Advertisement

Reaction Kinetics, Mechanisms and Catalysis

, Volume 128, Issue 1, pp 1–22 | Cite as

Ligand substitution in chromium(III)-aqua complexes by l-histidine: kinetic resolution of two long-lived intermediates

  • Joaquin F. Perez-BenitoEmail author
  • Xavier Julian-Millan
Article
  • 20 Downloads

Abstract

The kinetics of the reaction of substitution of aqua ligands in Cr(III) complexes by the amino acid l-histidine, in aqueous media and under acidic conditions (pH 3.60–5.79), has been studied with the aid of a spectrophotometric technique (at 530 nm). The rate-time profiles showed an initial acceleration period followed by a deceleration one. A model of three consecutive reactions has been applied, involving two long-lived intermediates (not reactive enough to be in steady state) and three rate constants: k1, k2 and k3, corresponding to the successive decays of the reactant, the first long-lived intermediate and the second, respectively. The three rate constants increased when the medium ionic strength was raised using KNO3 as background electrolyte, whereas the effect of KCl was of minor intensity, and showed base catalysis. The activation parameters for the reactions of Cr(III) with l-histidine, l-histidine methyl ester, l-arginine, l-lysine and 2-picolinic acid were also determined. The UV–Vis spectrum of the first long-lived intermediate was rather close to that of the inorganic reactant, whereas the spectrum of the second long-lived intermediate was somehow in between those corresponding to the inorganic reactant and the reaction product. The spectra of the final reactant mixtures revealed the co-existence of at least two complexes differing in the number of organic ligands, along with the corresponding protonated forms. The proposed mechanism involves the activation of the Cr(III) starting complex by deprotonation, as well as three rate-determining (slow) steps in which the breakage of a Cr(III)-aqua chemical bond takes place, thus leaving a vacant site to which the organic ligand can coordinate.

Keywords

Chromium(III) Complexation reaction l-Histidine Kinetics Long-lived intermediates 

Notes

Supplementary material

11144_2019_1637_MOESM1_ESM.doc (1.2 mb)
Supplementary material 1 (DOC 1220 kb)

References

  1. 1.
    Laidler KJ (1987) Chemical kinetics. Harper Collins, New York, pp 21–25Google Scholar
  2. 2.
    Levine IN (2002) Physical chemistry. McGraw-Hill, New York, pp 534–536Google Scholar
  3. 3.
    Atkins PW, de Paula J (2014) Physical chemistry. Oxford University Press, Oxford, pp 827–832Google Scholar
  4. 4.
    Hamm RE (1953) Complex ions of chromium. IV. The ethylenediaminetetraacetic acid complex with chromium(III). J Am Chem Soc 75:5670–5672CrossRefGoogle Scholar
  5. 5.
    Hedrick CE (1965) Formation of the chromium-EDTA complex. J Chem Educ 42:479–480CrossRefGoogle Scholar
  6. 6.
    Barreto JC, Brown D, Dubetz T, Kakareka J, Alberte RS (1965) A spectrophotometric determination of the energy of activation (E a) for a complexation reaction: the kinetics of formation of a Cr(III)/EDTA complex. Chem Educ 10:196–199Google Scholar
  7. 7.
    Abdel Messih MF, Abou-Gamra ZM (2012) Kinetics and mechanism of the reaction between chromium(III) and picolinic acid in weak acidic aqueous solution. Monatsh Chem 143:211–216CrossRefGoogle Scholar
  8. 8.
    Ramasami T, Taylor RS, Sykes AG (1976) Evidence for a dissociative mechanism in the reaction of glycine with [Cr(NH3)5(H20)]3+. Ionic strength contributions (as a 1:1 electrolyte) and ion-pairing (K IP) ability of the glycine zwitterion. Inorg Chem 15:2318–2320CrossRefGoogle Scholar
  9. 9.
    Khan IA, Kabir-ud-Din K (1981) Anation of hexaaquachromium(III) by glycine. J Inorg Nucl Chem 43:1082–1085CrossRefGoogle Scholar
  10. 10.
    Khan IA, Shadid M, Kabir-ud-Din K (1983) Kinetics of anation of hexaaquachromium(III) ion by serine in aqueous acidic medium. Indian J Chem A 22:382–385Google Scholar
  11. 11.
    Niogy BK, De GS (1983) Kinetics and mechanism of anation of hydroxopentaaquachromium(III) ion by DL-alanine in aqueous solution. Proc Indian Acad Sci Chem Sci 92:153–161Google Scholar
  12. 12.
    Khan IA, Kabir-ud-Din K (1984) Kinetics of anation of hexaaquachromium(III) ion by valine in aqueous acidic medium. Indian J Chem A 23:98–101Google Scholar
  13. 13.
    Niogy BK, De GS (1984) Kinetics and mechanism of anation of hydroxopentaaquachromium(III) ion by DL-phenylalanine in aqueous solution. J Indian Chem 61:389–392Google Scholar
  14. 14.
    Khan IA, Kabir-ud-Din K (1985) Studies on the composition and kinetics of chromium(III)-alanine system. Int J Chem Kinet 17:1263–1272CrossRefGoogle Scholar
  15. 15.
    Khan IA, Kabir-ud-Din K (1986) Kinetics of anation of hexaaquachromium(III) ion by aspartic acid—mechanism and activation parameters. Transit Met Chem 11:391–395CrossRefGoogle Scholar
  16. 16.
    Khan IA, Shahid M, Kabir-ud-Din K (1990) Kinetic and mechanistic studies on the complexation of aquachromium(III) with DL-tryptophan in aqueous acidic media. J Chem Soc Dalton Trans 10:3007–3012Google Scholar
  17. 17.
    Khan IA, Shahid M, Kabir-ud-Din K (1991) Methionine anation of aquachromium(III). Transit Met Chem 16:18–22CrossRefGoogle Scholar
  18. 18.
    Guindy NM, Abou-Gamra ZM, Abdel-Messih MF (1999) Kinetic studies on the complexation of aqua chromium(III) with DL-leucine in aqueous acidic media. J Chim Phys 96:851–864CrossRefGoogle Scholar
  19. 19.
    Guindy NM, Abou-Gamra ZM, Abdel-Messih MF (2000) Kinetic studies on the complexation of chromium(III) with some amino acids in aqueous acidic medium. Monatsh Chem 131:857–866CrossRefGoogle Scholar
  20. 20.
    Cerar J (2015) Reaction between chromium(III) and EDTA ions: an overlooked mechanism of case study reaction of chemical kinetics. Acta Chim Slov 62:538–545CrossRefGoogle Scholar
  21. 21.
    Bakac A, Espenson JH (1993) Chromium complexes derived from molecular oxygen. Acc Chem Res 26:519–523CrossRefGoogle Scholar
  22. 22.
    Perez-Benito JF (2006) Effects of chromium(VI) and vanadium(V) on the lifespan of fish. J Trace Elem Med Biol 20:161–170CrossRefGoogle Scholar
  23. 23.
    Pereira RFP, Tapia MJ, Valente AJM, Burrows HD (2012) Effect of metal ion hydration on the interaction between sodium carboxylates and aluminum(III) or chromium(III) ions in aqueous solution. Langmuir 28:168–177CrossRefGoogle Scholar
  24. 24.
    Christiansen JA (1953) The elucidation of reaction mechanisms by the method of intermediates in quasi-stationary concentrations. In: Frankenburg WG (ed) Advances in catalysis and related subjects. Academic Press, New York, pp 311–353Google Scholar
  25. 25.
    Volk L, Richardson W, Lau KH, Hall M, Lin SH (1977) Steady state and equilibrium approximations in reaction kinetics. J Chem Educ 54:95–97CrossRefGoogle Scholar
  26. 26.
    Perez-Benito JF (2017) Some considerations on the fundamentals of chemical kinetics: steady state, quasi-equilibrium, and transition state theory. J Chem Educ 94:1238–1246CrossRefGoogle Scholar
  27. 27.
    Perez-Benito JF (2017) Two rate constant kinetic model for the chromium(III)-EDTA complexation reaction by numerical simulations. Int J Chem Kinet 49:234–249CrossRefGoogle Scholar
  28. 28.
    Perez-Benito JF, Nicolas-Rivases J (2018) Kinetics of the chromium(III)/l-glutamic acid complexation reaction: formation, decay, and UV-Vis spectrum of a long-lived intermediate. Int J Chem Kinet 50:591–603CrossRefGoogle Scholar
  29. 29.
    Perez-Benito JF, Martinez-Cereza G (2018) Ligand sequential replacement on chromium(III)-aqua complexes by l-alanine and other biological amino acids: a kinetic perspective. J Phys Chem A 122:7962–7973CrossRefGoogle Scholar
  30. 30.
    Mertz W (1976) Chromium and its relation to carbohydrate metabolism. Med Clin N Am 60:739–744CrossRefGoogle Scholar
  31. 31.
    Mertz W (1993) Chromium in human nutrition. A review. J Nutr 123:626–633Google Scholar
  32. 32.
    Staniek H, Wojciak RW (2018) The combined effect of supplementary Cr(III) propionate complex and iron deficiency on the chromium and iron status in female rats. J Trace Elem Med Biol 45:142–149CrossRefGoogle Scholar
  33. 33.
    Stearns DM (2000) Is chromium a trace essential metal? BioFactors 11:149–162CrossRefGoogle Scholar
  34. 34.
    Vincent JB (2017) New evidence against chromium as an essential trace element. J Nutr 147:2212–2219CrossRefGoogle Scholar
  35. 35.
    Chen Y, Watson HM, Gao JJ, Sinha SH, Cassady CJ, Vincent JB (2011) Characterization of the organic component of low molecular weight chromium binding substance and its binding of chromium. J Nutr 141:1225–1232CrossRefGoogle Scholar
  36. 36.
    Schwarz K, Mertz W (1959) Chromium(III) and the glucose tolerance factor. Arch Biochem Biophys 85:292–295CrossRefGoogle Scholar
  37. 37.
    Berdicevsky I, Mirsky N (1994) Effects of insuline and glucose-tolerance factor (GTF) on growth of Saccharomyces cerevisiae. Mycoses 37:405–410CrossRefGoogle Scholar
  38. 38.
    Weksler-Zangen S, Mizrahi T, Raz I (2012) Glucose tolerance factor extracted from yeast: oral insulin-mimetic and insulin-potentiating: in vivo and in vitro studies. Br J Nutr 108:875–882CrossRefGoogle Scholar
  39. 39.
    Liu L, Cui WM, Zhang SW, Kong FH, Pedersen MA, Wen Y, Lv JP (2015) Effect of glucose tolerance factor (GTF) from high chromium yeast on glucose metabolism in insulin-resistant 3T3-L1 adipocytes. RSC Adv 5:3482–3490CrossRefGoogle Scholar
  40. 40.
    Vincent JB, Lukaski HC (2018) Chromium. Adv Nutr 9:505–506CrossRefGoogle Scholar
  41. 41.
    Vincent JB (2015) Is the pharmacological mode of action of chromium(III) as a second messenger? Biol Trace Elem Res 166:7–12CrossRefGoogle Scholar
  42. 42.
    Kitadai N, Oonishi H, Umemoto K, Usui T, Fukushi K, Nakashima S (2017) Glycine polymerization on oxide minerals. Orig Life Evol Biosph 47:123–143CrossRefGoogle Scholar
  43. 43.
    Remko M, Rode BM (2004) Catalyzed peptide bond formation in the gas phase. Role of bivalent cations and water in formation of 2-aminoacetamide from ammonia and glycine and in dimerization of glycine. Struct Chem 15:223–232CrossRefGoogle Scholar
  44. 44.
    Amir R, Galili G, Cohen H (2018) The metabolic roles of free amino acids during seed development. Plant Sci 275:11–18CrossRefGoogle Scholar
  45. 45.
    Watford M, Wu G (2018) Protein. Adv Nutr 9:651–653CrossRefGoogle Scholar
  46. 46.
    Hall JL (2002) Cellular mechanisms for heavy metal detoxification and tolerance. J Exp Bot 53:1–11CrossRefGoogle Scholar
  47. 47.
    Wu SL, Hu YJ, Zhang X, Sun YQ, Wu ZX, Li T, Lv JT, Li JL, Zhang J, Zheng LR, Huang LB, Chen BD (2018) Chromium detoxification in arbuscular mycorrhizal symbiosis mediated by sulfur uptake and metabolism. Environ Exp Bot 147:43–52CrossRefGoogle Scholar
  48. 48.
    Ma H, Li W, Zhou W, Liu J (2017) Site-selective labeling of chromium(III) as a quencher on DNA for molecular beacons. ChemPlusChem 82:1224–1230CrossRefGoogle Scholar
  49. 49.
    Chai J, Liu Y, Liu B, Yang B (2017) Effect of substituent groups (R = -CH3, -Br and -CF3) on the structure, stability and redox property of [Cr(R-pic)2(H2O)2]NO3·H2O complexes. J Mol Struct 1150:307–315CrossRefGoogle Scholar
  50. 50.
    Freeman F, Kappos JC (1985) Permanganate ion oxidations. 15. Additional evidence for formation of soluble (colloidal) manganese dioxide during the permanganate ion oxidation of carbon-carbon double bonds in phosphate-buffered solutions. J Am Chem Soc 107:6628–6633CrossRefGoogle Scholar
  51. 51.
    Freeman F, Chang LY (1986) Permanganate ion oxidations. 17. Kinetics and mechanism of the oxidation of (E)-3-(2-thyenyl)-2-propenoates and (E)-3-(3-thyenyl)-2-propenoates in phosphate-buffered solutions. J Am Chem Soc 108:4504–4509CrossRefGoogle Scholar
  52. 52.
    Perez-Benito JF, Arias C (1991) Occurrence of colloidal manganese dioxide in permanganate reactions. J Colloid Interface Sci 152:70–84CrossRefGoogle Scholar
  53. 53.
    Perez-Benito JF (2009) Autocatalytic reaction pathway on manganese dioxide colloidal particles in the permanganate oxidation of glycine. J Phys Chem C 113:15982–15991CrossRefGoogle Scholar
  54. 54.
    Wilkinson F (1980) Chemical kinetics and reaction mechanisms. Van Nostrand Reinhold, New York, pp 45–47Google Scholar
  55. 55.
    Engel T, Reid P (2010) Physical chemistry. Prentice Hall, New York, p 902Google Scholar
  56. 56.
    Espenson JH (1995) Chemical kinetics and reaction mechanisms. McGraw-Hill, New York, pp 113–115Google Scholar
  57. 57.
    Ni K, Kozak CM (2018) Kinetic studies of copolymerization of cyclohexene oxide with CO2 by a diamino-bis(phenolate) chromium(III) complex. Inorg Chem 57:3097–3106CrossRefGoogle Scholar
  58. 58.
    Ni K, Panjez-Grave V, Kozak CM (2018) Effect of azide and chloride binding to diamino-bis(phenolate) chromium complexes on CO2/cyclohexene oxide copolymerization. Organometallics 37:2507–2518CrossRefGoogle Scholar
  59. 59.
    Binter A, Goodisman J, Dabrowiak JC (2006) Formation of monofunctional cisplatin-DNA adducts in carbonate buffer. J Inorg Biochem 100:1219–1224CrossRefGoogle Scholar
  60. 60.
    Linert W, Jameson RF (1989) The isokinetic relationship. Chem Soc Rev 18:477–505CrossRefGoogle Scholar
  61. 61.
    Lei L, Guo QX (2001) Isokinetic relationship, isoequilibrium relationship, and enthalpy-entropy compensation. Chem Rev 101:673–695CrossRefGoogle Scholar
  62. 62.
    Yelon A, Movaghar B, Crandall RS (2006) Multi-excitation entropy: its role in thermodynamics and kinetics. Rep Prog Phys 69:1145–1194CrossRefGoogle Scholar
  63. 63.
    Barrie PJ (2012) The mathematical origins of the kinetic compensation effect: 1. The effect of random experimental errors. Phys Chem Chem Phys 14:318–326CrossRefGoogle Scholar
  64. 64.
    Barrie PJ (2012) The mathematical origins of the kinetic compensation effect: 2. The effect of systematic errors. Phys Chem Chem Phys 14:327–336CrossRefGoogle Scholar
  65. 65.
    Perez-Benito JF (2013) Some tentative explanations for the enthalpy-entropy compensation effect in chemical kinetics: from experimental errors to the Hinshelwood-like model. Monatsh Chem 144:49–58CrossRefGoogle Scholar
  66. 66.
    Perez-Benito JF, Mulero-Raichs M (2016) Enthalpy-entropy compensation effect in chemical kinetics and experimental errors: a numerical simulation approach. J Phys Chem A 120:7598–7609CrossRefGoogle Scholar
  67. 67.
    Shpanko IV, Sadovaya IV (2018) Enthalpy-entropy compensation effect and other aspects of isoparametricity in reactions between trans-2,3-bis(3-bromo-5-nitrophenyl)oxirane and arenesulfonic acids. React Kinet Mech Catal 123:473–484CrossRefGoogle Scholar
  68. 68.
    McBane GC (1998) Chemistry from telephone numbers: the false isokinetic relationship. J Chem Educ 75:919–922CrossRefGoogle Scholar
  69. 69.
    Salmasi Z, Shier WT, Hashemi M, Mandipour E, Parhiz H, Abnous K, Ramezani M (2015) Heterocyclic amine-modified polyethylenimine as gene carriers for transfection of mammalian cells. Eur J Pharm Biopharm 96:76–88CrossRefGoogle Scholar
  70. 70.
    Porter TL, Eastman MP, Bain E, Begay S (2001) Analysis of peptides synthesized in the presence of SAz-1 montmorillonite and Cu2+ exchanged hectorite. Biophys Chem 91:115–124CrossRefGoogle Scholar
  71. 71.
    Griffith EC, Vaida V (2012) In situ observation of peptide bond formation at the water–air interface. Proc Natl Acad Sci USA 109:15697–15701CrossRefGoogle Scholar
  72. 72.
    Rai D, Sass BM, Moore DA (1987) Chromium(III) hydrolysis constant and solubility of chromium(III) hydroxide. Inorg Chem 26:345–349CrossRefGoogle Scholar
  73. 73.
    Lopez-Gonzalez H, Peralta-Videa JR, Romero-Guzman ET, Rojas-Hernandez A, Gardea-Torresdey JL (2010) Determination of the hydrolysis constants and solubility product of chromium(III) from reduction of dichromate solutions by ICP-OES and UV-visible spectroscopy. J Solut Chem 39:522–532CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2019

Authors and Affiliations

  1. 1.Departamento de Ciencia de Materiales y Quimica Fisica, Seccion de Quimica Fisica, Facultad de QuimicaUniversidad de BarcelonaBarcelonaSpain

Personalised recommendations