• Title/Summary/Keyword: pK$_{a}$ of the Schiff base

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Molecular Cloning and Characterization of the Rod Opsin Gene in Olive Flounder Paralichthys olivaceus

  • Kim, Jong-Myoung;Kim, Sung-Wan;Kim, Sung-Koo
    • Fisheries and Aquatic Sciences
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    • v.10 no.1
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    • pp.8-15
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    • 2007
  • Rhodopsin, a dim-light receptor, is a model system for the study of G protein-coupled receptors that transduce extracellular signals into cells. To study the molecular mechanisms of visual systems in fish, the rod opsin gene of olive flounder Paralichthys olivaceus was characterized. The full-length P. olivaceus opsin gene was obtained by PCR amplification of genomic DNA, as well as cDNA synthesis. A comparison of clones obtained from both methods indicated that the olive flounder rod opsin gene lacks introns. Sequence analysis of the opsin gene indicated that it contains a 1,056-bp open reading frame encoding 352 amino acids. The deduced amino acid sequence contains features of typical rod opsins, such as sites for Schiff's base formation (K296) and its counterion (E113), disulfide formation (C110 and C187), and palmitoylation (C322 and C323). An opsin sequence alignment showed the highest similarity between P. olivaceus and Solea solea (95.1%), followed by Hippoglossus hippoglossus (94.5%). An opsin phylogenetic tree revealed a close relationship between olive flounder and teleost rod opsins.

Synthesis and Characterization of Homo Binuclear Macrocyclic Complexes of UO2(VI), Th(IV), ZrO(IV) and VO(IV) with Schiff-Bases Derived from Ethylene diamine/Orthophenylene Diamine, Benzilmonohydrazone and Acetyl Acetone

  • Mohapatra, R.K.;Ghosh, S.;Naik, P.;Mishra, S.K.;Mahapatra, A.;Dash, D.C.
    • Journal of the Korean Chemical Society
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    • v.56 no.1
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    • pp.62-67
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    • 2012
  • A series of homo binuclear complexs of the type $[M_2(L/L^')(NO_3)n].mH_2O$, [where $M=U{O_2}^{2+},\;Th^{4+},\;ZrO^{2+}$] and $[(VO)_2(L/L^')(SO_4)_2]{\cdot}2H_2O$, L=1,5,6,9,12,15,16,20 octaaza-7,813,14-tetraphenyl-2,4,17,19-tetramethyl-1,4,6,8,12,14,16,19-docosaoctene (OTTDO) or L'=10:11;21:22-dibenzo-1,5,6,9,12,15,16,20-octaaza-7,813,14-tetraphenyl-2,4,17,19-tetramethyl-1,4,6,8,12,14,16,19-docosaoctene (DOTTOT), n=4 for $U{O_2}^{2+}$, $ZrO^{2+}$ n=8 for $Th^{4+}$ m=1,2,3 respectively, have been synthesized in template method from ethylenediamine/orthophenylene diamine, benzil monohydrazone and acetyl acetone and characterized on the basis of elemental analysis, thermal analysis, molar conductivity, magnetic moment, electronic, infrared, $^1H$-NMR studies. The results indicate that the VO(IV) ion is penta co-ordinated yielding paramagnetic complexes; $UO_2(VI)$, ZrO(IV) ions are hexa co-ordinated where as Th(IV) ion is octa co-ordinated yielding diamagnetic complexes of above composition. The fungi toxicity of the ZrO(IV) and VO(IV) complexes against some fungal pathogen has been studied.

Synthesis, Antibacterial, Docking and Anticancer Evaluation of N-Substituted Benzoyl Derivatives

  • Arthi, P.;Shobana, S.;Srinivasan, P.;Rahiman, A. Kalilur
    • Journal of Integrative Natural Science
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    • v.7 no.4
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    • pp.241-252
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    • 2014
  • A series of N-benzoylated ligands incorporating three different benzoyl groups 2,2'-(benzoyliminodiethylene)-4-substituted phenols ($L^{1,4,7}$), 2,2'-(4-nitrobenzoyliminodiethylene)-4-substituted phenols ($L^{2,5,8}$) and 2,2'-(3,5-dinitrobenzoyliminodiethylene)-4-substituted phenols ($L^{3,6,9}$) were synthesized and characterized by IR, $^1H$ NMR, $^{13}C$ NMR and mass spectroscopy. The In vitro antibacterial activity of investigated ligands were tested against human pathogenic bacteria such as four Gram (-) Enterococcus faecalis, Pseudomonas aeruginosa, Staphylococcus aureus, Vibrio cholera, Vibrio harveyi and two Gram (+) Staphylococcus aureus, Streptococcus mutans. Furthermore, docking studies were undertaken to gain insight into the possible binding mode of these compounds with the binding site of the topoisomerase II (PDB: 4FM9) enzyme which is involved in DNA superhelicity and chromosome seggregation. The N-benzoylated derivatives $L^{5,7,8}$ have significant anticancer activity as Topoisomerase inhibitors. The ligands $L^5$ and $L^8$ were tested for their anticancer activity against human liver adenocarcinoma (HepG2) cell line with the MTT assay.

Template Synthesis of Polyaza Macrocyclic Copper(II) and Nickel(II) Complexes: Spectral Characterization and Antimicrobial Studies

  • Gurumoorthy, P.;Ravichandran, J.;Karthikeyan, N.;Palani, P.;Rahiman, A. Kalilur
    • Bulletin of the Korean Chemical Society
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    • v.33 no.7
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    • pp.2279-2286
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    • 2012
  • The template synthesis of copper(II) and nickel(II) complexes derived from 2,6-diformyl-4-methylphenol with diethylenetriamine or 1,2-bis(3-aminopropylamino)ethane produce the 12-membered $N_3O$ and 17-membered $N_4O$ macrocyclic complexes, respectively. The geometry of the complexes has been determined with the help of electronic and EPR spectroscopic values and found to be five coordinated square pyramidal and, six coordinated distorted tetragonal for 12-membered and 17-membered macrocyclic complexes, respectively. Electrochemical studies of the mononuclear $N_3O$ and $N_4O$ copper(II) complexes show one irreversible oneelectron reduction wave at $E_{pc}=-1.35$ and -1.15 V respectively, and the corresponding nickel(II) complexes show irreversible one-electron reduction wave at $E_{pc}=-1.25$ and -1.22 V, respectively. The nickel(II) complexes show irreversible one-electron oxidation wave at $E_{pa}=+0.84$ and +0.82 V, respectively. All the complexes were evaluated for in vitro antimicrobial activity against the human pathogenic bacteria and fungi.

Polymeric Lead(II)-selective Electrode Based on N,N'-Bis-thiophen-2-ylmethylene-pyridine-2,6-diamine as an Ion Carrier

  • Kim, Hee-Cheol;Lee, Hyo-Kyoung;Choi, A-Young;Jeon, Seung-Won
    • Bulletin of the Korean Chemical Society
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    • v.28 no.4
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    • pp.538-542
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    • 2007
  • Polymeric electrodes for lead ion based on N,N'-bis-thiophen-2-ylmethylene-pyridine-2,6-diamine as an ion carrier were prepared. The membrane electrode (m-3) containing o-NPOE as a plasticizer and 50 mol% additive of ionophore gives an excellent Nernstian response (29.59 mV/decade) and the limit of detection of ?log a (M) = 5.74 to Pb2+ in Pb(NO3)2 solution at room temperature. The prepared electrode provided good sensitivity and outstanding selectivity and response for Pb2+ over a wide variety of other metal ions in pH 7.0 buffer solutions. The good sensitivity and selectivity towards lead ion are attributed to the strong complexation of lead ion to N,N'-bis-thiophen-2-ylmethylene-pyridine-2,6-diamine which has geometrically the proper cavity to coordinate to the ligand.

Interaction of ct-DNA with 2,4-Dihydroxy Salophen

  • Azani, Mohammad-Reza;Hassanpour, Azin;Bordbar, Abdol-Khalegh;Mirkhani, Valiollah
    • Bulletin of the Korean Chemical Society
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    • v.30 no.9
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    • pp.1973-1977
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    • 2009
  • In the present study, at first, 2,4-Dihydroxy Salophen (2,4-DHS), has been synthesized by combination of 1, 2-diaminobenzene and 2,4-dihydroxybenzaldehyde in a solvent system. This ligand containing meta-quinone functional groups were characterized using UV-Vis and IR spectroscopies. Subsequently, the interaction between native calf thymus deoxyribonucleic acid (ct-DNA) and 2,4-DHS, was investigated in 10 mM Tris/HCl buffer solution, pH 7.2, using UV-visible absorption and fluorescence spectroscopies, thermal denaturation technique and viscosity measurements. From spectrophotometric titration experiments, the binding constant of 2,4-DHS with ct-DNA was found to be (1.1 ${\pm}\;0.2)\;{\times}\;10^4\;M^{-1}.$ The fluorescence study represents the quenching effect of 2,4-DHS on bound ethidium bromide to DNA. The quenching process obeys linear Stern-Volmer equation in extended range of 2,4-DHS concentration. Thermal denaturation experiments represent the increasing of melting temperature of DNA (about 3.5 ${^{\circ}C}$) due to binding of 2,4-DHS. These results are consistent with a binding mode dominated by interactions with the groove of ct-DNA.

Kinetic Studies of the Hydrolysis of 1-Arylpyrrole Imine (1-Arylpyrrole Imine의 가수분해 반응의 속도론적 연구)

  • Hak-Soo Lyu;Hee-Ju Chae
    • Journal of the Korean Chemical Society
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    • v.27 no.2
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    • pp.133-141
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    • 1983
  • The kinetics of the acid-catalyzed hydrolysis of a series of 1-aryl-2-pyrrylideneaniline (3) have been studied in 20% MeOH solution using UV spectrophotometer. Substituents in 3 showed a relatively small effect, with hydrolysis facilitated by electron withdrawing group. By obtaing linear plots of $log k_{obs}$ against Hammett ${\sigma}$ constants, it was able to show that substituents had a considerable contribution to the aromaticity of pyrrole compounds. The small positive ${\rho}$ values were consistent with the rate-determining addition of water to the protonated schiff base in the buffer solution of pH 4 to 8, whereas the addition of water to the free imine seemed to be the rate-determining in the solution of acidities greater than pH 8.

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Study on Solvent Extraction Using Salen(NEt2)2 as a Chelating Agent for Determination of Trace Cu(II), Mn(II), and Zn(II) in Water Samples

  • In, Gyo;Kim, Young-Sang;Choi, Jong-Moon
    • Bulletin of the Korean Chemical Society
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    • v.29 no.5
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    • pp.969-973
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    • 2008
  • Solvent extraction using a Schiff-base, salen$(NEt_2)_2$, as a chelating agent has been conducted on several water samples to study the determination of trace Cu(II), Mn(II) and Zn(II). Experimental conditions for the formation and extraction of metal complexes were optimized with an aqueous solution similar in composition to the samples. The matrix difference between the sample and standard solutions was approximately matched, and the pH of each sample solution was adjusted to 9.5 with $NaHCO_3/NaOH$ buffer. The concentration of salen$(NEt_2)_2$ was $7.3\;{\times}\;10^{-3}$ mol/L, and the complexes were extracted into MIBK solvent followed by the measurement of AAS absorbance. The potential interference of concomitant ions was investigated, but no interference from alkaline and alkali earth ions was shown in this procedure. The given procedure is precise, as judged from the relative standard deviation of less than 5% for five measured data. The recovery of 93-103% shows that this method is quantitative for such trace metal analysis.

Influence of Arg72 of pharaonis Phoborhodopsin on M-intermediate Decay and Proton Pumping Activity

  • Ikeura, Yukako;Shimono, Kazumi;Iwamoto, Masayuki;Sudo, Yuki;Kamo, Naoki
    • Journal of Photoscience
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    • v.9 no.2
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    • pp.311-313
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    • 2002
  • X-ray structures of pharaonis phoborhodopsin (ppR) show the different direction of the side chain of Arg72 from that of the corresponding residue (Arg82) of bacteriorhodopsin, BR. For BR, this residue is considered to play an important role in the proton pumping. In order to investigate the role of Arg72 in ppR, we constructed Arg72 mutants of R72A, R72K and R72Q, and measured the photocycle and proton pumping activities. The pH-titration curves on the absorption maximum of the mutants were shifted to alkaline in comparison of that of the wild-type. This may imply the increase of pKa of D75, suggesting the presence of the (probably electric) interaction between D75 and Arg72. Rate constants of the M-decay were 3-7 times faster than that of the wild-type, and the time for the completion of the photocycling was also reduced. Using Sn0$_2$ electrode, the rate of transmembrane proton transport was measured upon illumination. The photo-induced proton pumping activities were estimated after the corrections that are the percentages of the associated form of D75 (which has no pumping activity) and the photocycling rates. R72A and R72Q showed the reduced activity while R72K did not reduce the activity.

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PHOTOCATALYTIC SYNTHESIS OF L-PIPECOLINIC ACID FROM $N_{varepsilon}$-CARBAMYL-L-LYSINE BY AQUEOUS SUSPENSION OF PLATINIZED TITANIUM(IV) OXIDE

  • Ohtani, Bunsho;Aoki, Eishiro;Iwai, Kunihiro;Nishimoto, Sei-Ichi
    • Journal of Photoscience
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    • v.1 no.1
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    • pp.31-37
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    • 1994
  • Photoirradiation at > 300 nm onto a suspension of platinized TiO$_2$ (TiO$_2$-Pt) particles in an aqueous solution. of N$_{\varepsilon}$-carbamyI-L-lysine (Lys(CONH)$_2$) induced the selective N-cyclization of Lys(CONH$_2$) into almost optically pure L-pipecolinic acid (PCA) under argon atmosphere at ambient temperature. Among various TiO$_2$-Pt catalysts, a P-25 (Degussa) powder platinized via impregnation from chloroplatinic acid followed by hydrogen reduction at 753 K exhibited the highest photocatalytic activity for Lys(CONH$_2$) consumption and L-PCA production. GC-MS analyses of L-PCA obtained photocatalytically from $^{15}$N$\alpha$-Lys(CONH$_2$) revealed the selective formation $^{15}$N-substituted L-PCA. This implies that the mechanism for L-PCA production contains selective cleavage of C$_{\varepsilon}$-N bond and intramolecular alkylation at $\alpha$-amino group. Effect of pH on the rate of this photocatalytic reaction was investigated in detail and compared with the pH-dependent charge distribution in Lys(CONH$_2$) molecule. It is clarified that protonation-deprotonation of $\alpha$-amino group gives marked influence on the rate and selectivity of the photocatalytic reaction. On the basis of these results, it is concluded that the selective production of optically pure L-PCA, especially in an acidic suspension of TiO$_2$-Pt, was attributed to the enhanced protonation of $\alpha$-amino group to prevent undesirable oxidation by photogenerated positive holes and blocking of $\varepsilon$-amino group to yield racemic Schiff base intermediate.

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