nm. The enhancement of emission intensity was attributed to the restricted rotational mobility of ligand of the cation bound to densely coiled PMA molecules at pH < 5.5. The sharp decrease in emission intensity with increasing pH near pH 5.6 was accounted for conformational transition of the polymer to more extended structure, which was also revealed in viscosity measurement. The enhancement of emission intensity became higher as NaCl concentration of the solution increased. The binding constant of $Ru(bpy)_3^{2+}$ with two carboxylate groups of PMA was calculated as $2{\times}10^5\;M^{-1}$ in 0.1 M NaCl at pH 5.2. The pH dependence of luminescence quenching rate of $Ru(bpy)_3^{2+}$ by $Cu^{++}$ also showed maximum near pH 5, and the rate was more than $10^3$ times higher than that in water, whereas the maximum enhancement of quenching rate (about 20 times) in poly(acrylic acid) (PAA) solution occurred at pH 4.5. On the other hand, the pH dependence for neutral water soluble nitrobenzene (NB) exhibited opposite trend to that of $Cu^{++}$. The quenching constant vs pH curve for $MV^{++}$ was composite of those for $Cu^{++}$ and NB. The anomalous high quenching rate for $Cu^{++}$ in PMA solution at pH < 5.5 was attributed to the binding of $Ru(bpy)_3^{2+}$ and $Cu^{++}$ to the same region of PMA, when it conforms densely coiled structure in the pH range. The observation of mininium quenching rate for NB near pH 5.5 indicated that the $Ru(bpy)_3^{2+}$ bound to the densely coiled PMA is not accessible by NB, which is in bulk water phase. The composite nature of the pH dependence of quenching rate for $MV^{++}$ in PMA solution was attributed to the smaller binding affinity of the cation to PMA, compared to that of $Cu^{++}$. The sharp, cooperative conformational transition with pH observed in PMA was not revealed in PAA. But, the pH dependence of quenching rates in this polymer reflected increased charge density and, thus, binding of cations to the polymer, and expansion of the polymer chain with pH.

• Journal of the Korean Institute of Telematics and Electronics
• /
• v.25 no.11
• /
• pp.1335-1341
• /
• 1988

A pH-ISEFET microprobe for in vivo measurements has been fabricated by combining ISFET (SL-IIS) chip and capillary thin film reference electrode. A two-step TCE oxidation for the gate oxide layer and multilayer encapsulation using silicone rubber and epoxy were specially used for the improvement of the stability and temperature dependence of the ISFET's. The measured sensitivit, response time and temperature dependence of the pH-ISFET microprobes are 50 mV/pH, less than one second, and - 0.01 pH/$^{\circ}$ , respectively. By operating continuously more than 40 days, a long term stability of 0.016 pH/day is obtained. The result of pH monitoring of femoral arterial blood in a rabbit is fairly good agreement with the value of blood gas analysis.

• Journal of Life Science
• /
• v.10 no.2
• /
• pp.210-217
• /
• 2000

A kinetic profile of the catalytic domain of stromelysin-1 (SCD) using the fluorescent peptide substrate has been determined by the stopped-flow technique. The pH profile has a pH optimum of about 5.5 with an extended shoulder above pH 7. Three pKa values, 5.0, 5.7, and 9.8 are found for the free enzyme state and two pH independent Kcat/Km values of 4.1$\times$104 M-1 s-1 and 1.4$\times$104 M-1 s-1 at low and high pH, respectively. The profile is quite different in shape with other MMP family which has been reported, having broad pH optimum with two pKa values. The substrate specificity of SCD towards fluorescent heptapeptide substrates has been also examined by thin layer chromatography. The cleavage sites of the substrates have been identified using reverse-phase HPLC method.SCD cleaves Dns-PLA↓L↓WAR and Dns-PLA↓L↓FAR at two positions. However, the Dns-PLA↓LRAR, Dns-PLE↓LFAR, adn Dns-PLSar↓LFAR are cleaved exclusively at one bond. The double cleavages of Dns-PLALWAR and Dns-PLALFAR by SCD are in marked contrast to the close structurally related matrilysin. A notable feature of SCD catalysis agrees with the structural data that the S1' pocket of SCD is deeper than that of matriysin. The differences observed between SCD and matrilysin may form the basis of understanding the structural relationships and substrate specificities of the MMP family in vivo.

• Korean Chemical Engineering Research
• /
• v.50 no.2
• /
• pp.379-384
• /
• 2012

It is investigated that that the physical properties of Glutathione layer formed on gold surfaces may make an effect on the distribution of either gold particle adsorbed to the $TiO_2$ surface or vice versa with the adjustment of the electrostatic interactions. For the investigation, the atomic force microscope (AFM) was used to measure the surface forces between the surfaces as a function of the salt concentration and pH value. With the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, the forces were quantitatively analyzed to acquire the surface potential and charge density of the surfaces for each salt concentration and each pH value. The surface potential and charge density dependence on the salt concentration was described with the law of mass action, and the pH dependence was explained with the ionizable groups on the surface. The salt concentration dependence of the surface properties, found from the measurement at pH 8 and 11, was consistent with the prediction from the law. It was found that the Glutathione layer had higher values for the surface charge densities and potentials than the titanium dioxide surfaces at pH 8 and 11, which may be attributed to the ionized-functional-groups of the Glutathione layer.

• Journal of the Korean Chemical Society
• /
• v.24 no.1
• /
• pp.86-89
• /
• 1980

• Korean Chemical Engineering Research
• /
• v.52 no.4
• /
• pp.538-543
• /
• 2014

It is investigated that that the physical properties of Glutathione layer formed on gold surfaces may make an effect on the distribution of either gold particle adsorbed to the $ZrO_2$ surface or vice versa with the adjustment of the electrostatic interactions. For the investigation, the atomic force microscope (AFM) was used to measure the surface forces between the surfaces as a function of the salt concentration and pH value. The forces were quantitatively analyzed with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory to estimate the surface potential and charge density of the surfaces for each condition of salt concentration and pH value. The estimated-value dependence on the salt concentration was described with the law of mass action, and the pH dependence was explained with the ionizable groups on the surface. The salt concentration dependence of the surface properties, found from the measurement at pH 4 and 8, was consistent with the prediction from the law. It was found that the Glutathione layer had higher values for the surface charge densities and potentials than the zirconium dioxide surfaces at pH 4 and 8, which may be attributed to the ionized-functional-groups of the Glutathione layer.