• 제목/요약/키워드: Ligand-exchange

검색결과 120건 처리시간 0.018초

Palladium(II) Aryloxides of Pd(2,6-(CH2NMe2)2C6H3)(OC6H4-X-p) (X = Me, NO2): Synthesis, Property and Reactivity towards Diphenyliodium Chloride

  • Jung, Hyun-Sang;Park, Yun-Sik;Seul, Jung-Min;Kim, Jong-Sook;Lee, Ho-Jin;Park, Soon-Heum
    • Bulletin of the Korean Chemical Society
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    • 제32권8호
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    • pp.2711-2716
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    • 2011
  • para-Substituted phenoxide derivatives of Pd(II) having an NCN pincer, Pd(NCN)($OC_6H_4$-p-X) (NCN = 2,6-$(CH_2NMe_2)_2C_6H_3$; X = $NO_2$ (1), Me (2)) were prepared by the reaction of Pd(NCN)($OSO_2CF_3$) with equi-molar amount of $NaOC_6H_4$-p-X. Treatment of Pd(NCN)($OSO_2CF_3$) with an excess amount of $NaOC_6H_4$-p-Me affords the hydrogen-bonding adduct complex 3 ($2{\cdot}HOC_6H_4$-p-Me). Complex 3 can also be obtained from benzene solution of 2 in the presence of free $HOC_6H_4$-p-Me. Complex 1 does not undergo adduct formation with $HOC_6H_4-p-NO_2$ neither from metathesis reaction of Pd(NCN)($OSO_2CF_3$) with an excess amount of $NaOC_6H_4-p-NO_2$ nor from treatment of 1 with free $HOC_6H_4-p-NO_2$. Complex 3 undergoes fast exchange of the coordinated p-cresolate with the hydrogen-bonding p-cresol. Complex 2 undergoes ${\sigma}$-ligand exchange reaction with $HOC_6H_4-p-NO_2$ to give 1. The exchange reaction, however, is irreversible as readily anticipated from their respective $pK_a$ values of the phenol derivatives. Reaction of 2 with diphenyliodium chloride quantitatively produced Pd(NCN)Cl and PhI along with liberation of O-phenylated product $PhOC_6H_4$-p-Me which was identified by GC/MS spectroscopy.

금속-PDC 착물의 음이온교환 수지 상 흡착에 의한 흔적량 코발트와 니켈의 동시 예비농축 및 정량 (Preconcentration and Determination of Trace Cobalt and Nickel by the Adsorption of Metal-PDC Complexes on the Anion-Exchange Resin Suspension)

  • 한철우;인교;최종문;김선태;김영상
    • 분석과학
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    • 제13권5호
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    • pp.608-615
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    • 2000
  • 물 시료에 존재하는 극 미량의 니켈과 코발트를 착물로 형성시켜 이온 교환수지 서스펜션에 흡착시켜 분리 농축하여 정량하는 방법을 연구하였다. 리간드로 APDC (ammonium pyrrolidine dithiocarbamnate)를 사용하여 극 미량 이온들을 착물로 형성시켜 농축한 다음, 전열 원자흡수 분광광도법으로 정량하였다. 이때 착물 형성을 위한 수용액의 pH와 착화제인 APDC의 양, 흡착을 위한 이온교환 수지의 종류 및 저어주는 시간, 역 분산에 사용하는 산의 종류 및 농도, 초음파 진동시간 등의 실험조건들을 최적화 하였다. 시료용액의 pH를 5로 조절하고 APDC의 양을 몰 비로 분석원소 전체의 430배 이상 첨가하여 코발트와 니켈을 정량적으로 착물을 형성시켰다. 이온교환 수지는 음이온 형태의 Dowex 2-X8이 우수하였다. pH를 조절한 시료용액, 리간드 및 수지 서스펜션을 혼합하고 1분간 저어주어 흡착을 완전하게 하였다. 역 분산을 위해서는 0.1 M 염산이 가장 좋았고, 이때 막 필터로 거른 교환 수지를 초음파 진동기에서 7분간 진동하면 충분하였다. 팔라듐을 염산과 함께 사용하면 매트릭스를 개선하여 재현성과 감도가 개선되었다. 바탕흡수 신호표준편차의 세배에 해당하는 검출한계는 Co 0.36 ng/mL, Ni 0.27 ng/mL로 극미량 검출이 가능하였고 시료에 일정량 첨가한 분석원소의 회수율은 각각 99-102%와 100-105% 이었다.

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Indium(III) 화합물의 Acetonitrile 과 DMAP 착물의 합성 및 특성 (Synthesis and Characterization on Acetonitrile and DMAP Complexes of Indium(III) compounds)

  • 최철호
    • 대한화학회지
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    • 제42권2호
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    • pp.184-189
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    • 1998
  • Indium(III) trihalides (halogen=Cl, Br)와 bis(pentafluorophenyl)cadmiumd을 acetonitrile에서 반응시켜 acetonitrile이 배위된 tris(pentafluorophenyl)indium을 합성하였으며 원소분석, 핵자기 공명과 질량분석 스펙트럼을 이용하여 특성을 조사하였다. 그 결과 acetonitrile과 배위한 tris(pentafluorophenyl)indium는 pentafluorophenylindium화합물과 acetonitrile이 1:1로 배위된다는 것을 알 수 있었다. 또한 In$(C_6F_5)_3{\cdot} CH_3CN$과 DMAP(dimethylaminopyridine)를 dichloro methane 용매에서 리간드를 치환반응시켜 In$In(C_6F_5)_3{\cdot}DMAP$를 합성하였다. 리간드들의 치환은 acetonitrile보다 주개 성질이 강한 DMAP가 acetonitrile의 자리에 배위하는 것으로 생각된다.

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OenNen-Styrene DVB 합성수지에 의한 U(VI), Fe(II), Sm(III) 이온들의 흡착 (Adsorption of U(VI), Fe(II), Sm(III) Ions on OenNen-Styrene DVB Synthetic Resin)

  • 이치영;김준태
    • 환경위생공학
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    • 제22권3호
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    • pp.77-87
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    • 2007
  • The ion exchange resins have been synthesized from chlormethyl styrene - 1,4 - divinylbenzene(DVB) with 1%, 3%, and 5%-crosslinking and macro cyclic ligand of OenNen-$H_4$ by copolymerization method and the adsorption characteristics of uranium(VI), iron(II) and samarium(III) metallic ions have been investigated in various experimental conditions. The synthesis of these resins was confirmed by content of chlorine, element analysis, and IR-spectrum. The effects of pH, time, dielectric constant of solvent and crosslink on adsorption of metallic ions were investigated. The uranium ion was showed fast adsorption on the resins above pH 3. The optimum equilibrium time for adsorption of metallic ions was about two hours. The adsorption selectivity determined in ethanol was in increasing order uranium ${UO_2}^{2+}>Fe^{2+}>Sm^{3+}$ ion. The adsorption was in order of 1%, 3%, and 5% crosslink resin and adsorption of resin decreased in proportion to order of dielectric constant of solvent.

OenNdien수지에 의한 금속 이온의 흡착 (Adsorption of Metal Ions on OenNdien Resin)

  • 강영식;노기환;김준태
    • 환경위생공학
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    • 제20권3호
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    • pp.27-35
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    • 2005
  • The ion exchange resins have been synthesized from chlormethyl styrene - 1,4 -divinyl-benzene(DVB) with $1\%,\;4\%,\;and\;10\%$-crosslinking and macrocyclic ligand of cryptand type by copolymerization method and the adsorption characteristics of uranium(VI), calcium(II) and lutetium(III) metallic ions have been investigated in various experimental conditions. The synthesis of these resins was confirmed by content of chlorine, element analysis, and IR-spectrum. The effects of pH, time, dielectric constant of solvent and crosslink on adsorption of metallic ions were investigated. The uranium ion was showed fast adsorption on the resins above pH 3. The optimum equilibrium time for adsorption of metallic ions was about two hours. The adsorption selectivity determined in ethanol was in increasing order uranium $(UO_2^{2+})>calcium(Ca^{2+})>lutetium(Lu^{3+})$ ion. The adsorption was order of $1\%,\;4\%,\;and\;10\%$ crosslink resin and adsorption of resin decreased in proportion to order of dielectric constant of solvents.

Possible target for G protein antagonist: Identification of specific amino acid residue responsible for the molecular interaction of G$\alpha$ 16 with chemoattractant C5a receptor.

  • 이창호
    • 한국응용약물학회:학술대회논문집
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    • 한국응용약물학회 2000년도 춘계학술대회
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    • pp.17-19
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    • 2000
  • Heterotrimeric G Proteins transduce ligand binding to a wide variety of seven transmembrane cell surface receptors into intracellular signals. The currently accepted model for the activation of G protein suggests that ligand-activated receptor accelerates GDP-GTP exchange reactions on the ${\alpha}$ subunit of the heterotrimeric G protein. At least seventeen distinct isoforms of the G${\alpha}$ subunit protein have been identified in mammalian organisms. Among them, the G${\alpha}$q family consists of five members whose ${\alpha}$ subunits show different expression patterns. G${\alpha}$q and G${\alpha}$11 seem to be almost ubiquitously expressed, whereas G${\alpha}$14 is predominantly expressed in spleen, lung, kidney and testis. G${\alpha}$16 and its murine counterpart G${\alpha}$15 are expressed in hematopoietic cells and has been shown to couple a wide variety of receptors to phosphoinositide-specific phospholipase C activity. Beta-isoforms of phospholipase C were shown to be activated by all members of G${\alpha}$q family, i.e., G${\alpha}$q, G${\alpha}$11, G${\alpha}$l4 and G${\alpha}$16 subunits either in reconstitution system. or in experiments using cDNA transfection with intact Cos-7 cells.

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질소-주게 합성수지를 이용한 U(VI), Cu(II), Dy(III) 이온들의 흡착특성 (Adsorption Characteristic of U(VI), Cu(II), Dy(III) Ions Utilizing Nitrogen-Donator Synthetic Resin)

  • 노기환;김준태;김희정
    • 환경위생공학
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    • 제21권3호
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    • pp.52-60
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    • 2006
  • The ion exchange resins have been synthesized from chlormethyl styrene-1,4-divinylbenzene(DVB) with 1%, 2%, and 20%-crosslinking and macrocyclic ligand of cryptand 21 by copolymerization method and the adsorption characteristics of uranium(VI), copper(II) and dysprosium(III) metallic ions have been investigated in various experimental conditions. The synthesis of these resins was confirmed by content of chlorine, element analysis, and IR-spectrum. The effects of pH, equilibrium time, dielectric constant of solvent and crosslink on adsorption of metallic ions were investigated. The metal ion was showed fast adsorption on the resins above pH 3. The optimum equilibrium time for adsorption of metallic ions was about two hours. The adsorption selectivity determined in ethanol was in increasing order uranium$(UO^{2+}_2)\;>\;copper(Cu^{2+})\;>\;dysprosium(Dy^{3+})$ ion. The adsorption was in order of 1%, 2%, and 20% crosslink resin and adsorption of resin decreased in proportion to order of dielectric constant of solvents.

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

  • Kim, Gang-Il;Sung, Yun-Mo
    • 한국재료학회지
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    • 제19권1호
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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.

Solvent Effects on the Isotropic NMR Shifts in Quinuclidine and Pyridine-Type Ligands Coordinated to the Paramagnetic Polyomometalate, $[SiW_{11}Co^{II}o_{39}]^{6-}$

  • Hyun, Jaewon;Park, Suk-Min;So, Hyunsoo
    • Bulletin of the Korean Chemical Society
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    • 제18권10호
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    • pp.1090-1093
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    • 1997
  • The solvent effects on the isotropic NMR shifts in conformationally rigid ligands such as quinuclidine, pyridine, and 4-aminopyridine coordinated to the paramagnetic polyoxometalate, [SiW11CoⅡO39]6- (SiW11Co), are reported. For these complexes the ligand exchange is slow on the NMR time scale and pure 1H NMR signals have been observed at room temperature. The signals for the SiW11Co complexes are shifted upfield whe dimethyl sulfoxide-d6 (DMSO) is added to a D2O solution. The isotropic shifts are separated into contact and pseudocontact contributions by assuming that the contact shifts are proportional to the isotropic shifts of the same ligands coordinated to [SiW11NiⅡO39]6-. It is shown that both the contact and pseudocontact shifts decrease (the absolute values of the pseudocontact shifts increase), when D2O is replaced by DMSO. It is suggested that D2O, a strong hydrogen bond donor, withdraws electron density from [SiW11CoⅡO39]6-, increasing the acidity of the cobalt ion toward the axial ligand. When D2O is replaced by DMSO, the acidity of the cobalt ion in SiW11Co decreases, weakening the Co-N bond. Then both the contact and pseudocontact shifts are expected to decrease in agreement with the observed solvent effects.

전이금속착물의 구조와 그 반응성 (I). 암민류를 포함하는 Ethylenediamine-triacetatocobalt (III) 착물의 합성과 기하이성질현상 (Structure and Chemical Reactivity of the Transition Metal Complexes (I). Synthesis and Geometrical Isomerism of the Ethylenediamine-triacetatocobalt (III) Complexes with Ammine or Diamines)

  • 이동진;김봉곤;도명기
    • 대한화학회지
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    • 제29권5호
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    • pp.516-521
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    • 1985
  • 한자리 리간드로써 암민, 에틸렌디아민, 트리메틸렌디아민 등을 포함하는 ethylenediamine-triacetatocobalt (III) 착물을 합성하고, Dowex 50W-X8, 수소이온형 양이온 교환수지를 사용하여 각각 한 종류의 이성질체를 분리하였으며, 원소분석, pH적정, 적외선 분광법, 핵자기공명 및 전자흡수스펙트럼으로 가능한 기하이성질체중에서 cis-equatorial형이라고 추정하였다. 여러자리 리간드를 동시에 포함하는 meridional 형의 $[CoN_3O_3]$계에서 나타난 제 1흡수띠는 크게 분열된 양상을 보여주었고, 에틸렌디아민, 트리메틸렌디아민 등이 코발트(III) 이온에 한자리 리간드로 배위되었다는 사실도 확인하게 되었다.

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