• Title/Summary/Keyword: H-Chelate

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Synthesis and Reaction Chemistry of Some Ferrocene-Containing Chelate Ligands with Dirhodium Acetate: X-ray Crystal Structure of $(\eta^1-(S,R)-CPFA)_2Rh_2(OAc)_4$

  • Kim, Eun-Jin;Kim, Tae-Jeong
    • Bulletin of the Korean Chemical Society
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    • v.15 no.11
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    • pp.990-996
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    • 1994
  • New ferrocene-based chelate amines, $Fe[C_5H_4CH(Me)NMe_2]_2\;(3), \;Fe[C_5H-3(CH(Me)NMe_2)(PPh_2)-1,2]_2\;(4),\;(C_5H_5)Fe(C_5H_3(CH_2NMe_2)(CH(CN)NMe_2-1,2)\;(6),\;and\;(C_5H_5)Fe(C_5H_3(CH_2NMe_2)(CH(Me)NMe_2-1,2)$ (7) have been prepared. The reaction and the coordination chemistry of 4 and other related compounds (S,R)-(1-N,N-dimethylaminoethyl)-2-dicyclohexylphosphino)ferrocene (CPFA) and 1,1'-bis-(diphenylphosphino)ferrocene (BPPF) with $Rh_2(OAc)_4(MeOH)_2$ were investigated. The reaction of the chiral ligand (S,R)-CPFA forms a complex of the type (${\eta}^1$-(S,R)-CPFA-P)$_2Rh_2(OAc)_4$ (8) in which the ligand is coordinated to both rhodium centers in a monodentate fashion through phosphorus. In contrast, the bisphosphine analogues such as BPPF and 4 afford chelate complexes of the type (${\eta}^2-PP)Rh_2(OAc)_4$ (9 & 10) where both ligands act as a chelate bidentate to a single rhodium atom. All these complexes were characterized by microanalytical and spectroscopic techniques. In one case, the structure of 8 was determined by X-ray crystallography. Crystals are monoclinic, space group C2 (No. 5), with a=26.389 (3), b=12.942 (1), c=11.825 (1) A, ${\beta}$=111.22(1)$^{\circ}$, V=3964.7 (8) $A^3$, Z=4, and $D_{calc}$=1.58 g $cm^{-3}$. Two Rh(II) centers are bridged by four $AcO^-$ groups in the ${\eta}^1$ : ${\eta}^1$ mode across a Rh-Rh single bond, and octahedral coordination at Rh(1) and Rh(1') is completed by axially coordinating (S,R)-CPFA and a briding $AcO^-$, respectively.

The spectrophotometric determination of undecylenic acid using tris (1,10-phenanthroline) Fe(II) chelate (Tris(1,10-phenathroline) Fe(II) chelate에 의한 undecylenic acid의 흡광광도 정량법)

  • 강삼식;백남호
    • YAKHAK HOEJI
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    • v.16 no.4
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    • pp.180-185
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    • 1972
  • A new spectrophotometric method was established for the determination of undecylenic acid. The method is based on the solvent extraction into nitrobenzene of the ion pair formed between tris(1,10-phenanthroline)Fe(II) chelate and the anion of undecylenic acid. The maximum absorbance of the extract in the organic phase was at 518nm. A maximum extraction was obtained at pH 9-11, when excess of at least 50-fold(molar) of the phenanthroline-Fe(II) chelate to undecylenic acid was present. The color intensity of the extracted species remained constant at room temperature for the several hours after separation of the organic layer. A linear relationship was obtained over the tested range of 5-20${\gamma}$/ml of undecylenic acid. The effect of several other fungicids on this method was investigated. The method was applied to the determination of undecylenic acid in preparations and the results were in good agreement with those added amounts.

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Enantiomeric Separation of Free Amino Acids Using N-alkyl-L-proline Copper(Ⅱ) Complex as Chiral Mobile Phase Additive in Reversed Phase Liquid Chromatography

  • Lee Sun Haing;Oh Tae Sub;Lee Hae Woon
    • Bulletin of the Korean Chemical Society
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    • v.13 no.3
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    • pp.280-285
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    • 1992
  • Enantiomeric separation of free amino acids has been achieved by a reversed phase liquid chromatography with addition of a Cu(Ⅱ) complex of N-alkyl-L-proline (alkyl: propyl, pentyl or octyl) to the mobile phase. The amino acids eluted were detected by a postcolumn OPA system. N-alkyl-L-proline was prepared and used as a chiral ligand of Cu(Ⅱ) chelate for the enantiomeric separation. The concentration of the Cu(Ⅱ) chelate, the organic modifier and pH affect the enantiomeric separation of free amino acids. The retention behaviour, varied with change in pH and the concentration of the Cu(Ⅱ) chelate, was different compared with those of the derivatized amino acids. The elution orders between D- and L-forms were consistent except histidine showing that L-forms elute earlier than D-forms. The retention mechanism for the enantiomeric separation can be illustrated by the stereospecificity of the ligand exchange reaction and the hydrophobic interaction between the substituent of amino acids and reversed phase, $C_18$.

Study on the Solid Phase Extraction of Hg(II)-SBDTR Chelate with C18 Disks and Its Application to the Determination of Mercury in Tobacco and Tobacco Additive

  • Yang, Guan-Gyu;Xia, Zhen-Yuang;Wu, Yu-Ping;Sun, Han-Dong;Yin, Jia-Yuan
    • Bulletin of the Korean Chemical Society
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    • v.25 no.4
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    • pp.549-552
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    • 2004
  • A sensitive, selective and rapid method has been developed for the determination of mercury based on the rapid reaction of mercury(II) with p-sulfobenzylidenethiorhodanine (SBDTR) and the solid phase extraction of the colored chelate with $C_{18}$ disks. In the presence of pH 3.5 sodium acetate-acetic acid buffer solution and Emulsifier-OP medium, SBDTR reacts with mercury(II) to form a red chelate of a molar ratio 1 : 2 (mercury to SBDTR). This chelate was prconcentrated by solid phase extraction with $C_{18}$ disks. An enrichment factor of 50 was achieved. The molar absorptivity of the chelate is $1.28{\times}10^5 L{\cdot}mol^{-1}{\cdot}cm^{-1}$ at 545 nm in measured solution. Beer's law is obeyed in the range of 0.01-3 ${\mu}$g/mL. The relative standard deviation for eleven replicates sample of 0.01 ${\mu}$g/mL is 1.65%. This method was applied to the determination of mercury in tobacco and tobacco additive with good results.

Effects of Cu and Zn-Methionine Chelates Supplementation on the Performance of Broiler Chickens (사료 內 Cu 및 Zn-Methionine Chelates 첨가가 육계의 생산성에 미치는 영향)

  • Hong, S.J.;Lim, H.S.;Paik, I.K.
    • Journal of Animal Science and Technology
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    • v.44 no.4
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    • pp.399-406
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    • 2002
  • An experiment was conducted to investigate the effects of supplemental copper or/and zinc methionine chelates(Cu-Met or/and Zn-Met) on the performance, nutrient digestibility, serum IgG level, gizzard erosion, and the contents of Cu and Zn in liver and excreta of broiler chickens. One thousand d-old broiler chickens (Ross$^{(R)}$) were assigned to 4 treatments: control, 100 ppm Cu in methionine chelate(Cu-Met), 100 ppm Zn in methionine chelate(Zn-Met) and 100 ppm Cu plus 100 ppm Zn in methionine chelate(Cu-Zn-Met). Each treatment had five replications of 50 (25 male + 25 female) birds each. Average weight gains of chicks fed chelated Cu or/and Zn were significantly higher than that of chicks fed the control (P<0.05). Moreover, feed conversion rates of chicks were better in the chicks fed chelated Cu or/and Zn than in the chicks fed the control (P<0.05). The birds fed the chelated Cu and Zn(Cu-Zn-Met) tended to perform the best growth rate and feed conversion rate. Nutrient digestibilities were not affected by the dietary treatments. Serum IgG level of chicks fed Cu-Zn-Met was significantly higher than that of chicks fed the control (P<0.05). Gizzard erosion index was not significantly different among the treatments. The contents of Cu and Zn in liver were not significantly affected by the dietary treatments. The excreta contents of Cu or/and Zn were significantly high in the birds fed supplementary Cu or/and Zn. It was concluded that dietary supplementation of Cu or/and Zn in methionine chelated form improved growth and feed conversion efficiency of broilers.

Optical Resolution of Dabsyl Amino Acids in Reversed-Phase Liquid Chromatography

  • Lee, Sun-Haing;Oh, Tae-Sub;Lee, Young-Cheal
    • Bulletin of the Korean Chemical Society
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    • v.11 no.5
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    • pp.411-415
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    • 1990
  • The dabsylation of amino acids has been applied to resolve their optical isomers with the use of chiral mobile phase in high performance liquid chromatography. The dabsyl amino acids were successfully separated on reversed phase column($C_{18}$) by adding a chiral L-benzylproline-Cu(II) chelate to the mobile phase. The separation selectivity of the dabsyl amino acid enantiomers was not less than that of dansyl amino acids. The retention order of the dabsyl amino acid enantiomers was as those of the dansyl amino acid enantiomers except dabsyl threonine. The optical selectivity of the dabsyl amino acids increase with pH of the mobile phase and concentration of the chelate, but slightly decreases with concentration of buffer and organic solvent composition. However serine, methionine, valine, and leucine showed a slight decrease in the optical selectivity with increase in pH. The retention times of the dabsyl amino acids decreases with increasing pH and acetonitrile concentration but increases with the concentration of the chiral chelate added. The mechanism of the optical resolution is based on a stereospecific interaction including a intramolecular hydrophobic effect and SN-2 reactivity of the ligand exchange chromatography.It is advantageous to detect absorption at 436 nm, which is less interferent them the other detection systems. The derivatized dabsyl amino acids are stable for a month.

Effects of Supplementary Copper Chelates in the Form of Methionine, Chitosan and Yeast on the Performance of Broilers

  • Lim, H.S.;Paik, I.K.;Sohn, T.I.;Kim, W.Y.
    • Asian-Australasian Journal of Animal Sciences
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    • v.19 no.9
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    • pp.1322-1327
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    • 2006
  • An experiment was conducted to investigate the effects of supplemental copper (Cu) chelates (methionine, chitosan and yeast) on the performance, nutrient digestibility, serum IgG level, gizzard erosion, Cu content in the liver and excreta and the level of total cholesterol in breast muscle and serum of broiler chickens. Two hundred and forty hatched broiler chickens (Ross$^{(R)}$ 208) were assigned to 4 treatments: control, 100 ppm Cu in methionine chelate (Met-Cu), 100 ppm Cu in chitosan chelate (Chitosan-Cu) and 100 ppm Cu in yeast chelate (Yeast-Cu). Each treatment had six replicates of 10 (5 males+5 females) birds each. Weight gain and feed intake tended to be higher in Cu chelate treatments than the control; weight gain was significantly higher in the Met-Cu chelate treatment and feed intake was significantly higher in the Yeast-Cu chelate treatment than the control (p<0.05). Feed/gain was significantly different between treatments in which Met-Cu was lowest followed by the control, Chitosan-Cu and Yeast-Cu. DM availability was increased by Cu chelates among which chitosan-Cu showed the highest DM availability. Cu chelates supplementation tended to increase gizzard erosion index, and Cu content in the liver was highest in the Met-Cu treatment. Supplementation of Cu chelates tended to decrease total cholesterol level in breast muscle and serum but tended to increase the level of HDL in serum. It was concluded that dietary supplementation of 100 ppm Cu in chelates increased weight gain, feed intake and DM availability. Met-Cu was more effective than Chitosan-Cu or Yeast-Cu in improving productivity of broiler chickens.

The Synthesis of Pyrimidine Derivatives Containing H-Chelate (H-킬레이트가 있는 피리미딘 유도체들의 합성)

  • Kim, Jeong Hwan;Seo, Jeong Hyeop
    • Journal of the Korean Chemical Society
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    • v.34 no.6
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    • pp.637-640
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    • 1990
  • Bis (4,6-dichloropyrimidine-5-yl) alkanes as the frame of "intramolecular electronic energy transfer" system have been synthesized and the H-chelates of $\alpha$-(4-cyanomethylquinoline-6-chloropyrimidine-5-yl)-$\omega$-(4,6-dichloropyrimidine-5-yl) alkanes have been synthesized from bis (4,6-dichloropyrimidine-5-yl) alkanes and 2-cyanomethylquinoline. The structures of the compounds have been studied by spectral methods.

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Studies on Drug Analysis by Metal Chelate Ion II. Colorimetric Determination of Sulfa-Drugs with Dimethylglyoxime-Fe(II) (금속 chelate ion에 의한 의약품 정량에 관한 연구 (II) Dimethyglyoxime Fe(II)에 의한 Sulfa 제의 비색정량)

  • 이왕규;옥치완;김박광
    • YAKHAK HOEJI
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    • v.13 no.1
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    • pp.28-32
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    • 1969
  • For the colorimetric determination of Sulfa-drugs by means of solvent extraction, the sample solutions were added into dimethylglyoxime-Fe(II) complex solution, and extracted with pyridine-chloroform mixture (1:50) is a range of pH 7.5-8.5. The extracted solution shows stability and maximum absorption at 402m${\mu}$.

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Studies on Drug Analysis by Metal Chelate Ion. I. Colorimetric Determination of Nicotinamide with Dimethyglyoxime-Fe (II) (금속 chelate ion에 의한 의약품 정량에 관한 연구(I) Dimethylglyoxime-Fe(II)에 의한 Nicotinamide의 비색정량)

  • 이왕규
    • YAKHAK HOEJI
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    • v.13 no.1
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    • pp.22-27
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    • 1969
  • Nicotinamide Complex Compound was not formed in simple alkaline solution under two to one molar ratio of dimethyglyoxime and Fe (II), but it was formed with ammonia or pyridine under the same molar ratio. Based on this fact, nicotinamide solution was added into dimethyglyoxime-Fe (II) complex solution, and the chelation product was extracted with chloroform. The extraction was Completed in a range of pH 8.4-11.0. The chloroform solution shows stability and maximum absorption at 516 m${\mu}$.

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