Application on high performance liquid chromatography for multielemantal analysis at trace levels using keto anime sheif basis

Abstract

During this report period Oct. 1987-0ct. 1990, the allowing new complexing reagents were prepared. 1. Bir;( trif luoro isopropanoylacetone )d 1-st i lbened i imi e

2. Bis(trifluoroisopropanoyl cetone)meso-stilbenediimine (m so-H2F3PAzS). 3. Bis(Bis(trifluoroacetylmesityloxide)ethylenediimine

4. Bis(trifluoroacetylmesityloxide)propylenediimine(H2F3AM2pn) 5. Bis(trifluoroacetylmesityloxide)dl-stilbenediimine (dl-H2F3AM2S) 6. Bis(trifluoroacetylmesityloxide)meso-stilbened'i ine (meso-H2F3AM2S). 7. Bis(acetylpivaloylmethane)propylenediim·ne(H2APM2p ). 8. Bis(isovaleroylacetone)propylenediimine(HzIVA2pn) 9 Bis(trifluoroisovaleroyl cetone)eth"lenediimine(HzF3IVA2en) 10 Bis(trifluoroisovaleroylacetone)propylenediimine(H2F3IVA2pn) 11 Bis(trifluo·o·sovaleroyl cetone)dl-·tilbenediimin (dl-HzF3IVAzS) 12 Bis(trifluoroisovaleroylacetone)phenylethylenediimine (HzF3IVA2Pen) The copper and nickel ch•lates of the reagents dl-H2 3PA2S,

dl- HzF3IVAzS, copper, nickel and palladium chelates of HzAPHzpn,

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H2IVA2pn and H2F3IVA2pn and copper, nickel, palladium and oxovanadium chelates of H2F3IVA2en, H2F3IVA2pn were prepa ed. The palladium and oxovanadium chelates of the following reagents reported earlier, together with their copper nd nickel chelates were also prepared. Bis(isovaleroylacetone)ethylenediimine(H2IVA2en) 2. Bis(isovaleroylacetone)dl-stilbenediimine(dl-H2IVA2S) 3. Bis(isovaleroylacetone)meso-stilbenediimine(meso-H2IVA2S) 4. Bis(acetylpivaloylmethane)ethylenediimine(HzAPH2en) 5. Bis(acetylpivaloylmethane)dl-stilbenediim·ne(H2APH2S) 6. Bis(acetylpivaloylmethane)meso-stilbenedii ine (meso-H2APM2S). 7. Bis(acetylacetone)dl-stilbenediimin (dl-H2AA2S) 8 Bis(acetylacetone)meso-stilbenediim:ne(meso-H2AAzS) 9 Bis(trifluoroacetylacetone)dl-stilbenediimine(dl-H2AA2S) 10 Bis(trifluoroacetylacetone)meso-stilbenediimine(meso-HzAA2S) The reagent and their metal chelates were characterized by elemental micro-analysis, IR, UV, 1 HNMR and mass spectroscopic techniques.

The copper and nickel chelates of dl-H2F3PA2S, meso- H2F3PAzS, HzF3AH2en, H2F3AHzpn, dl-HzF3PA2S, meso-H2F3AM2S,

copper, nickel and palladium chelates of H2F3IVA2Pen and copper, nickel, palladium and oxovanadium chelates of dl-HzIVA2s were •J separated using normal phase column (250 x 4mm) packed with lichrosorb si, 100, 5μ .. The copper, nickel, palladium and oxovanadium chelates of dl-H2AA2S, meso-H2AA2s, dl-H2F3AA2s, meso-H2F3AAzS using normal phase column Hicrosorb (200x 4.6 n) eked with Si, 100, Su .. All the complexe? w re separ ted u ing

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binary mixture of chloroform: n-hexane or chloroform, l,2-dichloroethane and n-hexar?.

ternary mixture of The detection was achieved using UV detector and detection limits were obtained at sub ng level of metal ions. The reversed phase mode of HPLC was also used for the separation of copper and nickel complexes of dl-H2F3IVA2S, copper, nickel and palladium chelates of HzIVAzpn, HzAPMzpn, copper, nickel, palladium and oxovanadium chelates of HzAPHzS, dl-H2IVA2S and meso-H2IVA2s on columns (250 x 4mm) packed with Hypersil ODS, 5μ., Nova pack C-18 (15 x3.9 mm) with guard ODS columns and Hicrosorb C-18 column (150x4.6 mm). The complexes were eluted using binary mixture of methanol: water or ternary mixture of methanol, acetonitrile and water. The detection was achieved using UV detector with detection limit at sub ng level of copper, nickel, palladium .nd vanadium. The reagents, H2IVA2en, H2APH2en and H2IVA2pn have been used for the determination of copper, nickel, palladium and platinum in aqueous solutions, copper ions, nickel-aluminium alloy and copper-nickel alloy after necessary complexation in aqueous solution, followed by·solvent extraction and subsequent determinations using HPLC. The relative elution of copper, nickel, palladium and oxovanadium of different ligands was ex mined on reversed phase HPLC and effect of different substituents on the elution of metal chelates was evaluated. Finally H2IVA2pn and

the copper, H2APHzpn

nickel and and copper,

palladium chelates ickel, palladium of and

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area of its applicatiori in science, technology and industry. In addition to the traditional field, such as separat on and det rmination of o ganic ompounds, biological active substances, and in environmental pollution monitoring, HPLC is also used for inorganic systems for the separation and determination of metals both in ionic state, and in the form of organometallic and complex compounds. Metal Chelates appear to be convenient species for th? determination of metal by HPLC, since the structure and properties of the chelates are close to those of organic compounds, which make them possible the direct transfer of the w?de experience obtained in organic HPLC [2]. The applications of HPLC to coordination compounds at trace levels have been reviewed [3-5]. The complexing reagents with respect to HPLC are mostly various dialkyldithiocarbamates (6-18], different ?- diketon s [19-22], bis-acetylbisthiobenzoylhydrozone (23], dithiozone (26], 1,2-diketobisthiobenzhydrazones, 1,2- diketobisthiosemicarbazone [27], 1,10-phenanthroline [24,25], 3- mercapto-1,5-diphenylformazan [28], 1-(2-pyridylazo)-2-naphthol [29,30] 4-(2'-pyridylazo)res?rcinol [?1], Arsuazo(III) [32], isopropylthroplone [33], N-methylfurohydroxamic acid (34], 8-hydroxyquinoline (35] and tetradentate Schiff bases [36-45]. The ?-ketoamines and related Schiff bases ligands are of considerable potential in quantitative analysis using HPLC, because the Jeactions are quantitative and at all concentration levels, free from interferences.

fairly for rapid eta ls and and are relati el

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Uden and his coworkers [36,37,39] have studied the normal and reversed phase HPLC for the separation of copper and nickel,

and copper, nickel and palladium using bis(acetylacetone)ethylene- diimine, bis(acetylacetone)butelenediimine, bis(salicylaldehyde)

ethylenediimine and fluorinated, semifluorinated and nonfluori- nated ligands derived by the condensation of ethylenediamine,

propylenediamine or butylenediamine with acetylacetone and trifluoroacetylacetone. Gaetani et al [38] have also reported similar reversed and normal phase HPLC of copper, nickel, cobalt and palladium chelates of bis(acety]acetone)ethylenediimine, bis(acetylacetone)trimethylenediimine ard bis(benzoylacetone)- ethylenediimine. Khuhawar (41-45] and his coworkers have r port d adsorption HPLC separation of copper and nickel chelates

of bis(O-hydroxyacetophenone)dl-stilbene iimine, bis(O-hydroxy- acetophenone)meso-stilbenediimine, bis(salicylaldehyde)dl-stil- benediimine, bis(salicylaldehyde)meso-stilb nediimine, bis(ben- zoylacetone)meso-stilbenediimi e, bis(O-hydroxyacetophenone)ethyl

enediimine, HzF3AM2en, HzF3AMzpn, dl-HzF3AMzS, meso-H2F3AMzS, dl- H2F3PA2S and meso-H2F2PA2S. Khuhawar et al (46] have also

reported reversed phase HPLC separation of copper, nickel and cobalt chelates of bis(O-hydroxyacetophenone)dl-stilbenediimine and bis(O-hydroxyacetophenone)meso-stilbenediimine. In the present work the ligands prepared have been investigated, their potentials for the HPLC determination of met· 1 ions using UV detector.