• Bulletin of the Korean Chemical Society
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• v.25 no.7
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• pp.997-1002
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• 2004

A hydrogenperoxide sensor containing peroxidase extracted from horseradish was constructed and pH effect on its sensing ability was investigated. Current profiles of the biosensor with pH and the electrophoretic analysis showed that horseradish peroxidase consists of two isozymes. Assuming that it is a hypothetical twoisozyme mixture, the current profiles were deconvoluted into two Gaussians. Application of the new Michaelis-Menten equation connoting pH concept to this system enabled to find all the related dissociation constants of the isozyme-substrates and the isozyme-proton complexes and to determine pHs for the maximal isozyme activities.

• Analytical Science and Technology
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• v.9 no.4
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• pp.345-354
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• 1996

Algal(II) Multidentate N, O-Schiff base ligands, such as bis(salicylaldehyde) ethylenediimine(SED), bis(salicylaldehyde) propylenediimine(SPD), bis(salicylaldehyde) diethylenetriimine(SDT), bis (salicylaldehyde) triethylenetetraimine(STT) and bis(salicyl-aldehyde)tetraethylenepentaimine(STP) were prepared. Stepwise proton dissociation constants of the Schiff base were measured potentiometrically in ethanol and a mixture of 70% dioxane and 30% $H_2O$. The stability constants of copper(II)-Schiff base complexes were in the order of Cu(II)-SPD${\leq}$Cu(II)-SED~STT${\leq}$Cu(II)-STP. Oxidation-reduction process of the Cu(II)-Schiff base complexes was involved with one-electron reaction.

• Analytical Science and Technology
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• v.13 no.5
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• pp.558-564
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• 2000

Mononuclear schiff base ligand N,N'-bissalicylidene-1,2-phenylenediamine(BSPD) and binuclear schiff base ligands N,N',N',N'''-tetrasalicylidene-3,3',4,4'-tetraaminodiphenyl-methane (TSTM), N,N',N'',N'''-tetrasalicylidene-3,3'-diaminobenzidine (TSDB) have been synthesized. Proton dissociation constants of the ligands were determined by potentiometric method. The synthesized ligands and complexes formed with Cu(II) ion. These complexes were investigated by cyclic voltammetry and differential pulse voltammetry. The results revealed two step diffusion controlled redox process. The mononuclear complex Cu(II)-BSPD and binuclear complexes $Cu(II)_2$-TSDB and $Cu(II)_2$-TSTM were used in the oxidation reaction of ascorbic acid. The reaction rates were in the order of $Cu(II)_2$-TSTM>$Cu(II)_2$-TSDB>Cu(II)-BSPD, indicating that the binuclear $Cu(II)_2$-TSTM complex had the fastest values.

• Journal of the Korean Chemical Society
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• v.54 no.5
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• pp.541-550
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• 2010

A new $N_4O_3$ heptadentate ligand, N,N'-Bis(2-hydroxybenzyl)-1,3-bis[(2-aminoethyl)amino]-2-propanol(H-BAP 4HCl)was synthesized. The hydrochloric acid salts of Br-BAP 4HCl, Cl-BAP 4HCl, $CH_3O$-BAP 4HCl and $CH_3$-BAP 4HCl containing Br-, Cl-, H-, $CH_3O-$ and $CH_{3^-}$ groups at the para-site of the phenol group of the H-BAP were synthesized. The structures of the ligands were confirmed by C. H. N. atomic analysis and $^1H$ NMR, $^{13}C$ NMR, UV-visible and mass spectra. The elemental stepwise protonation constants(${logK_n}^H$) of the synthesized $N_4O_3$ ligands showed six steps of the proton dissociation. The orders of the overall dissociation constants($log{\beta}_p$) of the ligands were Br-BAP < Cl-BAP < H-BAP < $CH_3O$-BAP < $CH_3$-BAP. The orders agreed well with that of Hammett substituent constants($\sigma_p$). The calculated stability constants($logK_{ML}$) between the ligands and transition metal ions agreed well with the order of the overall proton dissociation constants of the ligands but they showed a reverse order in Hammestt substituent constants($\sigma_p$). The order of the stability constants between the transition metal ions with the ligands were Co(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II).

• The Korean Journal of Physiology
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• v.30 no.2
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• pp.197-208
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• 1996

Endosomes lower their internal pH by an ATP-driven proton pump, which is critical to dissociation of many receptor-ligand complexes, the first step in the intracellular sorting of internalized receptors and ligands. Endosomes are known to exhibit n great range of pH values that can vary between 5.0 and 7.0 within a single cell although the factors that regulate endosomal pH remain uncertain. To evaluate the morphological and topological differences of endosomes in the different stages, confocal microscopy was used. The early endosomes labeled with fluorescein isothiocyanate-dextran for 10 min at $37^{\circ}C$ were identifiable at the peripheral and tubule-vesicular endosome compartment. In contrast, the late endosomes formed by 10 min pulse and 20 min trace were located deeper in the cytoplasm and showed more vesicular features than early endosomes. For the purpose of determining whether ATP-dependent acidification was heterogeneous and whether the differences in acidification were attributed to differences in the activity of $Na^{+}-K^{+}$-ATPase and/or $Cl^{-}$ channel, endocytic compartments were fractionated into subpopulation using percoll gradient and measured ATP-dependent acidification. While all fractions exhibited ATP-dependent acidification activity, both the initial rate of acidification and extent of proton translocation were lower in early endosomes and gradually increased in late endosomes. Phosphorylation by PKA and ATP enhanced ATP-dependent acidification in both early and late endosomes, hut there was no difference in the degree of enhancement by phosphorylation between two subpopulations. When ATP-dependent acidification was determined in the presence or absence of vanadate ($Na_{3}VO_{4}$) or ouabain, only early endosomes exhibited the vanadate or ouabain dependent stimulation of acidification activity, suggesting the inhibition of $Na^{+}-K^{+}$-ATPase. Therefore, it seems probable that the inhibition of early endosome acidification by $Na^{+}-K^{+}$-ATPase observed in vitro at least in part plays a physiological role in controlling the acidification of early endosomes in vivo.

• Bulletin of the Korean Chemical Society
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• v.20 no.1
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• pp.85-88
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• 1999

Me3NO selectively abstracts the proton from [IrH(CO)(PPh3)2L(A)]0.1+,2+ (1) (A: -CCPh, Cl-, CH3CN and L: CH3CN, Cl-, C1O4-) to give the trans-elimination products, Ir(CO)(PPh3)2(A) (2). The reductive elimination of H+ and Cl- from Ir(H)Cl2(CO)(PPh3)2 (lb) to give IrCl(CO)(PPh3)2 (2b) is first order in both lb and Me3NO. The rate law d[2b]/dt=kobs[lb]=k2[lb][Me3NO] suggests the formation of (PPh3)2(CI)2(CO)Ir-H-ON+Me3 in the rate determining step (k2) followed by the fast dissociation of both H-ON+Me3 and the trans ligand Cl-. The rate significantly varies with the cis liaand A and the trans ligand L and is slower with both A and L being Cl- than other ligands. Me3NO selectively eliminates CO from [Ir(H)2(CO)(PPh3)2L]0,+ (3) (L=CH3CN, C1O4-) to produce [Ir(H)2(PPh3)2L'(CH3CN)]+ (4) (L'=CH3CN, PPh3) in the presence of L. Me3NO does not readily remove either H+ or CO from cis, trans- and trans, trans-lr(H)(-CCPh)2(CO)(PPh3)2 and cis, trans-Ir(H)2Cl(CO)(PPh3)2. The choice whether hydridocarbonyls, 1 and 3 undergo the deprotonation or decarbonylation may be understood mostly in terms of thermodynamic stability of the products and partly by kinetic preference of Me3NO on proton and CO.

• Polymer(Korea)
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• v.26 no.3
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• pp.293-299
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• 2002

By the reaction of m-cresol as a microbicide with acryloyl chloride m-cresyl acrylate (CA) was synthesized, and polymers with the moiety of m-cresol were prepared by the radical terpolymerization of CA -methylmethacrylate -acrylic acid. The contents of CA unit in the polymers were found to be 4.7 mol% and 10.1 mol% from their nuclear magnetic resonance spectra. The number -average molecular weights of the polymers were in the range of 12000 to 15000. Through the hydrolysis of the polymers m-cresol was released. The release rate of the microbicide increased with increasing PH of the release medium. This result can be attributed to enhanced proton dissociation of carboxyl group of the acrylic acid unit in the polymers. These polymers showed microbicidal activities for S. aureus as a positive microbe and E. coli as a negative microbe.

• Analytical Science and Technology
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• v.12 no.5
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• pp.397-402
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• 1999

The open-chain hexadentate $N_6$, ligand containing two pyridyl groups, 1,15-bis(2-pyridyl)-2,6,10,14-tetraazapentadecane (bpyped) has been synthesized as its tetrahydroehloride salt and characterized by EA, IR, NMR, and Mass. Its proton dissociation constants($logK{^n}_H$) and stability constants ($log\;K_{ML}$) for Co(II), Ni(II), Cu(II) and Zn(II) ions were determined at $25^{\circ}C$ and ionic strength 0.10 M($KNO_3$) in aqueous solution by potentiometry and compared with those or analogous $N_6$ ligands contain one or two propylenic spacers, which make six-membered chelate rings, between the aliphatic nitrogen atoms.

• Journal of the Korean Chemical Society
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• v.42 no.5
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• pp.539-548
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• 1998

Multidentate N,O-containing ligands, such as N,N'-bis(2-hydroxybenzyl)-ethylenediamine(BHED), N,N'-bis(2-hydroxybenzyl)-propylenediamine(BHPD), N,N'-bis(2-hydroxybenzyl)-diethylenetriamine(BHDT), N,N'-bis(2-hydroxybenzyl)-triethylenetriamine(BHTT) and N,N'-bis(2-hydroxybenzyl)-tetraethylenepentaamine (BHTP) were synthesized by reduction of the imine group of Bis(salicylidene)-ethylendiamine(BSED), Bis (salicylidene)-propylenediamine(BSPD), Bis(salicylidene)-diethylentriamine(BSDT), Bis(salicylidene)-triethylenetetraamine(BSTT) and Bis(salicylidene)-tetraethylenepentaamine(BSTP). Proton dissociation constants of the ligands and stability constants of transition metal(Ⅱ) ion complexes with BHED, BHPD, BHDT, BHTT, and BHTP were determined by potentiometic titration. The sequence of stability constants $(logK_{ML})$ of complex increases as BHED Zn(Ⅱ) which follows the Irving-Williams series.

• Journal of the Korean Chemical Society
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• v.44 no.6
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• pp.518-525
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• 2000

The open-chain hexadentate N$_4$, O$_2$ ligands 1,13-bis(2-hydroxybenzyl)-2,5,9,12-tetraazatridecane-tetrahydrochloride (BSATD${\cdot}$4HCl) and 1,14-bis (2-hydroxybenzyl)-2,6,9,12-tetraazatetradecane-tetrahydrochloride (BSATED${\cdot}$ 4HCl) have been synthesized as their tetrahydrochloride salt and characterized by EA, IR, NMR and Mass. Their proton dissociation constants(log$K^{n}_{H}$) and stability constants(log$K_{ML}$) for Cu(II), Ni(II), Co(II), and Zn(II) ions were determined in aqueous solution by potentiometry and compared with those of analogous N$_4$, O$_2$ ligands contain ethylenic spacers or propylenic spacers, which make six-membered chelate rings between the aliphatic nitrogen atoms. Synthesis and characterization of [Cu(BSATD)]ClO$_4$ and [Cu(BSATED)](ClO$_4$)$_2$ complexes are described.