Skip to main content
SpringerLink
Log in

Adsorption of cysteine on hematite, magnetite and ferrihydrite: FT-IR, Mössbauer, EPR spectroscopy and X-ray diffractometry studies

  • Original Article
  • Published:
Amino Acids Aims and scope Submit manuscript

Abstract

In the present paper, the adsorption of cysteine on hematite, magnetite and ferrihydrite was studied using FT-IR, electron paramagnetic resonance (EPR), Mössbauer spectroscopy and X-ray diffractometry. Cysteine was dissolved in artificial seawater (two different pHs) which contains the major constituents. There were two main findings described in this paper. First, after the cysteine adsorption, the FT-IR spectroscopy and X-ray diffractometry data showed the formation of cystine. Second, the Mössbauer spectroscopy did not show any increase in the amount of Fe2+ as expected due the oxidation of cysteine to cystine. An explanation could be that Fe2+ was oxidized by the oxygen present in the seawater or there occurred a reduction of cystine by Fe2+ generating cysteine and Fe3+. The specific surface area and pH at point of zero charge of the iron oxides were influenced by adsorption of cysteine. When compared to other iron oxides, ferrihydrite adsorbed significantly (p < 0.05) more cysteine. The pH has a significant (p < 0.05) effect only on cysteine adsorption on hematite. The FT-IR spectroscopy results showed that cystine remains adsorbed on the surface of the iron oxides even after being mixed with KCl and the amine and carboxylic groups are involved in this interaction. X-ray diffractometry showed no changes on iron oxides mineralogy and the following precipitated substances were found along with the iron oxides after drying the samples: cysteine, cystine and seawater salts. The EPR spectroscopy showed that cysteine interacts with iron oxides, changing the relative amounts of iron oxides and hydroxide.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2

References

  • Amirbahman A, Sigg L, von Gunten U (1997) Reductive dissolution of Fe(III) (hydr) oxides by cysteine: kinetics and mechanism. J Colloid Interface Sci 194:194–206

    Article  CAS  PubMed  Google Scholar 

  • Aryal S, Remant BKC, Dharmaraj N, Bhattarai N, Kim CH, Kim HY (2006) Spectroscopic identification of S–Au interaction in cysteine capped gold nanoparticles. Spectrochimica Acta Part A 63:160–163

    Article  CAS  Google Scholar 

  • Baalousha M (2009) Aggregation and disaggregation of iron oxide nanoparticles: influence of particle concentration, pH and natural organic matter. Sci Total Environ 407:2093–2101

    Article  CAS  PubMed  Google Scholar 

  • Basiuk VA (2002) Adsorption of biomolecules at silica. Encyclopedia of surface and colloid science. Marcel Dekker Inc., New York, pp 277–293

    Google Scholar 

  • Basiuk VA, Gromovoy TY (1996) Comparative study of amino acid adsorption on bare and octadecyl silica from water using high performance liquid chromatography. Colloids Surf A Physicochem Eng Asp 118:127–140

    Article  CAS  Google Scholar 

  • Baumgartner E, Blesa MA, Maroto AJG (1982) Kinetics of the dissolution of magnetite in thioglycolic acid solutions. J Chem Soc Dalton Trans 9:1649–1654

    Article  Google Scholar 

  • Bebié J, Schoonen MAA (2000) Pyrite surface interaction with selected organic aqueous species under anoxic conditions. Geochem Trans 1:47–53

    Article  Google Scholar 

  • Benetoli LO, de Souza CM, da Silva KL, de Souza Junior IG, de Santana H, Paesano A Jr, Costa AC, Zaia CTBV, Zaia DAM (2007) Amino acid interaction with and adsorption on clays: FT-IR and Mössbauer spectroscopy and X-ray diffractometry investigations. Orig Life Evol Biosph 37:479–493

    Article  CAS  PubMed  Google Scholar 

  • Bernal JD (1951) The physical basis of life. Routledge and Kegan Paul Ltd., London

    Google Scholar 

  • Bishop JL, Murad E (2002) Spectroscopic and geochemical analyses of ferrihydrite from springs in Iceland and applications to Mars. Geol Soc Lond Spec Publ 202:350–370

    Google Scholar 

  • Brigatti MF, Luoli C, Montorsi S, Poppi L (1999) Effects of exchange cations and layer-charge location on cysteine retention by smectites. Clays Clay Miner 47:664–667

    Article  CAS  Google Scholar 

  • Brunauer S, Emmett PH, Teller E (1938) Adsorption of gases in multimolecular layers. J Am Chem Soc 60:309–319

    Article  CAS  Google Scholar 

  • Carbone C, di Benedetto F, Marescotti P, Sangregorio C, Sorace L, Lima N, Romanelli M, Luchetti G, Cipriani C (2005) Natural Fe-oxide and -oxyhydroxide nanoparticles: na EPR and SQUID investigation. Mineral Petrol 85:19–32

    Article  CAS  Google Scholar 

  • Catling DC, Moore JM (2003) The nature of course-grained crystalline hematite and its implications for the early environment of Mars. Icarus 165:277–300

    Article  CAS  Google Scholar 

  • Cohen H, Gedanken A, Zhong Z (2008) One step synthesis and characterization of ultrastable and amorphous Fe3O4 colloids capped with cysteine molecules. J Phys Chem C 112:15429–15438

    Article  CAS  Google Scholar 

  • Darnell J, Lodish H, Baltimore D (1990) Molecular cell biology. Scientific American Books, New York

    Google Scholar 

  • de Santana H, Paesano A Jr, da Costa AC, Di Mauro E, de Souza Junior IG, Ivashita FF, de Souza CM, Zaia CTBV, Zaia DAM (2010) Cysteine, thiourea and thiocyanate interactions with clays: FT-IR, Mossbauer and EPR spectroscopy and X- ray diffractometry. Amino Acids 38:1089–1099

    Article  CAS  PubMed  Google Scholar 

  • Doong RA, Schink B (2002) Cysteine- mediated reductive dissolution of poorly crystalline iron(III) oxides by Geobacter sulfurreducens. Environ Sci Technol 36:2939–2945

    Article  CAS  PubMed  Google Scholar 

  • Faivre D, Zuddas P (2006) An integrated approach for determining the origin of magnetite nanoparticles. Earth Planet Sci Lett 243:53–60

    Article  CAS  Google Scholar 

  • Guskos N, Papadopoulos GJ, Likodimos V, Patapis S, Yarmis D, Przepiera A, Przepiera K, Majszczyk J, Typek J, Wabia M, Aidinis K, Drazek Z (2002) Photoacoustic, EPR and electrical conductivity investigations of three synthetic mineral pigments: hematite, goethite and magnetite. Mater Res Bull 37:1051–1061

    Article  CAS  Google Scholar 

  • Kosmulski M, Maczka E, Jartych E, Rosenholm JB (2003) Synthesis and characterization of goethite and goethite-hematite composite: experimental study and literature survey. Adv Colloid Interface Sci 103:57–76

    Article  CAS  PubMed  Google Scholar 

  • Lahav N, Chang S (1976) The possible role of solid surface area in condensation reactions during chemical evolution: reevalution. J Mol Evol 8:357–380

    Article  CAS  PubMed  Google Scholar 

  • Lambert JF (2008) Adsorption and polymerization of amino acids on minerals surfaces: a review. Orig Life Evol Biosph 38:211–242

    Article  CAS  PubMed  Google Scholar 

  • Li L, Stanforth R (2000) Distinguishing adsorption and surface precipitation of phosphate on goethite (α-FeOOH). J Colloid Interface Sci 230:12–21

    Article  CAS  PubMed  Google Scholar 

  • Mantion A, Gozzo F, Schmitt B, Stern WB, Gerber Y, Robin AY, Fromm KM, Painsi M, Taubert A (2008) Amino acids in iron oxide mineralization: (incomplete) crystal phase selection is achieved even with single amino acids. J Phys Chem C 112:12104–12110

    Article  CAS  Google Scholar 

  • Marti EM, Methivier Ch, Pradier CM (2004) (S)-cysteine chemisorptions on Cu (110), from the gas or liquid phase: an FT-RAIRS and XPS study. Langmuir 20:10223–10230

    Article  CAS  Google Scholar 

  • Matrajt G, Blanot D (2004) Properties of synthetic ferrihydrite as an amino acid adsorbent and a promoter of peptide bond formation. Amino Acids 26:153–158

    Article  CAS  PubMed  Google Scholar 

  • Mota L, Toledo R, Faria RT Jr, da Silva EC, Vargas H, Deladillo-Hotfort I (2009) Thermally treated soli clays as ceramic raw materials: characterization by x-ray diffraction, photoacoustic spectroscopy and electron spin resonance. Appl Clay Sci 43:243–247

    Article  CAS  Google Scholar 

  • Pawlukojć A, Leciejewicz J, Ramirez-Cuesta AJ, Nowicka-Scheibe J (2005) l-Cysteine: neutron spectroscopy, Raman, IR and ab initio study. Spectrochimica Acta part A 61:2474–2481

    Article  CAS  Google Scholar 

  • Picquart M, Abedinzadeh Z, Grajcar L, Baron MH (1998) Spectroscopic study of N-acetylcysteine and N-acetylcistine/hydrogen peroxide complexation. Chem Phys 228:279–291

    Article  CAS  Google Scholar 

  • Rietmeijer FJM (1996) The ultrafine mineralogy of a molten interplanetary dust particle as an example of the quench regime of atmospheric entry heating. Meteorit Planet Sci 31:237–242

    CAS  Google Scholar 

  • Schwertmann U, Cornell RM (1991) Iron oxides in the laboratory—preparation and characterization. Verlagsgesells chat, Weinheim, p 137

    Google Scholar 

  • Shindo H, Brown TL (1965) Infrared spectra of complexes of l-cysteine and related compounds with zinc (II), cadmium (II), mercury (II) and lead (II). J Am Chem Soc 87:1904–1909

    Article  CAS  PubMed  Google Scholar 

  • Sposito G (1989) The chemistry of soil. Oxford University Press, New York, p 277

    Google Scholar 

  • Stewart S, Fredericks PM (1999) Surface-enhanced Raman spectroscopy of amino acids adsorbed on electrochemically prepared silver surface. Spectrochimica Acta Part A 55:1641–1660

    Article  Google Scholar 

  • Uehara G (1979) Mineral–chemical properties of oxisols. International Soil Classification Workshop, vol 2. Soil Survey Division—Land Development Department, Bangkok, Malaysia, pp 45–60

    Google Scholar 

  • Wade ML, Agresti DG, Wdowiak TJ, Armendarez LP (1999) A Mössbauer investigation of iron rich terrestrial hydrothermal vent systems: lessons for Mars exploration. J Geophys Res 104:8489–8507

    Article  CAS  PubMed  Google Scholar 

  • Wolpert M, Hellwig P (2006) Infrared spectra and molar absorption coefficients of the 20 alpha amino acids in aqueous solutions in the spectral range from 1800 to 500 (cm-1). Spectrochimica Acta part A 64:987–1001

    Article  CAS  Google Scholar 

  • Zaia DAM (2004) Review of adsorption of amino acids on minerals: was it important for origin of life. Amino Acids 27:113–118

    Article  CAS  PubMed  Google Scholar 

  • Zaia DAM, Ribas KC, Zaia CTBV (1999) Spectrphotometric determination of cysteine and: or carbocysteine in a mixture of amino acids, shampoo, and pharmaceutical products using p-benzoquinone. Talanta 50:1003–1010

    Article  CAS  PubMed  Google Scholar 

  • Zaia DAM, Zaia CTBV, de Santana H (2008) Which amino acids should be used in prebiotic chemistry studies? Orig Life Evol Biosph 38:469–488

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgments

This research was supported by grant from Fundação Araucária (15279). The authors are grateful to Dr. Antonio A. da Silva Alfaya for the suggestions and discussion when the manuscript was being prepared.

Author information

Authors and Affiliations

  1. Departamento de Química-CCE, Universidade Estadual de Londrina, Londrina, PR, 86051-990, Brazil

    Alessandra P. Vieira, Henrique de Santana & Dimas A. M. Zaia

  2. Departamento de Física-CCE, Universidade Estadual de Maringá, Maringá, PR, 87020-900, Brazil

    Graciele Berndt & Andrea Paesano Jr

  3. Departamento de Agronomia-CCA, Universidade Estadual de Maringá, Maringá, PR, 87020-900, Brazil

    Ivan G. de Souza Junior & Antonio Carlos S. da Costa

  4. Laboratório de Fluorescência e Ressonância Paramagnética Eletrônica (LAFLURPE)-CCE, Universidade Estadual de Londrina, Londrina, PR, 86051-990, Brazil

    Eduardo Di Mauro

  5. Departamento de Ciências Fisiológicas-CCB, Universidade Estadual de Londrina, Londrina, PR, 86051-990, Brazil

    Cássia T. B. V. Zaia

Authors
  1. Alessandra P. Vieira
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Graciele Berndt
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Ivan G. de Souza Junior
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Eduardo Di Mauro
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Andrea Paesano Jr
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Henrique de Santana
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Antonio Carlos S. da Costa
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Cássia T. B. V. Zaia
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Dimas A. M. Zaia
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Dimas A. M. Zaia.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Vieira, A.P., Berndt, G., de Souza Junior, I.G. et al. Adsorption of cysteine on hematite, magnetite and ferrihydrite: FT-IR, Mössbauer, EPR spectroscopy and X-ray diffractometry studies. Amino Acids 40, 205–214 (2011). https://doi.org/10.1007/s00726-010-0635-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00726-010-0635-y

Keywords

Search

Navigation