• 제목/요약/키워드: Schiff-base

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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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    • 제29권5호
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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.

Structures of Zymomonas 2-Keto-3-Deoxy-6-Phosphogluconate Aldolase with and without a Substrate Analog at the Phosphate-Binding Loop

  • Seo, Pil-Won;Ryu, Ho-Chang;Gu, Do-Heon;Park, Hee-Sae;Park, Suk-Youl;Kim, Jeong-Sun
    • Journal of Microbiology and Biotechnology
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    • 제28권8호
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    • pp.1339-1345
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    • 2018
  • 2-Keto-3-deoxy-6-phosphogluconate (KDPG) aldolase, which catalyzes aldol cleavage and condensation reactions, has two distinct substrate-binding sites. The substrate-binding mode at the catalytic site and Schiff-base formation have been well studied. However, structural information on the phosphate-binding loop (P-loop) is limited. Zymomonas mobilis KDPG aldolase is one of the aldolases with a wide substrate spectrum. Its structure in complex with the substrate-mimicking 3-phosphoglycerate (3PG) shows that the phosphate moiety of 3PG interacts with the P-loop and a nearby conserved serine residue. 3PG-binding to the P-loop replaces water molecules aligned from the P-loop to the catalytic site, as observed in the apostructure. The extra electron density near the P-loop and comparison with other aldolases suggest the diversity and flexibility of the serine-containing loop among KDPG aldolases. These structural data may help to understand the substrate-binding mode and the broad substrate specificity of the Zymomonas KDPG aldolase.

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

  • Arthi, P.;Shobana, S.;Srinivasan, P.;Rahiman, A. Kalilur
    • 통합자연과학논문집
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    • 제7권4호
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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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    • 제33권7호
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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.

Halide (Cl-, Br-, I-) Influence on the Electronic Properties of Macrocyclic Nickel(II) Complexes: Ab-initio DFT Study

  • Zarei, Seyed Amir;Akhtari, Keivan;Hassanzadeh, Keyumars;Piltan, Mohammad;Saaidpour, Saadi;Abedi, Marjan
    • 대한화학회지
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    • 제57권3호
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    • pp.311-315
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    • 2013
  • The geometry structures of hexa-coordinated [NiLX]X complexes ($X=Cl^-,\;Br^-,\;I^-$) {L = 8,9,18,19-tetrahydro-7H,17H-dibenzo[f,o] [1,5,9,13]dioxadiaza cyclohexadecine-8,18-diol} are optimized by density functional theory (DFT) using B3LYP/LANL2DZ. The calculated geometric parameters are in good agreement with the corresponding experimental values. Calculation results about these complexes show that dipole moment decreases, and the energy levels of HOMOs descend from iodo-complex to chloro-complex. The energy levels of HOMOs descend gently from iodo-complex to chloro-complex, while the energy levels of LUMOs in the present complexes are almost similar; therefore the energy gapes between HOMOs and LUMOs increased from iodo-complex to chloro-complex.

Synthesis and Liquid Crystalline Properties of the Compounds Consisting of a Schiff Base Type Mesogen and a Dyad Type Aromatic Ester Structure Interconnected Through the Central Hexamethylene Spacer

  • Jung-Il Jin;Hyo-Seok Kim;Jin-Wook Shin;Bong Young Chung;Byung-Wook Jo
    • Bulletin of the Korean Chemical Society
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    • 제11권3호
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    • pp.209-214
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    • 1990
  • A series of compounds consisting of 4'-oxybenzylidene-4-n-butylaniline, a mesogen, and a p-substituted phenoxyterephthaloyl structure a non-mesogen, interconnected through a central hexamethylene spacer were synthesized and their thermal behavior and liquid crystallinity were studied. p-Substituents included in this study are H, Cl, CN, $NO_2,\;n-C_4H_9O$ and phenyl groups. The compounds having phenyl and $n-C_4H_9O$ substituents are enantiotropic and form smectic-A(SA) and nematic (N) phases. The compound with $NO_2$ substituent is monotropic and forms only a nematic phase on heating the solid, whereas it forms nematic as well as $S_A$ phases on cooling the isotropic liquid. The rest compounds were found to be non-liquid crystalline. This is in great contrast to the fact that the monomesogenic model compound 4'-n-hexyloxybenzylidine-4-n-butylaniline forms $S_B,\;S_C,\;S_A$ and N phases enantiotropically.

Tris(2-cyclohexylaminoethyl)amine-Zn(II) 착물의 안정성 (Stability of Tris(2-cyclohexylaminoethyl)amine-Zn(II) Complex)

  • 신용운;백현숙;양재경;김진은;서무룡
    • 대한화학회지
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    • 제47권2호
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    • pp.121-126
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    • 2003
  • Cyclohexanone,과 tris(2-aminoethyl)amine을 이용하여 Schiff 연기 축합반응으로 tren의 유도체인 tris(2-cyclohexylaminoethyl)amine (L)을 합성하였다. 또한 합성한 tren의 유도체인 tris(2-cyclohexylaminoethyl)amine (L)과 Zn(II) 착물의 열역학적 특성과 안정도 상수, Zn(II)와의 착물 조성비 등을 순환전압전류법과 열량계법으로 측정하였다. Zn(II)과 [Zn(II)-L] 순환전압전류 곡선을 0${sim}$-1.5 V vs. Ag/AgCl의 가전압 범위에서 측정하였다. 금속인 경우, -1.02V와 -0.48V vs. Ag/AgCl에서 각각 환원피이크와 산화피이크가 나타났으며, 금속착물인 경우에는 -1.19V와 -0.45V vs. Ag/AgCl에서 각각 환원피이크와 산화피이크가 나타났다. 또한 피이크 전류(IP)는 주사속도의 평방근 $(v^{1/2})$에 비례하였으며 이것은 전류의 유형이 확산 지배적인 전류임을 나타낸다. 그리고 [Zn-L] 착물에 대해서 전압전류법적으로 구한 안정도상수는 logK$_f$ = 5.8, 결합비는 1:1을 나타내었다. 또한 열량계법적으로 [Zn-L] 착물의 열역학적 파라메타를 조사한 결과, 리간드 L과 Zn(II)는 1:1의 4 배위수를 가지는 착물을 이룬다는 것을 알 수 있었고, 이때 25 ${\circ}$C에서 logK=5.4, ${\Delta}H$= -53.0 kJ/mol, ${\Delta}$G의 값은 -31.1 kJ/mol이었으며 T${\Delta}$S는 -21.9 J/K${\cdot}$mole이었다.

Low-Temperature FTIR Spectroscopy of Bacteriorhodopsin and Phoborhodopsin

  • Kandori, Hideki;Furutani, Yuji;Shimono, Kazumi;Iwamoto, Masayuki;Sudo, Yuki;Shichida, Yoshinori;Kamo, Naoki
    • Journal of Photoscience
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    • 제9권2호
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    • pp.106-109
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    • 2002
  • Archaeal rhodopsins possess retinal molecule as their chromophores, and their light-energy and light-signal conversions are triggered by all-trans to 13-cis isomerization of the retinal chromophore. Relaxation through structural changes of protein then leads to functional processes, proton pump in bacteriorhodopsin (bR) and transducer activation in phoborhodopsin (pR). It is known that sensory rhodopsins can pump protons in the absence of their transducers. Thus, there should be common and specific features in their protein structural changes for function. In this paper, our r ecent studies on pR from Natronobacterium pharaonis (ppR) by means of low-temperature Fourier-transform infrared (FTIR) spectroscopy are compared with those of bR. In particular, protein structural changes upon retinal photoisomerization are studied. Comparative investigation of ppR and bR revealed the similar structures of the polyene chain of the chromophore and water-containing hydrogen-bonding network, whereas the structural changes upon photoisomerization were more extended in ppR than in bR. Extended protein structural changes were clearly shown by the assignment of the C=O stretch of Asnl05. FTIR studies of a ppR mutant with the same retinal binding site as in bR revealed that the Schiff base region is important to determine their colors.

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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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    • 제9권2호
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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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근접장 마이크로파 현미경을 이용한 로돕신의 광학적 특성 연구 (Optical Characterization of Sensory Rhodopsin II Thin Films using a Near-field Scanning Microwave Microscope)

  • 유경선;김송희;윤영운;이기진;이정하;최아름;정광환
    • 한국전기전자재료학회논문지
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    • 제20권1호
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    • pp.80-85
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    • 2007
  • We report the electro-optical properties of the sensory rhodopsin II using a near-field scanning microwave microscope(NSMM). Rhodopsin was known as a photoreceptor pigment with a retinal as a chromophore via a protonated Schiff base and consists of seven ${\alpha}-helical$ transmembrane segments. The sensory rhodopsin II, expressing E. coli UT5600 with endogenous retinal biosynthesis system and purified with $Ni^{-2}-NTA$ affinity chromatography in the presence of 0.02 % DM (Dodecyl Maltoside) from Natronomonas pharaonis. We measured the absorption spectra and the transients difference of sensory rhodopsin II from Natronomonas pharaonis using a UV/VIS spectrophotometer with Nd-Yag Laser (532 nm). The absorption spectra of NpSR II showed a typical rhodopsin spectrum with a left shoulder region and the photointermediates spectra of NpSR II-ground state (${\lambda}max=498\;nm$), NpSR II-M state (${\lambda}max=390\;nm$), and NpSR II-O state (${\lambda}max=550\;nm$) during the photocycle. The observed photocycle reaction was confirmed by measuring the microwave reflection coefficient $S_{11}$ at an operating frequency of f=3.93-3.95 GHz and compared with the results of a photocycle of NpSR II.