This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev. Cite this: DOI: 10.1039/c2cs35112a Mineral–organic interfacial processes: potential roles in the origins of lifew H. James Cleaves II, a Andrea Michalkova Scott, bc Frances C. Hill, bc Jerzy Leszczynski, bc Nita Sahai de and Robert Hazen f Received 2nd April 2012 DOI: 10.1039/c2cs35112a Life is believed to have originated on Earth B4.4–3.5 Ga ago, via processes in which organic compounds supplied by the environment self-organized, in some geochemical environmental niches, into systems capable of replication with hereditary mutation. This process is generally supposed to have occurred in an aqueous environment and, likely, in the presence of minerals. Mineral surfaces present rich opportunities for heterogeneous catalysis and concentration which may have significantly altered and directed the process of prebiotic organic complexification leading to life. We review here general concepts in prebiotic mineral-organic interfacial processes, as well as recent advances in the study of mineral surface-organic interactions of potential relevance to understanding the origin of life. 1. Introduction Mineral–organic interactions are important for a variety of modern geochemical phenomena including petroleum forma- tion and maturation 1 and the global carbon cycle. 2 These sorts of interactions were potentially also important for the origin of life on Earth, 3–11 and on extra-terrestrial bodies. It is notoriously difficult to define ‘‘life’’, which causes significant problems for efforts to understand its origin (see, for example, the special section in the journal Astrobiology (2010) volume 10, pp. 1001–1042). One popular definition is that life is a ‘‘self-sustained chemical reaction capable of undergoing Darwinian evolution’’ 12 (i.e., one capable of a Blue Marble Space Institute of Science, Washington, DC 20016, USA b U.S. Army Engineer Research and Development Center (ERDC), Vicksburg, MS 39180, USA c Interdisciplinary Nanotoxicity Center, Jackson State University, Jackson, MS 39217, USA d Department of Polymer Science, University of Akron, Akron OH 44325, USA e NASA Astrobiology Institute, University of Akron, Akron, OH 44325, USA f Carnegie Institution of Washington, 5251 Broad Branch Rd. NW, Washington, DC 20015, USA w Part of the prebiotic chemistry themed issue. H. James Cleaves II Dr Cleaves received his PhD in chemistry in 2001 from the University of California, San Diego, then conducted post-doctoral research at the Scripps Institution of Oceano- graphy and the Carnegie Institution of Washington. His research concerns organic geochemistry, abiotic organic synthesis, the question of how life arose on Earth, methods for detecting Life on other planets and the interactions of organic compounds with mineral surfaces. Presently he is exploring the application of chemoinformatics to prebiotic chemistry and the analysis of extraterrestrial materials. He is a research scientist at the Blue Marble Space Institute of Science. Andrea Michalkova Scott Andrea Michalkova Scott was born in Slovak Republic. She received MS in Mathematics and Chemistry in 1997 and PhD in Inorganic Chemistry in 2002 (working with Daniel Tunega) from Comenius University in Bratislava, Slovakia. This was followed by nine years of post-doctoral work in Jerzy Leszczynski’s group at Jackson State University, Jackson, MS. In 2011 she joined the U.S. Army Engineer Research and Development Center (ERDC) in Vicksburg, MS where she works now as a Research Chemist. Chem Soc Rev Dynamic Article Links www.rsc.org/csr CRITICAL REVIEW Downloaded by University of Sussex on 28 June 2012 Published on 28 June 2012 on http://pubs.rsc.org | doi:10.1039/C2CS35112A View Online / Journal Homepage
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This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev.
Cite this: DOI: 10.1039/c2cs35112a
Mineral–organic interfacial processes: potential roles in the origins of
lifew
H. James Cleaves II,aAndrea Michalkova Scott,
bcFrances C. Hill,
bc
Jerzy Leszczynski,bc
Nita Sahaide
and Robert Hazenf
Received 2nd April 2012
DOI: 10.1039/c2cs35112a
Life is believed to have originated on Earth B4.4–3.5 Ga ago, via processes in which organic
compounds supplied by the environment self-organized, in some geochemical environmental
niches, into systems capable of replication with hereditary mutation. This process is generally
supposed to have occurred in an aqueous environment and, likely, in the presence of minerals.
Mineral surfaces present rich opportunities for heterogeneous catalysis and concentration which
may have significantly altered and directed the process of prebiotic organic complexification
leading to life. We review here general concepts in prebiotic mineral-organic interfacial processes,
as well as recent advances in the study of mineral surface-organic interactions of potential
relevance to understanding the origin of life.
1. Introduction
Mineral–organic interactions are important for a variety of
modern geochemical phenomena including petroleum forma-
tion and maturation1 and the global carbon cycle.2 These sorts
of interactions were potentially also important for the origin of
life on Earth,3–11 and on extra-terrestrial bodies.
It is notoriously difficult to define ‘‘life’’, which causes
significant problems for efforts to understand its origin (see,
for example, the special section in the journal Astrobiology
(2010) volume 10, pp. 1001–1042). One popular definition is
that life is a ‘‘self-sustained chemical reaction capable of
undergoing Darwinian evolution’’12 (i.e., one capable of
a Blue Marble Space Institute of Science, Washington,DC 20016, USA
bU.S. Army Engineer Research and Development Center (ERDC),Vicksburg, MS 39180, USA
c Interdisciplinary Nanotoxicity Center, Jackson State University,Jackson, MS 39217, USA
dDepartment of Polymer Science, University of Akron,Akron OH 44325, USA
eNASA Astrobiology Institute, University of Akron, Akron,OH 44325, USA
fCarnegie Institution of Washington, 5251 Broad Branch Rd. NW,Washington, DC 20015, USAw Part of the prebiotic chemistry themed issue.
H. James Cleaves II
Dr Cleaves received his PhDin chemistry in 2001 from theUniversity of California,San Diego, then conductedpost-doctoral research at theScripps Institution of Oceano-graphy and the CarnegieInstitution of Washington.His research concerns organicgeochemistry, abiotic organicsynthesis, the question of howlife arose on Earth, methodsfor detecting Life on otherplanets and the interactionsof organic compounds withmineral surfaces. Presently he
is exploring the application of chemoinformatics to prebioticchemistry and the analysis of extraterrestrial materials. He is aresearch scientist at the Blue Marble Space Institute of Science.
Andrea Michalkova Scott
Andrea Michalkova Scott wasborn in Slovak Republic. Shereceived MS in Mathematicsand Chemistry in 1997 andPhD in Inorganic Chemistryin 2002 (working with DanielTunega) from ComeniusUniversity in Bratislava,Slovakia. This was followedby nine years of post-doctoralwork in Jerzy Leszczynski’sgroup at Jackson StateUniversity, Jackson, MS. In2011 she joined the U.S.Army Engineer Researchand Development Center
(ERDC) in Vicksburg, MS where she works now as aResearch Chemist.
Chem. Soc. Rev. This journal is c The Royal Society of Chemistry 2012
replication with mutations which are able to be culled by
natural selection). According to some definitions, this system
must also be membrane-bounded.
The origin of life is generally envisioned as having pro-
ceeded from the formation of organic compounds from
environmentally-supplied precursors, to their self-organization
under various environmental conditions into self-replicating
and energy-transducing systems, and their further evolution
into modern biochemical systems.13,14 These ideas are open to
experimental investigation, where the types of chemistry and
plausible geochemical environments must be given due con-
sideration. For example, models for the origin of life include
schemes for the origin of membranes,15 metabolic cycles10 and
nucleic acids (e.g., the RNA World16), many of which invoke
catalytic or functional roles for mineral surfaces.
Given the many likely available mineral types, and the hetero-
geneity of their surfaces in natural environments,17 mineral
surfaces could potentially have provided almost any type of
general catalysis,18 albeit with low specificity and efficiency. The
ubiquity of mineral–water interfaces at the surface of the Earth
renders it almost impossible to discount the role of interfacial
process with organic molecules relevant to the origin of life.
Modern biochemistry mainly uses protein enzymes, which
are genetically-encoded polymers of a-amino acids, as cata-
lysts. Many of these include a cofactor such as an organic
coenzyme, a metal sulfide cluster or a metal ion. Some
enzymes have evolved to be almost perfect catalysts, in that
they represent an exquisite balance between the affinity of the
catalyst for both substrate and transition state binding, and
product release.19–21 Such enzymes provide rate enhancements
of as much as 1020 fold for specific chemical reactions, though
more typical values are on the order of 106 to 1015-fold).22 The
reasons evolution selected a-amino acids to construct catalysts
remain speculative,23,24 but recent laboratory results suggest
that once formed, such enzymes were able to explore an almost
limitless catalytic space.25
Frances C. Hill
Frances C. Hill is a native ofCleveland Heights, OH. Shereceived a BA in Chemistryfrom Case Western ReserveUniversity,MS in Geochemistryfrom Purdue University,and PhD in Mineralogy/Geochemistry from VirginiaTech. She completed post-doctoral research at theUniversity of Notre Dame,and Rutgers University. Shespent eight years at the ArmyHigh Performance ComputingResearch Center inMinneapolis,MN, as the lead computational
chemist. Since 2007 she has worked as a Research Chemist/Team Leader for the computational chemistry team at the USArmy Engineer Research and Development Center (ERDC) inVicksburg, MS.
Jerzy Leszczynski
Jerzy Leszczynski is aProfessor of Chemistry andthe President’s DistinguishedFellow at Jackson StateUniversity (JSU). He joinedthe faculty of the JSU Depart-ment of Chemistry in 1990. Hedirects the InterdisciplinaryNanotoxicity CREST Centerat JSU. His broad researchinterests include variousapplications of computationalchemistry. Dr Leszczynskiobtained his MS and PhDdegrees at the TechnicalUniversity of Wroclaw in
Poland, where he was also a fculty member from 1976–1986.In 1986 he moved to the USA, initially working at the Universityof Florida, Quantum Theory Project (1986–88) and at theUniversity of Alabama at Birmingham (1988–1990).
Nita Sahai
Professor Nita Sahai has beenthe Ohio Research Scholar Chairin Biomaterials, Departmentof Polymer Science, Universityof Akron since August 2011.Prior to this, she was aProfessor in the Departmentof Geoscience, University ofWisconsin-Madison for 11 years.Prof. Sahai’s research focuseson the physical-chemicalaspects of cellular and bio-molecular interactions atmineral surfaces, of relevanceto prebiotic chemistry, bio-mineralization and bone tissue
engineering. Her research is supported by NSF, NASA andACS-PRF. Prof. Sahai has been interviewed on National PublicRadio’s, ‘‘To the Best of Our Knowledge,’’ for her research onthe origin of life.
Robert Hazen
Robert M. Hazen, SeniorResearch Scientist at theCarnegie Institution ofWashington’s GeophysicalLaboratory and the ClarenceRobinson Professor of EarthScience at George MasonUniversity, received the BSand SM in geology at theMassachusetts Institute ofTechnology (1971), and thePhD at Harvard Universityin earth science (1975).The Past President of theMineralogical Society ofAmerica, Hazen’s recent
research focuses on the possible roles of minerals in the originof life. He is also Principal Investigator of the Deep CarbonObservatory (http://dco.ciw.edu).
Chem. Soc. Rev. This journal is c The Royal Society of Chemistry 2012
from research conducted under the Environmental Quality
Technology Program of the United States Army Corps of
Engineers by the USAERDC. Permission was granted by the
Chief of Engineers to publish this information. The findings of
this report are not to be construed as an official Department of
the Army position unless so designated by other authorized
documents.
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