Skip to main content Accessibility help
Hostname: page-component-559fc8cf4f-6pznq Total loading time: 0.317 Render date: 2021-03-06T05:43:54.750Z Has data issue: true Feature Flags: { "shouldUseShareProductTool": true, "shouldUseHypothesis": true, "isUnsiloEnabled": true, "metricsAbstractViews": false, "figures": false, "newCiteModal": false, "newCitedByModal": true }

Histidine adsorption onto modified montmorillonite under prebiotic chemistry conditions: a thermodynamic and kinetic study

Published online by Cambridge University Press:  01 December 2020

Rafael Block Samulewski
Universidade Tecnológica Federal do Paraná, Campus Apucarana, Centro, 86812460 Apucarana, PR, Brazil
Regiane Tamires Damasceno Guimarães
Laboratório de Química Prebiótica-LQP, Departamento de Química-CCE, Universidade Estadual de Londrina – UEL, CEP 86812-460 Londrina, PR, Brazil
Dimas Augusto Morozin Zaia
Laboratório de Química Prebiótica-LQP, Departamento de Química-CCE, Universidade Estadual de Londrina – UEL, CEP 86812-460 Londrina, PR, Brazil
E-mail address:


The origin of life from inanimate matter is still an open question, and our knowledge is still very limited. In this sense, prebiotic chemistry seeks to study and understand how chemical reactions may have contributed to the origin of life. Minerals are of great relevance to prebiotic chemistry, as they may have preconcentrated precursors of biomolecules or biomolecules from diluted solutions, provided protection for biomolecules against UV radiation and hydrolysis, catalysing their reactions and played the role of a primitive genetic code. Montmorillonite, a prebiotic mineral, was shown to be able to adsorb adenine and later also histidine. In addition, histidine adsorption did not displace adenine from the montmorillonite. Kinetic experiments showed that using a whole period of time (7 days) it was not possible to adjust the data to any mathematical kinetic model. Thus, the data were separated into four different adsorption ranges: range 1 (0–60 min), range 2 (60–4320 min), range 3 (4320–7200 min) and range 4 (7200–10 080 min). Range 1 showed adsorption that was too fast, meaning no variations in the adsorption data, and the data of range 3 did not fit in any model used in this work. Thus, range 2 (60–4320 min) and range 4 (7200–10 080 min) were analysed. The adsorption kinetics of histidine adsorption indicated two reaction steps, a quick step (60–4320 min), following the pseudo-first-order model, followed by a slower step (7200–10 080 min) of the pseudo-second order. With these results, isotherms were constructed with times of 1 h and 7 days. The results of the quick step (1 h) showed a reaction that was not thermodynamically favoured. For this time range, Gibbs energy values obtained ranged between 5 and 10 kJ mol−1 at temperatures of 20, 35 and 50°C, and the adsorption occurred due to the balance shift of increase in histidine concentrations. The isotherms of the slow step (7 days) presented negative values, showing a more favourable reaction with Gibbs energy values ranging between −5 and −11 kJ mol−1. The mathematical modelling of the data indicates that seawater ions are crucial in the adsorption process. Thus, the study provided essential information for prebiotic chemistry, showing that time and the reaction medium should always be taken into account.

Research Article
Copyright © The Author(s) 2020. Published by Cambridge University Press

Access options

Get access to the full version of this content by using one of the access options below.


Anizelli, PR, Baú, JPT, Gomes, FP, da Costa, ACS, Carneiro, CEA, Zaia, CTBV and Zaia, DAM (2015) A prebiotic chemistry experiment on the adsorption of nucleic acids bases onto a natural zeolite. Origins of Life and Evolution of Biospheres 45, 289306.CrossRefGoogle ScholarPubMed
Anizelli, PR, Baú, JPT, Valezi, DF, Canton, LC, Carneiro, CEA, Di Mauro, E, da Costa, ACS, Galante, D, Braga, AH, Rodrigues, F, Coronas, J, Casado-Coterillo, C, Zaia, CTBV and Zaia, DAM (2016) Adenine interaction with and adsorption on Fe-ZSM-5 zeolites: a prebiotic chemistry study using different techniques. Microporous and Mesoporous Materials 226, 493504.CrossRefGoogle Scholar
Aufdenkampe, AK, Hedges, JI, Richey, JE, Krusche, AV and Llerena, CA (2001) Sorptive fractionation of dissolved organic nitrogen and amino acids onto fine sediments within the Amazon Basin. Limnology and Oceanography 46, 19211935.CrossRefGoogle Scholar
Basiuk, VA (2002). Adsorption of biomolecules at silica. In Hubbard, AT (ed). Encyclopedia of Surface and Colloid Science. Boca Raton, Florida: CRC-Press, p. 359.Google Scholar
Basiuk, VA and Gromovoy, TY (1996) Comparative study of amino acid adsorption on bare and octadecyl silica from water using high-performance liquid chromatography. Colloids and Surfaces A: Physicochemical and Engineering Aspects 118, 127140.CrossRefGoogle Scholar
Baú, JPT, Carneiro, CEA, de Souza Junior, IG, de Souza, CMD, da Costa, ACS, di Mauro, E, Zaia, CTBV, Coronas, J, Casado, C, de Santana, H and Zaia, DAM (2012) Adsorption of adenine and thymine on zeolites: FT-IR and EPR spectroscopy and X-ray diffractometry and SEM studies. Origins of Life and Evolution of Biospheres 42, 1929.CrossRefGoogle ScholarPubMed
Ben-Taleb, A, Vera, P, Delgado, AV and Gallardo, V (1994) Electrokinetic studies of monodisperse hematite particles: effects of inorganic electrolytes and amino acids. Materials Chemistry and Physics 37, 6875.CrossRefGoogle Scholar
Benetoli, LOB, de Souza, CMD, da Silva, KL, de Souza, IG, de Santana, H, Paesano, A, da Costa, ACS, Zaia, CTBV and Zaia, DAM (2007) Amino acid interaction with and adsorption on clays: FT-IR and Mössbauer spectroscopy and X-ray diffractometry investigations. Origins of Life and Evolution of Biospheres 37, 479493.CrossRefGoogle ScholarPubMed
Benetoli, LOB, de Santana, H, Zaia, CTBV and Zaia, DAM (2008) Adsorption of nucleic acid bases on clays: an investigation using Langmuir and Freundlich isotherms and FT-IR spectroscopy. Monatshefte Für Chemie-Chemical Monthly 139, 753761.CrossRefGoogle Scholar
Bera, PP, Stein, T, Head-Gordon, M and Lee, TJ (2017) Mechanisms of the formation of adenine, guanine, and their analogues in UV-irradiated mixed NH3:H2O molecular ices containing purine. Astrobiology 17, 771785.CrossRefGoogle ScholarPubMed
Bernal, JD (1951) The physical basis of life. London, UK: Routledge and Kegan Paul Ltd.Google Scholar
Boyd, GE, Adamson, AW and Myers, LS (1947) The exchange adsorption of ions from aqueous solutions by organic zeolites. II. Kinetics. Journal of the American Chemical Society 69, 28362848.CrossRefGoogle Scholar
Butyrskaya, EV, Zapryagaev, SA and Izmailova, EA (2019) Cooperative model of the histidine and alanine adsorption on single-walled carbon nanotubes. Carbon 143, 276287.CrossRefGoogle Scholar
Carneiro, CEA, de Santana, H, Casado, C, Coronas, J and Zaia, DAM (2011a) Adsorption of amino acids (Ala, Cys, His, Met) on zeolites: Fourier transform infrared and Raman spectroscopy investigations. Astrobiology 11, 409418.CrossRefGoogle Scholar
Carneiro, CEA, Berndt, G, de Junior, IGS, de Souza, CMD, Paesano, A, da Costa, ACS, di Mauro, E, de Santana, H, Zaia, CTBV and Zaia, DAM (2011b) Adsorption of adenine, cytosine, thymine, and uracil on sulfide-modified montmorillonite: FT-IR, Mössbauer and EPR spectroscopy and X-ray diffractometry studies. Origins of Life and Evolution of Biospheres. doi: 10.1007/s11084-011-9244-3.CrossRefGoogle Scholar
Churchill, H, Teng, H and Hazen, RM (2004) Correlation of pH-dependent surface interaction forces to amino acid adsorption: implications for the origin of life. American Mineralogist 89, 10481055.CrossRefGoogle Scholar
Darnell, J, Lodish, D and Baltimore, D (1990) Molecular Cell Biology. New York, USA: Scientific American Books, pp. 771777.Google Scholar
Ding, X and Henrichs, SM (2002) Adsorption and desorption of proteins and polyamino acids by clay minerals and marine sediments. Marine Chemistry 77, 225237.CrossRefGoogle Scholar
Dotto, GL, Vieira, MLG, Gonçalves, JO and Pinto, LAA (2011) Remoção dos corantes azul brilhante, amarelo crepúsculo e amarelo tartrazina de soluções aquosas utilizando carvão ativado, terra ativada, terra diatomácea, quitina e quitosana: estudos de equilíbrio e termodinâmica. Química Nova 34, 11931199.CrossRefGoogle Scholar
Farias, APSF, Tadayozzi, YS, Carneiro, CEA and Zaia, DAM (2014) Salinity and pH affect Na+-montmorillonite dissolution and amino acid adsorption: a prebiotic chemistry study. International Journal of Astrobiology 13, 259270.CrossRefGoogle Scholar
Farias, APSF, Carneiro, CEA, de Batista Fonseca, IC, Zaia, CTBV and Zaia, DAM (2016) The adsorption of amino acids and cations onto goethite: a prebiotic chemistry experiment. Amino Acids 48, 14011412.CrossRefGoogle ScholarPubMed
Ferrero, F (2010) Adsorption of methylene blue on magnesium silicate: kinetics, equilibria and comparison with other adsorbents. Journal of Environmental Sciences 22, 467473.CrossRefGoogle ScholarPubMed
Ferris, JP (1993) Catalysis and prebiotic RNA synthesis. Origins of Life and Evolution of the Biosphere 23, 307315.CrossRefGoogle ScholarPubMed
Ferris, JP and Hagan, WJ Jr (1984) HCN and chemical evolution: the possible role of cyano compounds in prebiotic synthesis. Tetrahedron 40, 10931120.CrossRefGoogle ScholarPubMed
Ferris, JP, Joshi, PC, Edelson, EH and Lawless, JG (1978) HCN: a plausible source of purines, pyrimidines and amino acids on the primitive earth. Journal of Molecular Evolution 11, 293311.CrossRefGoogle ScholarPubMed
Foo, KY and Hameed, BH (2010) Insights into the modeling of adsorption isotherm systems. Chemical Engineering Journal 156, 210.CrossRefGoogle Scholar
Fripiat, J (1984) A.G. Cairns-Smith. Genetic Takeover and the Mineral Origins of Life. Cambridge University Press, 1982. 477 pp. Price £15.00. Clay Minerals 19, 121122.CrossRefGoogle Scholar
Hardy, PM (1985) Chapter 2: The protein amino acids. In Barret, GC (ed). Chemistry and Biochemistry of the Amino Acids. London: Chapman and Hall, pp. 624.CrossRefGoogle Scholar
Hazen, RM, Papineau, D, Bleeker, W, Downs, RT, Ferry, JM, McCoy, TJ, Sverjensky, DA and Yang, H (2008) Mineral evolution. American Mineralogist 93, 16931720.CrossRefGoogle Scholar
Hedges, JI and Hare, PE (1987) Amino acid adsorption by clay minerals in distilled water. Geochimica et Cosmochimica Acta 51, 255259.CrossRefGoogle Scholar
Henrichs, SM and Sugai, SF (1993) Adsorption of amino acids and glucose by sediments of Resurrection Bay, Alaska, USA: functional group effects. Geochimica et Cosmochimica Acta 57, 823835. DOI: 10.1016/0016-7037(93)90171-R.CrossRefGoogle Scholar
Holm, NG and Andersson, E (2005) Hydrothermal simulation experiments as a tool for studies of the origin of life on earth and other terrestrial planets: a review. Astrobiology 5, 444460.CrossRefGoogle ScholarPubMed
Jaber, M, Georgelin, T, Bazzi, H, Costa-Torro, F, Lambert, JF, Bolbach, G and Clodic, G (2014) Selectivities in adsorption and peptidic condensation in the (arginine and glutamic acid)/montmorillonite clay system. The Journal of Physical Chemistry C 118, 2544725455.CrossRefGoogle Scholar
Jackson, TA (1971) Preferential polymerization and adsorption of L-optical isomers of amino acids relative to D-optical isomers on kaolinite templates. Chemical Geology 7, 295306.CrossRefGoogle Scholar
Kotova, DL, Krysanova, TA and Vasil'eva, SY (2020) Equilibrium sorption of histidine on clinoptilolite. Colloid Journal 82, 284287.CrossRefGoogle Scholar
Lahav, N (1994) Minerals and the origin of life – hypotheses and experiments in heterogeneous chemistry. Heterogeneous Chemistry Reviews 1, 159179.Google Scholar
Lahav, N and Chang, S (1976) The possible role of solid surface area in condensation reactions during chemical evolution: reevaluation. Journal of Molecular Evolution 8, 357380.CrossRefGoogle ScholarPubMed
Lambert, JF (2008) Adsorption and polymerization of amino acids on mineral surfaces: a review. Origins of Life and Evolution of the Biosphere 38, 211242.CrossRefGoogle ScholarPubMed
Largitte, L and Pasquier, R (2016) A review of the kinetics adsorption models and their application to the adsorption of lead by an activated carbon. Chemical Engineering Research and Design 109, 495504.CrossRefGoogle Scholar
Lazcano, A and Miller, SL (1996) The origin and early evolution of life: prebiotic chemistry, the pre-RNA world, and time. Cell 85, 793798.Google ScholarPubMed
Lee, N, Sverjensky, DA and Hazen, RM (2014) Cooperative and competitive adsorption of amino acids with Ca2+ on rutile (α-TiO2). Environmental Science & Technology 48, 93589365.CrossRefGoogle Scholar
Li, F, Fitz, D, Fraser, DG and Rode, BM (2010) Arginine in the salt-induced peptide formation reaction: enantioselectivity facilitated by glycine, l- and d-histidine. Amino Acids 39, 579585.CrossRefGoogle ScholarPubMed
Lowe, CU, Rees, MW and Markham, R (1963) Synthesis of complex organic compounds from simple precursors: formation of amino acids, amino acid polymers, fatty acids and purines from ammonium cyanide. Nature 199, 219222.CrossRefGoogle ScholarPubMed
Martins, Z, Botta, O, Fogel, ML, Sephton, MA, Glavin, DP, Watson, JS, Dworkin, JP, Schwartz, AW and Ehrenfreund, P (2008) Extraterrestrial nucleobases in the Murchison meteorite. Earth and Planetary Science Letters 270, 130136.CrossRefGoogle Scholar
Montluçon, DB and Lee, C (2001) Factors affecting lysine sorption in a coastal sediment. Organic Geochemistry 32, 933942.Google Scholar
Paecht-Horowitz, M (1977) The mechanism of clay catalyzed polymerization of amino acid adenylates. Biosystems 9, 9398.CrossRefGoogle ScholarPubMed
Perezgasga, L, Serrato-Díaz, A, Negrón-Mendoza, A, Gal'N, LDP and Mosqueira, FG (2005) Sites of adsorption of adenine, uracil, and their corresponding derivatives on sodium montmorillonite. Origins of Life and Evolution of Biospheres 35, 91110.CrossRefGoogle ScholarPubMed
Plankensteiner, K, Reiner, H and Rode, BM (2006) Amino acids on the rampant primordial earth: electric discharges and the hot salty ocean. Molecular Diversity 10, 37.CrossRefGoogle ScholarPubMed
Rao, M, Odom, DG and Oró, J (1980) Clays in prebiological chemistry. Journal of Molecular Evolution 15, 317331.CrossRefGoogle ScholarPubMed
Roy, D, Najafian, K and von Rague Schleyer, P (2017) Chemical evolution: the mechanism of the formation of adenine under prebiotic conditions. Proceedings of the National Academy of Sciences U.S.A. 104, 1727217277.CrossRefGoogle Scholar
Schoonen, M, Smirnov, A and Cohn, C (2004) A perspective on the role of minerals in prebiotic synthesis. AMBIO: A Journal of the Human Environment 33, 539551.CrossRefGoogle ScholarPubMed
Shen, C, Yang, L, Miller, SL and Oró, J (1990) Prebiotic synthesis of histidine. Journal of Molecular Evolution 31, 167174.CrossRefGoogle ScholarPubMed
Stoks, PG and Schwartz, AW (1979) Nature 282, 709710.CrossRefGoogle Scholar
Suzuki, T, Yano, T, Hara, M and Ebisuzaki, T (2018) Cysteine and cystine adsorption on FeS2(100). Surface Science 674, 612.CrossRefGoogle Scholar
Tanaka, H, Miyajima, K, Nakagaki, M and Shimabayashi, S (1989) Interactions of aspartic acid, alanine and lysine with hydroxyapatite. Chemical & Pharmaceutical Bulletin 37, 28972901.CrossRefGoogle Scholar
Uehara, G (1979) Mineral–Chemical properties of oxisols. In International Soil Classification Workshop, Volume 2; Soil Survey Division-Land Development Department: Bangkok, Thailand, pp. 4546.Google Scholar
Vieira, AP, Berndt, G, de Souza Junior, IG, Di Mauro, E Jr, Paesano, A, de Santana, H, da Costa, ACS, Zaia, CTBV and Zaia, DAM (2011) Adsorption of cysteine on hematite, magnetite and ferrihydrite: FT-IR, Mössbauer, EPR spectroscopy and X-ray diffractometry studies. Amino Acids 40, 205214.CrossRefGoogle ScholarPubMed
Villafañe-Barajas, SA, Baú, JPT, Colín-García, M, Negrón-Mendoza, A, Heredia-Barbero, A, Pi-Puig, T and Zaia, DAM (2018) Salinity effects on the adsorption of nucleic acid compounds on Na-montmorillonite: a prebiotic chemistry experiment. Origins of Life and Evolution of Biospheres 48, 181200.CrossRefGoogle ScholarPubMed
Winter, D and Zubay, G (1995) Binding of adenine and adenine-related compounds to the clay montmorillonite and the mineral hydroxylapatite. Origins of Life and Evolution of the Biosphere 25, 6181.CrossRefGoogle ScholarPubMed
Yasunaga, T and Ikeda, T. (1987) Adsorption-Desorption Kinetics at the Metal-Oxide-Solution Interface Studied by Relaxation Methods. In Geochemical Processes at Mineral Surfaces, ACS Symposium Series, vol. 323, pp. 230250.CrossRefGoogle Scholar
Zaia, DAM (2012) Adsorption of amino acids and nucleic acid bases onto minerals: a few suggestions for prebiotic chemistry experiments. International Journal of Astrobiology 11, 229234.CrossRefGoogle Scholar
Zaia, DAM, Vieira, HJ and Zaia, CTBV (2002) Adsorption of L-amino acids on sea sand. Journal of the Brazilian Chemical Society 13, 679681.CrossRefGoogle Scholar
Zaia, DAM, de Carvalho, PCG, Samulewski, RB, de Carvalho Pereira, R and Zaia, CTBV (2020) Unexpected thiocyanate adsorption onto ferrihydrite under prebiotic chemistry conditions. Origins of Life and Evolution of Biospheres 50, 5776.CrossRefGoogle ScholarPubMed
Zenebon, O, Pascuet, NS and Tiglea, P (2008) Minerais e contaminantes inorgânicos. In Oldair, Zenebon, Neus Sadocco, Pascuet and Paulo, Tiglea (eds). Métodos Físico-Químicos Para Análise de Alimentos, 4th edition edn, São Paulo-SP, Brasil: Editora do Instituto Adolfo Lutz, pp. 735754.Google Scholar

Samulewski et al. supplementary material

Tables S1-S2

File 27 KB

Full text views

Full text views reflects PDF downloads, PDFs sent to Google Drive, Dropbox and Kindle and HTML full text views.

Total number of HTML views: 31
Total number of PDF views: 18 *
View data table for this chart

* Views captured on Cambridge Core between 01st December 2020 - 6th March 2021. This data will be updated every 24 hours.

Send article to Kindle

To send this article to your Kindle, first ensure is added to your Approved Personal Document E-mail List under your Personal Document Settings on the Manage Your Content and Devices page of your Amazon account. Then enter the ‘name’ part of your Kindle email address below. Find out more about sending to your Kindle. Find out more about sending to your Kindle.

Note you can select to send to either the or variations. ‘’ emails are free but can only be sent to your device when it is connected to wi-fi. ‘’ emails can be delivered even when you are not connected to wi-fi, but note that service fees apply.

Find out more about the Kindle Personal Document Service.

Histidine adsorption onto modified montmorillonite under prebiotic chemistry conditions: a thermodynamic and kinetic study
Available formats

Send article to Dropbox

To send this article to your Dropbox account, please select one or more formats and confirm that you agree to abide by our usage policies. If this is the first time you use this feature, you will be asked to authorise Cambridge Core to connect with your <service> account. Find out more about sending content to Dropbox.

Histidine adsorption onto modified montmorillonite under prebiotic chemistry conditions: a thermodynamic and kinetic study
Available formats

Send article to Google Drive

To send this article to your Google Drive account, please select one or more formats and confirm that you agree to abide by our usage policies. If this is the first time you use this feature, you will be asked to authorise Cambridge Core to connect with your <service> account. Find out more about sending content to Google Drive.

Histidine adsorption onto modified montmorillonite under prebiotic chemistry conditions: a thermodynamic and kinetic study
Available formats

Reply to: Submit a response

Your details

Conflicting interests

Do you have any conflicting interests? *