Abstract

 Chromium is an element of interest due to its physiological properties in different oxidation states. Chromium (III) is believed to be beneficial in curbing effects of sugar diabetes in the body, and at the same time, chromium (VI) is carcinogenic. A lot of research has been conducted in an effort to conduct speciation to identify the Cr oxidation state available in a sample. Several methods have been used but with challenges. In this study, acetylacetonates and its derivatives was used to extract Cr(III) in urine and fresh water samples. It was observed that smaller ligands of acetylacetonate metal chelates gave high linear range, which decreased with increase in the size of the ligand. Cr(AA)₃, Cr(DPM)₃ and Cr(DBM)₃ gave linear range of 1 - 10000gn/ml, 1 - 1000 ng/mL and 1000 ng/mL respectively. The highest detection limit was observed when determining Cr(DBM)₃, which had benzene rings (0.84 ng/mL) as compared to the smaller ligand metal complex Cr(AA)₃ with 1.20 ng/mL. The use of ligand with benzene ring (DBM) further allowed for resolution of other metal complexes during the extraction of Cr(III), which avoided challenges of interferences. The method developed was applied successfully in real urine and fresh water samples using DBM as a chelating agent and obtained Cr(III) in the ranges 0.86 - 7.18 ng/mL and 5.94 - 8.99 ng/mL respectively. The percentage recovery was in the range 96 - 99% for fresh water and 99.8 - 105% for urine samples.

Keywords: Metal Chelates; Acetylacetonate;Dibenzoylmethane; Dipivaloylmethane; Chromium(III); High Performance Liquid Chromatography

References

1. Goldhaber SB. “Trace element risk assessment: essential vs. toxicity”.Regulatory Toxicology and Pharmacology 38 (2003): 232-242.
2. Wilson BE and Gondy A. “Effects of chromium supplementation on fasting insulin levels and lipid parameters in healthy, non-obese young subjects”.Diabetes Research and Clinical Practice 28 (1995): 179-184.
3. Yang X., et al. “A newly synthetic chromium chelate-chromium (phenylalanine)₃ improves insulin responsiveness and reduces whole body glucose tolerance”.FEBS Letter579(2005): 1458-1464.
4. Brown M. “Harnessing chromium in the fight against diabetes”.Drug Discovery Today 8 (2003): 962-963.
5. Goodrick G K and Bell SJ. “Functional food product for the management of weight”.Critical Reviews in Food Science and Nutrition42 (2002): 63-178.
6. Kobla HV and Volpe S L. “Chromium, exercise, and body composition”.Critical Reviews in Food Science and Nutrition40(2000): 291-308.
7. Cavalleri A and Minoia C. “Chromium in urine, serum and red blood cells in the biological monitoring of workers exposed to different chromium valency states”.Science of the Total Environment 71 (1988): 323-327.
8. Cordero MTS.,et al. “Development of a new system for the speciation of chromium in natural waters and human urine samples combining ion exchange and ETA-AAS”.Journal of Analytical Atomic Spectrometry 19 (2004): 398-403.
9. Tunceli A and Turker AR. “Speciation of Cr (III) and Cr (IV) in water after preconcentration of its 1,5-diphenylcarbaone chelate on amberlite XAD-16 resin and determination by FAAS”.Talanta57 (2002): 1199-1204.
10. Padrauskas A., et al. “On-line preconcentration and determination of chromium (VI) in waters by high-performance liquid chromatography using pre-column chelation with 1,5-diphenylcarbazide”. Journal of ChromatographyA 808(1998): 193-199.
11. Zhu X., et al. “Speciation of chromium (III) and chromium (IV) by in situ separation and sequential determination with electrothermal vaporization inductively coupled plasma atomic emission spectrometry”.Analytica Chimica Acta 471 (2002): 121-126.
12. Adrain MA.,et al. “Gas and liquid chromatography of metal chelates of pentamethylene dithiocarbamate”.Journal of Chromatography A 973 (2002): 235-241.
13. Filik H. “Preconcentration and speciation of chromium (III) in waters by using 5-palmitoyl-8-hydroxyquinoline immobilized on a nonpolar adsorbent”.Michrochimica Acta 140 (2002): 205-210.
14. Serby F., et al. “Chromium speciation by hyphenation of high-performance liquid chromatography to inductively coupled plasma-mass spectrometry-study of the influence of interfering ions”.Journal of Analytical Atomic Spectrometry 18(2003): 1386-1390.
15. Pantsar-KallioM and Manninen PKG. “Speciation of chromium in waste waters by coupled column ion chromatography-inductively coupled plasma mass spectrometry”.Journal of Chromatography A 750 (1996): 89-95.
16. Kocaoba S and Akcin G. “Removal and recovery of chromium and chromium speciation with MINTEQA2”.Talanta 57 (2002): 23-30.
17. Isshiki , et al. “Preconcentration of chromium (III) and chromium (VI) in sea water by chelateation with quinolin-8-ol and adsorption on macroporous resin”.Analytica Chimica Acta224 (1989): 55-64.
18. “Separation/preconcentration of trace heavy metals in urine, sediment and dialysis concentrates by coprecipitation with samarium hydroxide for atomic absorption spectrometry”.Talanta 59 (2003): 287-293.
19. Hu G and Deming RL. “Speciation of bio-available chromium in soils by solid-phase extraction and graphite furnace atomic absorption spectrometry”.Analytica Chimica Acta535 (2005): 237-242.
20. ,et al.“Determination of chromium (III) in water by solid-phase microextraction with a polyimide-coated fiber and gas chromatography-flame photometric detection”.Journal of Chromatography A 1062 (2005): 49-55.
21. Uden PC.,et al.“Analytical separations of Schiff-bases chelates by reversed-phase HPLC on a 10 micron C-18 bonded silica substrate”.Analytical Letter8 (1975): 795-798.
22. Uden PC., et al. “Separation of geometrical isomers and mixed-ligand forms of cobalt (III) and chromium (III) beta-diketonates by high-pressure liquid-chromatography”.Analytica Chimica Acta 100 (1978): 555-561.
23. Sievers RE.,et al. “Gas phase chromatography of metal chelates of acetylacetonate, trifluoroacetylacetone and hexafluoroacetylacetone”.Inorganic Chemistry2 (1963): 693-698.
24. Uden PC and Henderson DE. “Determination of metals by gas chromatography of metal chelates”.Analyst 102 (1977): 889-916.
25. Fung YS and Sham WC. ”Determination of chromium (VI) in river samples by electrothermal atomic-absorption”.Analyst 119 (1994): 1029-1032.
26. Bermejo BP. et al “Chromium speciation by ETAAS using 1,1,1-trifluoro-2,4-pentadione to form a volatile chelate with Cr (III)”.Atomic Spectroscopy(2003): 22-26.
27. Bermejo BP.,et al “Direct speciation analysis of Cr (VI) by electrothermal atomic absorption spectrometry, based on the volatilization of Cr (III) thenoyltrifluoracetonate from the graphite furnace”.Spectrochimica Acta Part B58 (2003): 167-173.
28. Gurira RC and Carr PW. “Reversed-Phase HPLC of beta-diketonate metalchelates”. Journal of Chromatography Science20 (1982): 461-465.
29. Uden PC.,et al “Separation of geometrical isomers and mixed-ligand forms of cobalt (III) and chromium (III) beta-diketonates by high-pressure liquid-chromatography”.Analytica Chimica Acta100 (1978): 555-561.
30. Chau KC., et al. “Determination of chromium by atomic absorption spectrophotometry of chromium acetylacetonate : Determination of chromium in sea water”.Analytica Chimica Acta43 (1968): 13-18.
31. Willert JD and Knight MM. “Determination of chromium in orchard leaves by reversed-phase high-performance liquid chromatography”.Journal of Chromatography A237 (1982): 99-105.
32. Arancibia V., et al. “Determination of chromium in urine samples by chelation supercritical fluid extraction and liquid and gas chromatography”.Journal of Chromatography B 785 (2003): 785, 303-309.
33. Gammelgaard B and Jons O. “Determination of selenium in urine by inductively coupled plasma mass spectrometry: interferences and optimization”.Journal of Analytical Atomic Spectrometry 14 (1999): 867-874.
34. Takuwa DT.
35. Gurira RC and Carr PW. “Reversed-phase HPLC of b-diketone metal chelates”.Journal of Chromatography Science20 (1982): 461-465.
36. Collman, JP., et al. “Reactions of metal chelates: III. Nitration and formylation of metal acetylacetonates”.Inorganic Chemistry3 (1962): 704-710.
37. Risby TH and Tollinche C A. “LC of metal chelates”.Journal of Chromatography Science16 (1978): 448-454.
38. Wenclawiak BW.,et al. “Rhodium and palladium beta-diketonate determination with on-line supercritical fluid extraction high performance liquid chromatography via solid phase extraction”.Fresenius Journal of Analytical Chemistry 358 (1997): 471-474.
39. Zhao J and Carr PW. “A comparative study of chromatographic selectivity of polystyrene-coated zirconia and other related reversed-phase materials”.Analytical Chemistry72 (2000): 302-309.
40. Hu Y. et al “Mixed-mode reversed-phase and ion-exchange separations of cationic analytes on polybutadiene-coated zirconia”.Journal of Chromatography A968 (2002): 968, 17-29.
41. Henry R. “Highly selective zirconia-based phases for HPLC applications”.American Laboratory 69 (2002): 18-25.
42. Shishu AKS and Kaur IP. “Inhibitory effect of dibenzoyl methane on mutagenicity of food-derived heterocyclic amine mutagens”.Phytomedicine 10 (2003): 575-582.
43. Jackson KM., et al. “Dibenzoyl methane induces cell cycle deregulation in human prostate cancer cells”. Cancer Letter178 (2002): 2161-2165.
44. Abu-Qare AW and Abu-Donia MB. “Determination of depleted uranium, pyridostigmine bromide and its metabolite in plasma and urine following combined administration in rats”.Journal of Pharmaceutical and Biomedical Analysis(2001): 281-289.

Citation

Citation: David TanyalaTakuwa. “Extraction of Chromium(III) from Urine and Water Samples Using Divalent Beta-diketonates Ligands and Determination with Reversed-Phase HPLC". Acta Scientific Pharmaceutical Sciences 4.8 (2020): 85-97.

Copyright

Copyright: © 2020 David TanyalaTakuwa. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.