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

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Importance of The Location of The Negative-charged Counter-ion against The Protonated Schiff Base on The Chromophore Configuration of pharaonis Phoborhodopsin

  • Shimono, Kazumi;Ikeura, Yukako;Sudo, Yuki;Iwamoto, Masayuki;Kamo, Naoki
    • Journal of Photoscience
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    • v.9 no.2
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    • pp.302-304
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    • 2002
  • pharaonis phoborhodopsin (ppR), a photophobic sensor of haloalkaliphilic bacteria, Natronobacterium phar-aonis, has retinal as a chromophore covalently bound to Lys in G-helix via a protonated Schiff base (PSB), as is the same as bacteriorhodopsin (bR). For ppR, the corresponding counter-ion is Asp residue (Asp75) located in C-helix. Here we investigated the influence of the protonated state of this counter-ion and its location on the chromophore configuration. Under alkaline condition, the chromophore configuration of D75E mutant was analyzed by HPLC. D75E had a much larger content of 13-cis isomer: the ratio of 13-cis to all-trans was 6:4 while the wild-type had this ratio of 1 :9. On the other hand, under acidic condition where Glu was associated, D75E had no 13-cis retinal isomer. Mutants whose Asp75 was replaced by neutral amino acids (D75N and D75Q) did not contain 13-cis retinal. Furthermore, retinal isomer compositions and the change in the visible ab- sorption spectra (indicating the dissociation state of Glu75) were measured under varying pH, and these were almost the same dependencies. These results indicate that an important factor determining the 13-cis isomer content is the presence of negative charge of the counter-ion against PSB, but not the size of this residue. Com- parison between the wild-type and D75E in alkaline solutions indicates the influence of the location of the counter-ion.

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Preparation of L-cysteine Salicylaldehyde Schiff-base Modified Macroporous Polystyrene Resin and Its Application to Determination of Trace Cadmium and Lead in Environmental Water Samples

  • Xie, Fazhi;Zhang, Fengjun;Xuan, Han;Ge, Yejun;Wang, Yin;Li, Guolian;Zhu, Lei;Oh, Won-Chun
    • Journal of the Korean Ceramic Society
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    • v.51 no.5
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    • pp.472-476
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    • 2014
  • In this work, a new method that utilizes L-cysteine salicylaldehyde Schiff-base modified macroporous polystyrene resin (PS-CSC) as an effective sorbent has been developed for preconcentration of trace cadmium and lead in environmental water samples. The effect of pH, the contact time, the elution conditions, the flow rate, the initial concentration of target metal ions, and the effects of interfering ions on the preconcentration of the analytes were investigated. The maximum adsorption capacity of PS-CSC under optimum conditions for cadmium and lead were found to be 6.03 - 18.17 mg/g and 12.58 - 36.13 mg/g when the initial concentration of metal ions between 5.0 - 90 mg/L. The limits of detection for cadmium and lead were 2.46 ng/L and $0.52{\mu}g/L$, with a preconcentration factor of 200. The developed method has been validated by analyzing certified reference material and successfully applied for the enrichment and determination of trace cadmium and lead from environmental water samples.

UO22+ Ion-Selective Membrane Electrode Based on a Naphthol-Derivative Schiff's Base 2,2'-[1,2-Ethandiyl bis(nitriloethylidene)]bis(1-naphthalene)

  • Shamsipur, Mojtaba;Saeidi, Mahboubeh;Yari, Abdullah;Yaganeh-Faal, Ali;Mashhadizadeh, Mohammad Hossein;Azimi, Gholamhasan;Naeimi, Hossein;Sharghi, Hashem
    • Bulletin of the Korean Chemical Society
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    • v.25 no.5
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    • pp.629-633
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    • 2004
  • A new PVC membrane electrode for $UO_2^{2+}$ ion based on 2,2'-[1,2-ethanediyl bis (nitriloethylidene)]bis(1-naphthalene) as a suitable ionophore was prepared. The electrode exhibites a Nernstian response for $UO_2^{2+}$ ion over a wide concentration range ($1.0{\times}10^{-1}-1.0{\times}10^{-7}$M) with a slope of 28.5 ${\pm}$ 0.8 mV/decade. The limit of detection is $7.0{\times}10^{-8}$M. The electrode has a response time of < 20 s and a useful working pH range of 3-4. The proposed membrane sensor shows good discriminating abilities towards $UO_2^{2+}$ ion with regard to several alkali, alkaline earth transition and heavy metal ions. It was successfully used to the recovery of uranyl ion from, tap water and, as an indicator electrode, in potentiometric titration of $UO_2^{2+}$ ion with Piroxycam.

Preparation and Mesomorphic Properties of tetramethylene-1,4-bis (p-oxybenzylidene p-substituted aniline) (Tetramethylene-1,4-bis(p-oxybenzylidene p-substituted aniline)의 합성과 액정성)

  • Choi, Ok-Byung;Park, Joo-Hoon;Lee, Yong-Seop;Lee, Whan-Myung;Kim, Ki-Hwan;Lee, Eun-Kyoung;Ko, Kyung-Kon;Lee, Eun-Sang;So, Bong-Keun;Lee, Chang-Joon;Lee, Soo-Min
    • Korean Chemical Engineering Research
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    • v.45 no.2
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    • pp.155-159
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    • 2007
  • A series of new dimesogenic compounds having two identical, terminal Schiff base type mesogens and a central tetramethylene spacer were synthesized. Their thermotropic and mesomorphic properties of the compounds were investigated by differential scanning calorimetry and polarizing microscopy. The compounds with X= -F, -Cl, -Br, -CN and $-OCH_3$ were enantiotropically nematic liquid crystal. In contrast, the compounds with X= -I and $-CF_3$ were non-liquid crystal. The nematic forming efficiency of the groups was in the order of -CN > $-OCH_3$ > -Br > -Cl > -F.

Fluorometric Quantitative Analysis of Al(III) Ion Using 5-Methoxy-2-phenyliminomethylphenol

  • Kim, Sun-Deuk;Lee, Hye-Won
    • Bulletin of the Korean Chemical Society
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    • v.30 no.5
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    • pp.1026-1030
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    • 2009
  • A novel Schiff base ligand (N, O system) 5-methoxy-2-phenyliminomethylphenol ($5-CH_3O-PMP$) was synthesized. Using the synthesized ligand as a fluorescent reagent, a fluorometric method was developed for the quantitative analysis of Al(III) ion. The quantitative analysis of Al(III) ion was performed by making the complex compound between Al(III) ion and $5-CH_3O-PMP$ in ethanol-water solution (85/15, v/v, pH 6.2). The excitation wavelength (${\lambda}em$) of the complex compound was 397 nm while the emmision wavelength (${\lambda}em$) was 498 nm. The quantitative analysis of Al(III) ion was carried out by estimating the fluorescence intensity. The various calibration curves were used for the quantitative analysis in the range of 0.27$\sim$27 ng/mL Al(III) ion concentrations. The detection limit was 0.027 ng/mL. Using the fluorometric method developed in this study, satisfying results were obtained from various samples such as tap water, hot spring water, river water, sea water and waste water, which contained considerable amounts of interfering ions.

FTIR spectroscopy of the two-photon product of sensory rhodopsin I

  • Sasaki, Jun;Kannaka, Masato;Kandori, Hideki;Tokunaga, Fumio
    • Journal of Photoscience
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    • v.9 no.2
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    • pp.534-536
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    • 2002
  • A halophilic archaeon, Halobacterium salinarum, exhibits phototactic behaviors, by which the organism is guided to red-orange light and evades shorter wavelengths of light. The phototaxis is mediated by two retinal proteins, sensory rhodopsin I and II (SRI and SRII), whose structures are analogous to the cognate protein bacteriorhodopsin, a light-driven proton pump. SRI mediates both attractant and repellent swimming behaviors to orange light and near- UV light, respectively. The two different signaling through the single photoreceptor have been ascribed to the presence of two active structures of SRI (S$\_$373/ and P$\_$520), which are produced upon orange light illumination of SRI and upon subsequent near-UV illumination of S$\_$373/, respectively. In the present study, we have measured the difference FTIR spectra of S$\_$373/ and P$\_$520/ states. In P$\_$520/, the isomeric structure of the chromophore is assignable to all-trans, and the Schiff base of the chromophore is protonated with concomitant deprotonation of Asp76, a combination which allows for the formation of a salt bridge between them. It was suggested that the way of interaction between the Schiff base and the counterion, which is different among SRI$\_$587/, S$\_$373/ and P$\_$520/ and which has been shown to drive the conformational changes in the cognate protein, bacteriorhodopsin, is the key to controlling conformational changes for the attractant and the repellent signaling by SRI.

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Electrochemical Properties of Binuclear Cobalt (II) Complexes with Tetradentate Schiff Base in Aprotic Solvents (III) (비수용매에서 이핵성 네자리 Schiff Base Cobalt(II) 착물들의 전기화학적 성질 (제 3 보))

  • Chjo Ki-Hyung;Choi Yong-Kook;Seo Seong-Seob;Lee Song-Ju
    • Journal of the Korean Chemical Society
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    • v.35 no.4
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    • pp.379-388
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    • 1991
  • We synthesized the binuclear Tetradentate Schiff base cobalt (II) complexes; [Co(II)$_2$(SMPD)$_2$(L)$_2$] and [Co(II)$_2$(SPPD)$_2$(L)$_2$] (where, SMPD: N,N'-bis(salicylaldehyde)-m-phenylenediimine, SPPD: N,N'-bis(salicylaldehyde)-p-phenylenediimine, L: Py, DMSO and DMF). We identified the binuclear structure of these complexes by elemental analysis, IR-spectrum, and T. G. A. According to the results of cyclic voltammetry and DPP measurements in aprotic solvents containing 0.1M TEAP as supporting electrolyte, it was found that diffusionally controlled redox process of two step for one electron was reversible or quasi reversible process in 0.1M TEAP-pyridine and 0.1M TEAP-DMSO solution at mononuclear complexes; [Co(II)(SOPD)(L)$_2$]. But, we knew that diffusionally controlled reduction processes of four steps with one electron for binuclear [Co(II)$_2$(SMPD)$_2$(L)$_2$] and [Co(II)$_2$(SPPD)$_2$(L)$_2$] complexes was Co(III)$_2\;{\longrightarrow^e}$ Co(III)Co(II) ${\longrightarrow^e}$ Co(II)$_2\;{\longrightarrow^e}$ Co(II)Co(I) ${\longrightarrow^e}$ Co(I)$_2$ in aprotic solvents.

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Liquid Crystalline Properties of Dimers Having o-, m- and p- Positional Molecular Structures

  • Park, Joo-Hoon;Choi, Ok-Byung;Lee, Hwan-Myung;Lee, Jin-Young;Kim, Sung-Jo;Cha, Eun-Hee;Kim, Dong-Hyun;Ramaraj, B.;So, Bong-Keun;Kim, Kyung-Hwan;Lee, Soo-Min;Yoon, Kuk-Ro
    • Bulletin of the Korean Chemical Society
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    • v.33 no.5
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    • pp.1647-1652
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    • 2012
  • With the objective to design and synthesis of Schiff's base symmetrical liquid crystal dimmers and to study the effect of molecular structure variation ($o-ortho$, $m-meta$, $p-para$) and change in alkoxy terminal chain length on mesomorphic properties of liquid crystals, We have synthesized Schiff base dimers from dialdehyde derivative containing 2-hydroxy-1,3-dioxypropylene as short spacer with aniline derivatives having different lengths of terminal alkoxy chains ($n$ = 5, 7, 9). The chemical structure of the final products was characterized by proton nuclear magnetic resonance ($^1H$ NMR) spectroscopy and fourier transform infrared (FT-IR) spectroscopy. The mesomorphic properties and optical textures of the resultant dimers were characterized by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The existence of smectic A phase transition was confirmed by the observation of batonnets and fan shaped textures in optical microscopy when compound were heated from crystalline phase. All of the dimers of this series, with the exception of $\mathbf{2S_5}$ -ortho, -meta, -para, were thermotropic liquid crystal. The compound $\mathbf{2S_9}$ -meta was monotropic, while the rest were enantiotropic. It was found that the change in terminal alkoxy chain length has pronounced effect on the mesomorphic properties. The temperature range of smectic A phase window widens with increasing alkoxy chain length.

Controlled Drug Delivery through O-Diethylaminoethyl Chitosan Membrane (O-디에칠아미노에칠 키토산막을 통한 약물방출조절)

  • Kim, Jin-Hong;Lee, Young-Moo
    • Journal of Pharmaceutical Investigation
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    • v.22 no.1
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    • pp.23-31
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    • 1992
  • A novel O-diethylaminoethyl chitosan (DEAE-chitosan) was synthesized via Schiff's reaction between chitosan and benzaldehyde. $C_2$ amino group was protected via Schiffs base reaction with benzaldehyde to form N-benzylidene chitosan. After reaction with diethylaminoethyl chloride, Schiffs base was removed by reacting O-diethylaminothyl-N-benzylidene chitosan and hydrochloric acid. Tensile strength of DEAE-chitosan was improved due to the incorporation of bulky side group in $C_6$ position of chitosan. DEAE-chitosan showed a pH-dependent swelling characteristics. Release rate of riboflavin was dependent on the water content of DEAE-chitosan that is a function of crosslinking degrees.

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Determination of Copper in Black, Red Pepper and the Waste Water Samples by a Highly Selective Sensitive Cu(II) Microelectrode Based on a New Hexadentates Schiff's Base

  • Norouzi, Parviz;Ganjali, Mohammad Reza;Faridbod, Farnoush;Salavati-Niasari, Masoud
    • Bulletin of the Korean Chemical Society
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    • v.27 no.9
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    • pp.1439-1444
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    • 2006
  • A $Cu^{2+}$ ion-selective membrane microelectrode has been fabricated from poly vinyl chloride (PVC) matrix membrane containing a new symmetrical hexadentate Schiff,s base 2-{1-(E)-2-((Z)-2-{(E)-2-[(Z)-1-(2-hydroxyphenyl)ethylidene]hydrazono}-1-methylpropylidene)hydrazono]ethyl}phenol (HDNOS) as a neutral carrier, Potassium tetrakis(4-chlorophenyl) borate (KTpClPB) as an anionic excluder and o-nitrophenyloctyl ether (NPOE) as a plasticizing solvent mediator. The microelectrode displays linear potential response in the concentration range of $1.0\;{\times}\;10^{-5}-1.0\;{\times}\;10^{-11}$ M of $Cu^{2+}$. The microelectrode exhibits a nice Nernstian slope of 25.9 ${\pm}$ 0.3 mV $decade^{-1}$ in the pH range of 3.1-8.1. The sensor has a relatively short response time in whole concentration ranges ($\sim$5 s). The detection limit of proposed sensor is $5.0\;{\times}\;10^{-12}$ M (320 pg/L), and it can be used over a period of eight weeks. The practical utility of the sensor has been demonstrated by using it as an indicator electrode in the potentiometric titration of $Cu^{2+}$ with EDTA. The proposed membrane electrode was used for the direct determining of $Cu^{2+}$ content in black and red pepper, and in waste water samples.