Hostname: page-component-78c5997874-fbnjt Total loading time: 0 Render date: 2024-11-19T23:59:12.404Z Has data issue: false hasContentIssue false

Interaction between adenine and Cu2+ and Fe3+-montmorillonites: a prebiotic chemistry experiment

Published online by Cambridge University Press:  29 March 2021

Rodrigo C. Pereira
Affiliation:
Laboratório de Química Prebiótica, Departamento de Química-CCE, Universidade Estadual de Londrina, 86051-990, Londrina-PR, Brazil
Bruna S. Teixeira
Affiliation:
Laboratório de Química Prebiótica, Departamento de Química-CCE, Universidade Estadual de Londrina, 86051-990, Londrina-PR, Brazil
Antonio C. S. da Costa
Affiliation:
Departamento de Agronomia-CCA, Universidade Estadual de Maringá, 87020-900, Maringá-PR, Brazil
Dimas A. M. Zaia*
Affiliation:
Laboratório de Química Prebiótica, Departamento de Química-CCE, Universidade Estadual de Londrina, 86051-990, Londrina-PR, Brazil
*
Author for correspondence: Dimas A. M. Zaia, E-mail: [email protected]

Abstract

The modification of minerals with metals can promote changes in their surface and, consequently, in their physicochemical properties. Minerals could have played an important role in the origin of life as they can protect molecules against degradation by radiation and hydrolysis, pre-concentrate molecules from dilute solutions and catalyse the formation of polymers. Thus, the current work studied the modification of montmorillonite with Cu2+ and Fe3+ ions. These modified montmorillonites were used to study the interaction with adenine dissolved in distilled water and artificial seawater 4.0 Gy (Gy = billion years ago). The most important result of this work is that the adsorption of adenine onto modified montmorillonites is a complex interaction among adenine, salts in seawater and Cu2+/Fe3+-montmorillonite (Cu2+/Fe3+-Mont) . The adsorption of Cu2+ and Fe3+ onto montmorillonite decreased its surface area and pore volume. The Sips isotherm model showed the best fit of the data and n values indicate that the adenine adsorption process was homogeneous. The highest adenine adsorption was obtained in artificial seawater 4.0 Gy onto Fe3+-Mont at 60°C and the lowest in distilled water or artificial seawater 4.0 Gy onto montmorillonite [montmorillonite washed with distilled water (Mont-STD)] at 60°C. Adenine adsorption onto Mont-STD/montmorillonite modified with 500 ml of 0.1 mol l−1 of CuCl2 and Fe3+-Mont was an exothermic process and an endothermic process, respectively. For all adsorptions ΔG was negative. The adsorption of adenine onto Fe3+-Mont was ruled out by entropy and the other samples by enthalpy and entropy, being a major contribution for Gibbs free energy from enthalpy. The Fourier transform-infrared data indicate that the interaction of adenine with minerals may occur through the NH2 functional group.

Type
Research Article
Copyright
Copyright © The Author(s), 2021. Published by Cambridge University Press

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Andreini, C, Bertini, I, Cavallaro, G, Holliday, GL and Thornton, JM (2008) Metal ions in biological catalysis: from enzyme databases to general principles. Journal of Biological Inorganic Chemistry 13, 12051218.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
Basile, B, Lazcano, A and Oró, J (1984) Prebiotic syntheses of purines and pyrimidines. Advances in Space Research 4, 125131.CrossRefGoogle ScholarPubMed
Basiuk, VA, Gromovoy, TY and Khil'Chevskaya, EG (1995) Adsorption of small biological molecules on silica from diluted aqueous solutions: quantitative characterization and implications to the Bernal's hypothesis. Origins of Life and Evolution of the Biosphere 25, 375393.CrossRefGoogle ScholarPubMed
Bassez, MP (2018) Water near its supercritical point and at alkaline pH for the production of ferric oxides and silicates in anoxic conditions. A new hypothesis for the synthesis of minerals observed in banded iron formations and for the related geobiotropic chemistry. Origins of Life and Evolution of the Biosphere 48, 289320.CrossRefGoogle ScholarPubMed
Baú, JPT, Carneiro, CEA, de Souza Junior, IG, de Souza, CMD, da Costa, ACS, di Mauro, E, Zaia, CTB, 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 the Biosphere 42, 1929.CrossRefGoogle ScholarPubMed
Baú, JPT, Villafañe-Barajas, SA, da Costa, ACS, Negrón-Mendoza, A, Colín-García, M and Zaia, DAM (2020) Adenine adsorbed onto montmorillonite exposed to ionizing radiation: essays on prebiotic chemistry. Astrobiology 20, 2638.CrossRefGoogle ScholarPubMed
Benetoli, LODB, 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 fur Chemie 139, 753761.CrossRefGoogle Scholar
Bernal, JD (1951) The Physical Basis of Life. London, UK: Routledge and Kegan Paul Ltd.Google Scholar
Borquez, E, Cleaves, HJ, Lazcano, A and Miller, SL (2005) An investigation of prebiotic purine synthesis from the hydrolysis of HCN polymers. Origins of Life and Evolution of the Biosphere 35, 7990.CrossRefGoogle ScholarPubMed
Braterman, PS, Cairns-Smith, AG and Sloper, RW (1983) Photo-oxidation of hydrated Fe2+-significance for banded iron formations. Nature 303, 163164.CrossRefGoogle Scholar
Briner, GP (1958) Stability of metal complexes with salicylic acid and related substances. Nature 182, 741742.Google Scholar
Brown, PG, Hildebrand, AR, Zolensky, ME, Grady, M, Clayton, RN, Mayeda, TK, Tagliaferri, E, Spalding, R, MacRae, ND, Hoffman, EL, Mittlefehldt, DW, Wacker, JF, Bird, JA, Campbel, MD, Carpenter, R, Gingerich, H, Glatiotis, M, Greiner, E, Mazur, MJ, McCausland, PJA, Plotkin, H and Mazur, TR (2000) The fall, recovery, orbit, and composition of the Tagish lake meteorite: a new type of carbonaceous chondrite. Science 290, 320325.CrossRefGoogle ScholarPubMed
Bryantsev, VS, Diallo, MS and Goddard, WA III (2009) Computational study of copper(II) complexation and hydrolysis in aqueous solutions using mixed cluster/continuum models. Journal of Physical Chemistry 113, 95599567.CrossRefGoogle ScholarPubMed
Bukka, K, Miller, JD and Shabtai, J (1992) FTIR study of deuterated montmorillonites: structural features relevant to pillared clay stability. Clays and Clay Minerals 40, 92102.CrossRefGoogle Scholar
Canhisares-Filho, JE, Carneiro, CEA, de Santana, H, Urbano, A, da Costa, ACS, Zaia, CTB and Zaia, DAM (2015) Characterization of the adsorption of nucleic acid bases onto ferrihydrite via Fourier transform infrared and surface enhanced Raman spectroscopy and X-ray diffractometry. Astrobiology 15, 728738.CrossRefGoogle ScholarPubMed
Carneiro, CEA, Berndt, G, de Souza Junior, IG, de Souza, CMD, Paesano, A Jr., da Costa, ACS, di Mauro, E, de Santana, H, Zaia, CTB and Zaia, DAM (2011) 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 the Biosphere 41, 453468.CrossRefGoogle ScholarPubMed
Catling, DC and Claire, MW (2005) How earth's atmosphere evolved to an oxic state: a status report. Earth and Planetary Science Letters 237, 120.CrossRefGoogle Scholar
Christensen, JJ, Rytting, JH and Izatt, RM (1970) Thermodynamic pK, ΔH, ΔS, and ΔCp values for proton dissociation from several purines and their nucleosides in aqueous solution. Biochemistry 9, 49074913.CrossRefGoogle Scholar
Cleaves, HJ II, Jonsson, CM, Jonsson, CL, Sverjensky, DA and Hazen, RM (2010) Adsorption of nucleic acid components on rutile (TiO2) surfaces. Astrobiology 10, 311323.CrossRefGoogle Scholar
Cleaves, HJ II, Scott, AM, Hill, FC, Leszczynski, J, Sahai, N and Hazen, RM (2012) Mineral organic interfacial processes: potential roles in the origins of life. Chemical Society Review 41, 55025525.CrossRefGoogle ScholarPubMed
Cohn, CA, Hansson, TK, Larsson, HS, Sowerby, SJ and Holm, NG (2001) Fate of prebiotic adenine. Astrobiology 1, 477480.CrossRefGoogle ScholarPubMed
Colthup, NB, Daly, LH and Wiberly, SE (1964) Introduction to Infrared and Raman Spectroscopy. New York: Academic.Google Scholar
Cornell, RM and Schwertmann, U (2003) The Iron Oxides: Structure, Properties, Reactions, Occurrences, and Uses. Weinheim: Wiley-VCH Verlag GmbH & KGaA, p. 664.CrossRefGoogle Scholar
Curi, R and Procopio, J (2017) Fisiologia Básica, 2nd Edn. Rio de Janeiro-RJ: Editora Guanabara Koogan Ltda.Google Scholar
Do, DD (1998) Adsorption Analysis: Equilibria and Kinetics. London: Imperial College Press.CrossRefGoogle Scholar
Do Nascimento Vieira, A, Kleinermanns, K, Martin, WF and Preiner, M (2020) The ambivalent role of water at the origin of life. FEBS Letters 594, 27172733.CrossRefGoogle Scholar
Feuillie, C, Daniel, I, Michot, LJ and Pedreira-Segade, U (2013) Adsorption of nucleotides onto Fe–Mg–Al rich swelling clays. Geochimica et Cosmochimica Acta 120, 97108.CrossRefGoogle Scholar
Feuillie, C, Sverjensky, DA and Hazen, RM (2015) Attachment of ribonucleotides on a-alumina as a function of pH, ionic strength and surface loading. Langmuir 31, 240248.CrossRefGoogle Scholar
Fitz, D, Reiner, H and Rode, BM (2007) Chemical evolution toward the origin of life. Pure and Applied Chemistry 79, 21012117.CrossRefGoogle Scholar
Foo, KY and Hameed, BH (2010) Insights into the modeling of adsorption isotherm systems. Chemical Engineering Journal 156, 210.CrossRefGoogle Scholar
Fornaro, T, Brucato, JR, Feuillie, C, Sverjensky, DA, Hazen, RM, Brunetto, R, D'Amore, M and Barone, V (2018) Binding of nucleic acid components to the serpentine-hosted hydrothermal mineral brucite. Astrobiology 8, 9891007.CrossRefGoogle Scholar
Hallman, PS, Perrin, DD and Watt, AE (1971) The computed distribution of copper(II) and zinc(II) ions among seventeen amino acids present in human blood plasma. Biochemistry Journal 121, 549555.CrossRefGoogle ScholarPubMed
Hammami, K, El-Feki, H, Marsan, O and Drouet, C (2015) Adsorption of nucleotides on biomimetric apatite: the case of adenosine 5′ monophosphate (AMP). Applied Surface Science 353, 165172.CrossRefGoogle Scholar
Hao, J, Mokhtari, M, Pedreira-Segade, U, Michot, LJ and Daniel, I (2019) Transition metals enhance the adsorption of nucleotides onto clays: implications for the origin of life. Earth and Space Chemistry 3, 109119.CrossRefGoogle Scholar
Haynes, WM (2017) Handbook of Chemistry and Physics, 97th Edn. New York: CRC Press, Taylor & Francis Group, 12-12, p. 2,087.Google Scholar
Hazen, RM (2013) Paleomineralogy of the Hadean Eon: a preliminary species list. American Journal of Science 313, 807843.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
Hua, LL, Kobayashi, K, Ochiai, EI, Gehrke, CW, Gerhardt, KO and Ponnamperuma, C (1986) Identification and quantification of nucleic acid bases in carbonaceous chondrites. Origins of Life and Evolution of the Biosphere 16, 226227.CrossRefGoogle Scholar
Iqubal, MA, Sharma, R, Kamaluddin, and Jheeta, S (2019) Synthesis of nucleic acid bases by metal ferrite nanoparticles from a single carbon atom precursor molecule: formamide. Origins of Life and Evolution of the Biosphere 49, 147162.CrossRefGoogle ScholarPubMed
Izawa, MRM, Nesbitt, HW, Macrae, ND and Hoffman, EL (2010) Composition and evolution of the early oceans: evidence from the Tagish lake meteorite. Earth and Planetary Science Letters 298, 443449.CrossRefGoogle Scholar
Kim, EK and Switzer, C (2014) Bis(6-carboxypurine)-Cu2+: a possibly primitive metal-mediated nucleobase pair. Organic Letters 16, 40594061.CrossRefGoogle ScholarPubMed
Knauth, LP (1998) Salinity history of the earth's early ocean. Nature 395, 554555.CrossRefGoogle ScholarPubMed
Krissansen-Totton, J, Arney, GN and Catling, DC (2018) Constraining the climate and ocean pH of the early earth with a geological carbon cycle model. Proceedings of the National Academy of Science USA 115, 41054110.CrossRefGoogle ScholarPubMed
Krupskaya, VV, Zakusin, SV, Tyupina, EA, Dorzhieva, OV, Zhukhlistov, AP, Belousov, PE and Timofeeva, MN (2017) Experimental study of montmorillonite structure and transformation of Its properties under treatment with inorganic acid solutions. Minerals 7, 4964.CrossRefGoogle Scholar
Lahav, N and Chang, S (1976) The possible role of solid surface area in condensation reactions during chemical evolution. Journal of Molecular Evolution 8, 357380.CrossRefGoogle ScholarPubMed
Lailach, GE and Brindley, GW (1969) Specific co-absorption of purines and pyrimidines by montmorillonite (clay-organic studies XV). Clays and Clay Minerals 17, 95100.CrossRefGoogle Scholar
Lailach, GE, Thompson, TD and Brindley, GW (1968a) Absorption of pyrimidines, purines, and nucleosides by Li-, Na-, Mg-, and Ca-montmorillonite (clay-organic studies XII). Clays and Clay Minerals 16, 285293.CrossRefGoogle Scholar
Lailach, GE, Thompson, TD and Brindley, GW (1968b) Absorption of pyrimidines, purines, and nucleosides by Co-, Ni-, Cu-, and Fe(III)-montmorillonite (clay-organic studies XIII). Clays and Clay Minerals 16, 295301.CrossRefGoogle Scholar
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
Larowe, DE and Regnier, P (2008) Thermodynamic potential for the abiotic synthesis of adenine, cytosine, guanine, thymine, uracil, ribose, and deoxyribose in hydrothermal systems. Origins of Life and Evolution of the Biosphere 38, 383397.CrossRefGoogle ScholarPubMed
Liang, MC, Hartman, H, Kopp, RE, Kirschvink, JL and Yung, YL (2006) Production of hydrogen peroxide in the atmosphere of snow-ball earth and origin of oxygenic photosynthesis. Proceedings of the National Academy of Science USA 103, 1889618899.CrossRefGoogle Scholar
Limousin, G, Gaudet, JP, Charlet, L, Szenknect, S, Barthès, V and Krimissa, M (2007) Sorption isotherms: a review on physical bases, modeling and measurement. Applied Geochemistry 22, 249275.CrossRefGoogle Scholar
Madejová, J (2003) FTIR techniques in clay mineral studies. Vibrational Spectroscopy 31, 110.CrossRefGoogle Scholar
Marshall-Bowman, K, Ohara, S, Sverjensky, DA, Hazen, RM and Cleaves, HJ (2010) Catalytic peptide hydrolysis by mineral surface: implications for prebiotic chemistry. Geochimica et Cosmochimica Acta 74, 58525861.CrossRefGoogle Scholar
Masoud, MS, El-Kaway, MYA, Hinddawy, AM and Soayed, AA (2012) Chemical speciation and equilibria of some nucleic acid compounds and their iron(III) complexes. Spectrochimica Acta A 92, 256282.CrossRefGoogle ScholarPubMed
Morrison, SM, Runyon, SE and Hazen, RM (2018) The paleomineralogy of the Hadean Eon revisited. Life 8, 64.CrossRefGoogle ScholarPubMed
Mortland, MM (1970) Clay–organic complexes and interactions. Advances in Agronomy 22, 75117.CrossRefGoogle Scholar
Mortland, MM, Shaobai, S and Boyd, SA (1986) Clay-organic complexes as adsorbents for phenol and chlorophenols. Clays and Clay Minerals 34, 581585.CrossRefGoogle Scholar
Mosqueira, FG, Albarran, G and Negrón-Mendoza, A (1996) A review of conditions affecting the radiolysis due to 40 K on nucleic acid bases and their derivatives adsorbed on clay minerals: implications in prebiotic chemistry. Origins of Life and Evolution of the Biosphere 26, 7594.CrossRefGoogle Scholar
Murad, E and Fischer, WR (1988) The geobiochemical cycle of iron, chapter 1. In Stucki, JW, Goodman, BA and Schwertmann, U (eds), Iron in Soils and Clay Minerals. Dordrecht, Holland: D. Reidel Publishing Company, pp. 118.Google Scholar
Ochiai, EI (1978) The evolution of the environment and its influence on the evolution of life. Origins of Life 9, 8191.CrossRefGoogle ScholarPubMed
Ochiai, EI (1983) Copper and the biological evolution. BioSystems 16, 8186.CrossRefGoogle ScholarPubMed
Orgel, LE (2004) Prebiotic adenine revisited: eutectics and photochemistry. Origins of Life and Evolution of the Biosphere 34, 361369.CrossRefGoogle ScholarPubMed
Paineau, E, Michot, LJ, Bihannic, I and Baravian, C (2011) Aqueous suspensions of natural swelling clay minerals. 2. Rheological characterization. Langmuir 27, 78067819.CrossRefGoogle ScholarPubMed
Pedreira-Segade, U, Feuillie, C, Pelletier, M, Michot, LJ and Daniel, I (2016) Adsorption of nucleotides onto ferromagnesian phyllosilicates: significance for the origin of life. Geochimica et Cosmochimica Acta 176, 8195.CrossRefGoogle Scholar
Pedreira-Segade, U, Hao, J, Razafitianamaharavo, A, Pelletier, M, Marry, V, Le Crom, S, Michot, LJ and Daniel, I (2018) How do nucleotides adsorb onto clays? Life 8, 59-159-25.CrossRefGoogle ScholarPubMed
Perrin, DD (1959) The stability of iron complexes. Part IV ferric complexes with aliphatic acids. Journal of the Chemical Society, 17101717.CrossRefGoogle Scholar
Perrin, DD (1960) Metal complexes with adenine 1-N-oxide and adenosine 1-N-oxide. Journal of the American Chemical Society 82, 56425645.CrossRefGoogle Scholar
Remko, M and Rode, BM (2001) Catalyzed peptide bond formation in the gas phase. Physical Chemistry Chemical Physics 3, 46674673.CrossRefGoogle Scholar
Rimola, A, Rodríguez-Santiago, L, Ugliengo, P and Sodupe, M (2007) Is the peptide bond formation activated by Cu2+ interactions? Insights from density functional calculations. Journal of Physical Chemistry B 111, 57405747.CrossRefGoogle Scholar
Rode, BM and Schwendinger, MG (1990) Copper catalyzed amino acid condensation in water a simple possible way of prebiotic peptide formation. Origins of Life and Evolution of the Biosphere 20, 401410.CrossRefGoogle Scholar
Rode, BM and Suwannachot, Y (1999) The possible role of Cu(II) for the origin of life. Coordination Chemistry Reviews 190–192, 10851099.CrossRefGoogle Scholar
Rode, BM, Son, HL, Suwannachot, Y and Budjdak, J (1999) The combination of salt induced peptide formation reaction and clay catalysis: a way to higher peptides under primitive earth conditions. Origins of Life and Evolution of the Biosphere 29, 273286.CrossRefGoogle ScholarPubMed
Savic, I, Stojiljkovic, S, Savic, I and Gajic, D (2014) Chapter 15: industrial application of clays and clay minerals. In Wesley, LR (ed.), Clays and Clay Minerals: Geological Origin, Mechanical Properties and Industrial Applications. New York: Nova Publishers, pp. 379402.Google Scholar
Schwartz, AW (2007) Intractable mixtures and the origin of life. Chemistry & Biodiversity 4, 656664.CrossRefGoogle ScholarPubMed
Schwendinger, MG and Rode, BM (1989) Possible role of copper and sodium chloride in prebiotic evolution of peptides. Analytical Sciences 5, 411414.CrossRefGoogle Scholar
Sowerby, SJ, Mörth, CM and Holm, NG (2001) Effect of temperature on the adsorption of adenine. Astrobiology 1, 481487.CrossRefGoogle ScholarPubMed
StrašáK, M (1991) An unsual reaction of adenine and adenosine on montmorillonite. Naturwissenschaften 78, 121122.CrossRefGoogle Scholar
Theng, BKG (2018) Clay mineral catalysis of organic reactions. Boca Raton: CRC Press, Taylor & Francis Group.CrossRefGoogle Scholar
Tyagi, B, Chudasama, CD and Jasra, RV (2006) Determination of structural modification in acid activated montmorillonite clay by FT-IR spectroscopy. Spectrochimica Acta A 64, 273278.CrossRefGoogle ScholarPubMed
Uddin, F (2018) Montmorillonite: An Introduction to Properties and Utilization. In Mansoor, and ZoveidavianpoorIntech, (eds). Current Topics in the Utilization of Clay in Industrial and Medical Applications. London: IntechOpen, pp. 323. doi: 10.5772/intechopen.71295.Google Scholar
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 the Biosphere 48, 181200.CrossRefGoogle ScholarPubMed
Westall, F (2004) Early life on earth: the ancient fossil record. Astrobiology: Future Perspectives. Dordrecht: Springer, pp. 287316.CrossRefGoogle Scholar
Williams, RJP (1985) The symbiosis of metal and protein functions. European of Journal Biochemistry 150, 231248.CrossRefGoogle ScholarPubMed
Williams, RJP (2007) Systems biology evolution: the involvement of metal ions. Biometals 20, 107112.CrossRefGoogle ScholarPubMed
Winter, D and Zubay, G (1995) Binding of adenine and adenine related compounds to the clay mineral montmorillonite and the mineral hydroxylapatite. Origins of Life and Evolution of the Biosphere 25, 6181.CrossRefGoogle ScholarPubMed
Yadav, M, Kumar, R and Krishnamurthy, R (2020) Chemistry of abiotic nucleotide synthesis. Chemical Reviews 120, 47664805.CrossRefGoogle ScholarPubMed
Zaia, DAM (2004) A review of adsorption of amino acids on minerals: was it important for origin of life? Amino Acids 27, 113118.CrossRefGoogle ScholarPubMed
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 and Zaia, CTB (2021) A few experimental suggestions using minerals to obtain peptides with high concentration of L-amino acids and protein amino acids. Symmetry 12, 2046.CrossRefGoogle Scholar