• Title/Summary/Keyword: Organic ligand

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Synthesis of a New α-Dioxime Derivative and Its Application for Selective Homogeneous Liquid-Liquid Extraction of Cu(II) into a Microdroplet Followed by Direct GFAAS Determination

  • Ghiasvand, A. R.;Shadabi, S.;Kakanejadifard, A.;Khajehkoolaki, A.
    • Bulletin of the Korean Chemical Society
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    • v.26 no.5
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    • pp.781-785
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    • 2005
  • A fast and reliable method for the selective separation and preconcentration of $Cu^{2+}$ ions using homogeneous liquid-liquid extraction was developed. A new $\alpha$-dioxime derivative (2H-1,4-benzothioazine-2,3(4H)dionedioxime, Dioxime I) was synthesized and investigated as a suitable selective complexing ligand for $Cu^{2+}$ ions. Zonyl FSA (FSA) was applied as a phase-separator agent under the slightly acidic pH conditions. Under the optimal experimental conditions ([FSA] = 3.2% w/v, [THF] = 19.5% v/v, [Dioxime I] = 1.9 ${\times}\;10^{-3}$ M, and pH = 4.7), 10 ${\mu}g\;of\;Cu^{2+}$ in 5.2 mL aqueous phase could be extracted quantitatively into 80 $\mu$L of the sedimented phase. The maximum concentration factor was 65-fold. The limit of detection of the proposed method was 0.005 ng $mL^{-1}$. The reproducibility of the proposed method, on the 10 replicate measurements, was 1.3%. The influence of the pH, type and volume of the water-miscible organic solvent, concentration of FSA, concentration of the complexing ligand and the effect of different diverse ions on the extraction and determination of $Cu^{2+}$ ions were investigated. The proposed method was applied to the extraction and determination of $Cu^{2+}$ ion in different synthetic and natural water samples.

Synthesis of Co(II), Ni(II) and Cu(II) Complexes from Schiff base Ligand and Reactivity Studies with Thermosetting Epoxy Resin

  • Lakshmi, B.;Shivananda, K.N.;Prakash, Gouda Avaji;Rama, Krishna Reddy K.;Mahendra, K.N.
    • Bulletin of the Korean Chemical Society
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    • v.32 no.5
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    • pp.1613-1619
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    • 2011
  • A hybrid thermosetting maleimido epoxy compound 4-(N-maleimidophenyl) glycidylether (N-MPGE) containing Co(II), Ni(II) and Cu(II) ions was prepared by curing N-MPGE and tetradentate Schiff base Co(II), Ni(II) and Cu(II) complexes. The curing polymerization reaction of N-MPGE with metal complexes as curing agents was studied. The cured samples were studied for thermal stability, chemical (acid/alkali/solvent) and water absorption resistance and homogeneity of the cured systems. The tetradentate Schiff base, 3-[(Z)-2-piperazin-1-yl-ethylimino]-1,3-dihydro indol-2-one was synthesized by the condensation of Isatin (Indole-2, 3-dione) with 1-(2-aminoethyl)piperazine (AEP). Its complexes with Co(II), Ni(II) and Cu(II) have been synthesized and characterized by microanalysis, conductivity, Uv-Visible, FT-IR, TGA and magnetic susceptibility measurements. The spectral data revealed that the ligand acts as a neutral tetradentate Schiff base and coordinating through the azomethine nitrogen, two piperazine nitrogen atoms and carbonyl oxygen.

Characterization and Synthesis of Titanium (IV) Isopropoxide Derivatives (Titanium(IV) isoproxide 유도체의 합성 및 특성연구)

  • Jung, Mie-Won
    • Analytical Science and Technology
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    • v.12 no.6
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    • pp.509-514
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    • 1999
  • The systematic modification of titanium(IV) isopropoxide with acetic acid as a organic additive was done and identifided by FT-IR, $^1H$, $^{13}C$ NMR and UV-Vis spectroscopy. The structure was cbanged after hydrolysis-condensation reaction and drying process. The hydrolysis-condensation rates of modified Ti alkoxide with acetic acid were investigated by $^1H$ NMR spectroscopy. This modified Ti(IV) alkoxide was less reactive toward hydrolysis-condensation reaction than $Ti(OPr^i)_4$, which can be attributed to the stable ligand structure between Ti alkoxide and ligand. The structural change on obtained from gel powders with heat treatment was also observed by FT-IR spectroscopy.

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Enzyme-Conjugated CdSe/ZnS Quantum Dot Biosensors for Glucose Detection

  • Kim, Gang-Il;Sung, Yun-Mo
    • Korean Journal of Materials Research
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    • v.19 no.1
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    • pp.44-49
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    • 2009
  • Conjugated nanocrystals using CdSe/ZnS core/shell nanocrystal quantum dots modified by organic linkers and glucose oxidase (GOx) were prepared for use as biosensors. The trioctylphophine oxide (TOPO)-capped QDs were first modified to give them water-solubility by terminal carboxyl groups that were bonded to the amino groups of GOx through an EDC/NHS coupling reaction. As the glucose concentration increased, the photoluminescence intensity was enhanced linearly due to the electron transfer during the enzymatic reaction. The UV-visible spectra of the as-prepared QDs are identical to that of QDs-MAA. This shows that these QDs do not become agglomerated during ligand exchanges. A photoluminescence (PL) spectroscopic study showed that the PL intensity of the QDs-GOx bioconjugates was increased in the presence of glucose. These glucose sensors showed linearity up to approximately 15 mM and became gradually saturated above 15 mM because the excess glucose did not affect the enzymatic oxidation reaction past that amount. These biosensors show highly sensitive variation in terms of their photoluminescence depending on the glucose concentration.

Portable Amperometric Perchlorate Selective Sensors with Microhole Array-water/organic Gel Interfaces

  • Lee, Sang Hyuk;Kim, Hyungi;Girault, Hubert H.;Lee, Hye Jin
    • Bulletin of the Korean Chemical Society
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    • v.34 no.9
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    • pp.2577-2582
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    • 2013
  • A novel stick-shaped portable sensing device featuring a microhole array interface between the polyvinylchloride-2-nitrophenyloctylether (PVC-NPOE) gel and water phase was developed for in-situ sensing of perchlorate ions in real water samples. Perchlorate sensitive sensing responses were obtained based on measuring the current changes with respect to the assisted transfer reaction of perchlorate ions by a perchlorate selective ligand namely, bis(dibenzoylmethanato)Ni(II) (Ni(DBM)2) across the polarized microhole array interface. Cyclic voltammetry was used to characterize the assisted transfer reaction of perchlorate ions by the $Ni(DBM)_2$ ligand when using the portable sensing device. The current response for the transfer of perchlorate anions by $Ni(DBM)_2$ across the micro-water/gel interface linearly increased as a function of the perchlorate ion concentration. The technique of differential pulse stripping voltammetry was also utilized to improve the sensitivity of the perchlorate anion detection down to 10 ppb. This was acquired by preconcentrating perchlorate anions in the gel layer by means of holding the ion transfer potential at 0 mV (vs. Ag/AgCl) for 30 s followed by stripping the complexed perchlorate ion with the ligand. The effect of various potential interfering anions on the perchlorate sensor was also investigated and showed an excellent selectivity over $Br^-$, $NO_2{^-}$, $NO_3{^-}$, $CO{_3}^{2^-}$, $CH_3COO^-$ and $SO{_4}^{2^-}$ ions. As a final demonstration, some regional water samples from the Sincheon river in Daegu city were analyzed and the data was verified with that of ion chromatography (IC) analysis from one of the Korean-certified water quality evaluation centers.

Influence of Preparation Conditions on the Formation of Copper (II) Architectures with Pyrazine-2,3,5-tricarboxylic Acid

  • Wang, Feng-Qin;Lin, Shu;Guo, Ming-Lin;Xu, Jun-Jian;Wang, Xiao-Qing;Zhao, Yong-Nan
    • Bulletin of the Korean Chemical Society
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    • v.32 no.7
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    • pp.2351-2357
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    • 2011
  • Three new metal-organic copper(II) complexes, $[Cu(H_2PZTC)_2]_n{\cdot}2nH_2O$ (1), $[Cu(HPZTC){\cdot}2H_2O]_n{\cdot}2nH_2O$ (2), and $Cu_2[(PZHD)(OH)(H_2O)_2]_n$ (3) ($H_3PZTC$ = pyrazine-2,3,5-tricarboxylic acid, $PZHD^{3-}$ = 2-hydroxypyrazine-3,5-dicarboxylate), have been synthesized from $Cu(II)/H_3PZTC$ system under different synthetic conditions, and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and thermogravimetric analysis. In complexes 1 and 2, $H_3PZTC$ ligands loose one and two protons, which were transformed into $H_2PZTC^-$ anion and $HPZTC^{2-}$ dianion under different preparation condition, respectively. Furthermore, two ligands coordinate with Cu(II) cations in different modes, leading to the formation of the different chain structures. In complex 3, $H_3PZTC$ ligand was converted into a new ligand-PZHD by in situ decarboxylation and hydroxylation under a higher pH value than that for complexes 1 and 2. PZHD ligands link the Cu(II) cations to form a 2D layer structure. These results demonstrate that the preparation conditions, including pH value and reaction temperature etc, play an important role in the construction of complexes based on $H_3PZTC$ ligand.

Chiral Mesoporous Silica for Asymmetric Metal-free Catalysis: Enhancement of Chirality thorough Confinement Space by Plug Effect

  • Jeong, Eun-Yeong;Im, Cheong-Rae;Park, Sang-Eon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.08a
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    • pp.199-199
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    • 2011
  • The addition of a carbanion to ${\yen}{\acute{a}}{\yen}{\hat{a}}$-unsaturated carbonyl compounds is of importance in the C-C bond formation reactions for modern pharmaceuticals and organic synthesis. Recently, heterogeneous asymmetric catalysis became more attractive area of research because of the easy recovery and separation of the catalyst from the reaction system. Most of synthetic methods for heterogeneous catalysts were grafting or immobilization of homogeneous catalyst onto the solid supports. Trans-1,2-Diaminocyclohexane(DACH) and L-proline ligands have been enormously used as chiral ligands in several catalytic transformation under homogenous conditions. Our group prepared l-proline functionalized mesoporous silica was synthesized under acidic condition using a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer template (EO20PO70EO20, Pluronic P-123, BASF). Furthermore, we successfully directly synthesized trans-1,2 diaminocyclohexane functionalized mesoporous silica by using microwave method. The direct functionalization of chiral ligand into the framework of mesoporous materials is expected to be useful for the heterogeneous asymmetric catalysis. So, we adopt the direct synthesis of chiral ligand functionalized mesoporous silica by using thermal and microwave irradiation. Then, chiral ligand functionalized mesoporous silicas were applied to enantioselective asymmetric catalytic reactions.

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Research Trend of Metal-Organic Frameworks for Magnetic Refrigeration Materials Application (자기 냉동 재료 응용을 위한 MOF의 연구 동향)

  • Kim, Suhwan;Son, Kwanghyo;Oh, Hyunchul
    • Korean Journal of Materials Research
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    • v.30 no.3
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    • pp.136-141
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    • 2020
  • The magnetocaloric effect (MCE), which is the reversible temperature change of magnetic materials due to an applied magnetic field, occurs largely in the vicinity of the magnetic phase transition temperature. This phenomenon can be used to induce magnetic refrigeration, a viable, energy-efficient solid-state cooling technology. Recently, Metal-organic frameworks (MOFs), due to their structural diversity of tunable crystalline pore structure and chemical functionality, have been studied as good candidates for magnetic refrigeration materials in the cryogenic region. In cryogenic cooling applications, MCE using MOF can have great potential, and is even considered comparable to conventional lanthanum alloys and magnetic nanoparticles. Owing to the presence of large internal pores, however, MOF also exhibits the drawback of low magnetic density. To overcome this problem, therefore, recent reports in literature that achieve high magnetic entropy change using a dense structure formation and ligand tuning are introduced.

Synthesis and Application of the Novel Azomethine Metal Complexes for the Organic Electroluminescent Devices

  • Kim, Seong Min;Kim, Jin Sun;Sin, Dong Myeong;Kim, Yeong Gwan;Ha, Yun Gyeong
    • Bulletin of the Korean Chemical Society
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    • v.22 no.7
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    • pp.743-747
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    • 2001
  • New azomethine metal complexes were synthesized systematically and characterized. Beryllium, magnesium, or zinc ions were used as a central metal cation and aromatic azomethines (L1-L4) were employed as a chelating anionic ligand. Emission peaks o f the complexes in both solution and solid states were observed mostly at the region of 400-500 nm in the luminescence spectra, where blue light was emitted. Three of them (BeL1 (Ⅰ), ZnL2 (Ⅱ), and ZnL3 (Ⅲ)) were sublimable and thus were applied to the organic light-emitting devices (OLED) as an emitting layer, respectively. The device including the emitting layer of Ⅰ exhibited white emission with the broad luminescence spectral range. The device with the emitting layer of Ⅱ showed blue luminescence with the maximum emission peak at 460 nm. Their ionization potentials, electron affinities, and electrochemical band gaps were investigated with cyclic voltammetry. The electrochemical gaps of 2.98 for I, 2.70 for Ⅱ, and 2.63 eV for Ⅲ were found to be consistent with their respective optical band gaps of 3.01, 2.95 and 2.61 eV within an experimental error. The structure of OLED manufactured in this study reveals that these complexes can work as electron transporting materials as well.

Effects of Organic Acids on Availability of Phosphate and Growth of Corn in Phosphate and Salts Accumulated Soil

  • Kim, Myung-Sook;Park, Seong-Jin;Lee, Chang-Hoon;Yun, Sun-Gang;Ko, Byong-Gu;Yang, Jae E.
    • Korean Journal of Soil Science and Fertilizer
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    • v.49 no.3
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    • pp.265-270
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    • 2016
  • Accumulated Phosphate can be released by ligand exchange reaction of organic acids. The objective of this study was to evaluate effects of the organic acids on the availability of phosphate and the growth of crop in phosphate and salts accumulated soil. Soil samples were collected from farmer's plastic film house. Available phosphate and electrical conductivity of soil were $3,005mg\;kg^{-1}$ and $16.63mg\;kg^{-1}$ which were 6 and 8 times higher than the optimum range of soil for crop growth, respectively. Corns were cultivated in pots for 2 months. Treatments were no treatment (control), phosphate fertilizer (P), citric acid (CA) 1, 5, 10 mM, and oxalic acid (OA) 1, 5, 10 mM. Water soluble phosphorus, available phosphate, corn growth and uptake were determined after cultivation. Results showed that organic acids increased water soluble phosphorus and available phosphate. For the level of 10 mM, the order of effectiveness of organic acids for water soluble P was citric acid (44%) > oxalic acid (32%). Height and dry weight of corns were increased significantly by the treatment of citric acid 1 and 5 mM. Also, corn absorbed more phosphorus, nitrogen, potassium, calcium and magnesium in the treatment of citric acid 1 mM than these of other treatments. Even though phosphate availability of soil was enhanced by addition of citric acid 10 mM, the growth of corns decreased because high concentration of citric acid caused salt damage by increasement of electrical conductivity. Thus, the citric acid of 1 mM has the potential to improve the availability of phosphate and the healthy growth of corns.