Persona: Ruiz-Bermejo, Marta
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Centro de Astrobiologia
El Centro de Astrobiología (CAB) es un centro mixto de investigación en astrobiología, dependiente tanto del Instituto Nacional de Técnica Aeroespacial (INTA) como del Consejo Superior de Investigaciones Científicas (CSIC).
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Ruiz-Bermejo
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Publicación Acceso Abierto Semiconducting Soft Submicron Particles from the Microwave-Driven Polymerization of Diaminomaleonitrile(Multidisciplinary Digital Publishing Institute (MDPI), 2022-08-24) Ruiz-Bermejo, Marta; García Armada, Pilar; Valles González, M. P.; de la fuente, Jose Luis; Ministerio de Ciencia e Innovación (MICINN); Instituto Nacional de Técnica Aeroespacial (INTA); Centro de Astrobiología del Instituto Nacional de Técnica Aeroespacial y CSIC, MDM-2017-0737The polymers based on diaminomaleonitrile (DAMN polymers) are a special group within an extensive set of complex substances, namely HCN polymers (DAMN is the formal tetramer of the HCN), which currently present a growing interest in materials science. Recently, the thermal polymerizability of DAMN has been reported, both in an aqueous medium and in bulk, offering the potential for the development of capacitors and biosensors, respectively. In the present work, the polymerization of this plausible prebiotic molecule has been hydrothermally explored using microwave radiation (MWR) via the heating of aqueous DAMN suspensions at 170–190 °C. In this way, polymeric submicron particles derived from DAMN were obtained for the first time. The structural, thermal decomposition, and electrochemical properties were also deeply evaluated. The redox behavior was characterized from DMSO solutions of these highly conjugated macromolecular systems and their potential as semiconductors was described. As a result, new semiconducting polymeric submicron particles were synthetized using a very fast, easy, highly robust, and green-solvent process. These results show a new example of the great potential of the polymerization assisted by MWR associated with the HCN-derived polymers, which has a dual interest both in chemical evolution and as functional materials.Publicación Acceso Abierto Prebiotic synthesis of noncanonical nucleobases under plausible alkaline hydrothermal conditions(Springer Nature, 2022-09-07) Pérez Fernández, Cristina; Vega, Jorge; Rayo Pizarroso, P.; Mateo Marti, Eva; Ruiz-Bermejo, Marta; Instituto Nacional de Técnica Aeroespacial (INTA); Ministerio de Economía y Competitividad (MINECO); Agencia Estatal de Investigación (AEI); Ministerio de Ciencia, Innovación y Universidades (MICIN); Centro de Astrobiología del Instituto Nacional de Técnica Aeroespacial y CSIC, MDM-2017-0737Herein, the potential of alkaline hydrothermal environments for the synthesis of possible ancestral pre-RNA nucleobases using cyanide as a primary source of carbon and nitrogen is described. Water cyanide polymerizations were assisted by microwave radiation to obtain high temperature and a relatively high pressure (MWR, 180 °C, 15 bar) and were also carried out using a conventional thermal system (CTS, 80 °C, 1 bar) to simulate subaerial and aerial hydrothermal conditions, respectively, on the early Earth. For these syntheses, the initial concentration of cyanide and the diffusion effects were studied. In addition, it is well known that hydrolysis conditions are directly related to the amount and diversity of organic molecules released from cyanide polymers. Thus, as a first step, we studied the effect of several hydrolysis procedures, generally used in prebiotic chemistry, on some of the potential pre-RNA nucleobases of interest, together with some of their isomers and/or deamination products, also presumably formed in these complex reactions. The results show that the alkaline hydrothermal scenarios with a relatively constant pH are good geological scenarios for the generation of noncanonical nucleobases using cyanide as a prebiotic precursor.Publicación Restringido Highly efficient melt polymerization of diaminomaleonitrile(Elsevier BV, 2021-01-15) Mas, I.; Hortelano, C.; Ruiz-Bermejo, Marta; de la fuente, Jose Luis; Agencia Estatal de Investigación (AEI); 0000-0002-8059-1335; Unidad de Excelencia Científica María de Maeztu Centro de Astrobiología del Instituto Nacional de Técnica Aeroespacial y CSIC, MDM-2017-0737HCN polymers are of great interest in research on the origin of life and, currently, in materials science because they have shown potential for the design of electrical devices, (photo)catalysts and biomedicine. Herein, calorimetric measurements have successfully described the bulk polymerization of HCN tetramer, diaminomaleonitrile (DAMN). Two series of nonisothermal experiments were carried out by differential scanning calorimetry (DSC), and low-heating rate (β) the thermograms (β ≤ 5 °C/min) indicated that the polymerization is initiated at temperatures lower than the DAMN melting point, ~180 °C; while higher heating rates results in a rapid polymerization reaction, which occurs entirely in the liquid phase. The DSC data were analysed using model-free linear iso-conversional methods to estimate kinetic parameters, such as activation energy, and a suitable kinetic model was proposed for these thermal polymerizations in the melt. A preliminary structural and morphological characterization by means of Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) was also completed. This study demonstrated the autocatalytic, highly efficient and straightforward character of this stimulated thermal polymerization of DAMN and, to the best of our knowledge, describes for the first time a systematic and extended kinetic analysis to gain mechanistic insights into this process. The latter was done through the help of simultaneous thermogravimetry (TG)-DSC and in situ mass spectrometry (MS) technique to investigate the gas products generated during these melt polymerizations. These analyses revealed that deamination and dehydrocyanation processes are two relevant reactions involved in DAMN polymerization mechanism.Publicación Acceso Abierto Multivariate Analysis Applied to Microwave-Driven Cyanide Polymerization: A Statistical View of a Complex System(Multidisciplinary Digital Publishing Institute (MDPI), 2023-01-12) Pérez Fernández, Cristina; González Toril, Elena; Mateo Marti, Eva; Ruiz-Bermejo, Marta; Ministerio de Ciencia e Innovación (MICINN)For the first time, chemometrics was applied to the recently reported microwave-driven cyanide polymerization. Fast, easy, robust, low-cost, and green-solvent processes are characteristic of these types of reactions. These economic and environmental benefits, originally inspired by the constraints imposed by plausible prebiotic synthetic conditions, have taken advantage of the development of a new generation of HCN-derived multifunctional materials. HCN-derived polymers present tunable properties by temperature and reaction time. However, the apparently random behavior observed in the evolution of cyanide polymerizations, assisted by microwave radiation over time at different temperatures, leads us to study this highly complex system using multivariate analytical tools to have a proper view of the system. Two components are sufficient to explain between 84 and 98% of the total variance in the data in all principal component analyses. In addition, two components explain more than 91% of the total variance in the data in the case of principal component analysis for categorical data. These consistent statistical results indicate that microwave-driven polymerization is a more robust process than conventional thermal syntheses but also that plausible prebiotic chemistry in alkaline subaerial environments could be more complex than in the aerial part of these systems, presenting a clear example of the “messy chemistry” approach of interest in the research about the origins of life. In addition, the methodology discussed herein could be useful for the data analysis of extraterrestrial samples and for the design of soft materials, in a feedback view between prebiotic chemistry and materials science.Publicación Restringido Ammonium affects the wet chemical network of HCN: feedback between prebiotic chemistry and materials science(Royal Society of Chemistry, 2023-06-21) de la fuente, Jose Luis; Vega, Jorge; Mateo Marti, Eva; Valles González, M. P.; Ruiz-Bermejo, Marta; Pérez Fernández, Cristina; Instituto Nacional de Técnica Aeroespacial (INTA); Universidad Complutense de Madrid (UCM); Agencia Estatal de Investigación (AEI); Consejo Superior de Investigaciones Científicas (CSIC); Ministerio de Ciencia, Innovación y Universidades (MICINN)Prebiotic chemistry one-pot reactions, such as HCN-derived polymerizations, have been used as stimulating starting points for the generation of new multifunctional materials due to the simplicity of the processes, use of water as solvent, and moderate thermal conditions. Slight experimental variations in this special kind of polymerization tune the final properties of the products. Thus, herein, the influence of NH4Cl on the polymerization kinetics of cyanide under hydrothermal conditions and on the macrostructures and properties of this complex system is explored. The kinetics of the process is consistent with an autocatalytic model, but important variations in the polymerization reaction are observed according to a simple empirical model based on a Hill equation. The differences in the kinetic behaviour against NH4Cl were also revealed when the structural, morphological, thermal, electronic and magnetic properties of the synthesized cyanide polymers were compared, and these properties were evaluated by elemental analysis, FTIR, XPS, UV-vis, and ESR spectroscopies, X-ray diffraction, SEM and thermoanalytical techniques. As a result, this hydrothermal prebiotic polymerization is not only pH dependent, as previously thought, but also ammonium subservient. From this result, a hypothetical reaction mechanism was proposed, which involves the active participation of ammonium cations via formamidine and serves as a remarkable point against previous reports. The results discussed here expand the knowledge on HCN wet chemistry, offer an extended view of the relevant parameters during the simulation of hydrothermal scenarios and describe the production of promising paramagnetic and semiconducting materials inspired by prebiotic chemistry.Publicación Acceso Abierto Detecting Nonvolatile Life- and Nonlife-Derived Organics in a Carbonaceous Chondrite Analogue with a New Multiplex Immunoassay and Its Relevance for Planetary Exploration(Mary Ann Liebert, 2018-08-01) Parro, Víctor; Moreno Paz, Mercedes; Gómez Cifuentes, Ana; Ruiz-Bermejo, Marta; Hofstetter, Oliver; Maquieira, Ángel; Manchado, J. M.; Morais, Sergi; Sephton, Mark A.; Niessner, Reinhard; Knopp, Dietmar; Zorzano, María-Paz; Instituto Nacional de Técnica Aeroespacial (INTA); Ministerio de Economía y Competitividad (MINECO)Potential martian molecular targets include those supplied by meteoritic carbonaceous chondrites such as amino acids and polycyclic aromatic hydrocarbons and true biomarkers stemming from any hypothetical martian biota (organic architectures that can be directly related to once-living organisms). Heat extraction and pyrolysis-based methods currently used in planetary exploration are highly aggressive and very often modify the target molecules, making their identification a cumbersome task. We have developed and validated a mild, nondestructive, multiplex inhibitory microarray immunoassay and demonstrated its implementation in the SOLID (Signs of Life Detector) instrument for simultaneous detection of several nonvolatile life- and nonlife-derived organic molecules relevant in planetary exploration and environmental monitoring. By utilizing a set of highly specific antibodies that recognize D- or L-aromatic amino acids (Phe, Tyr, Trp), benzo[a]pyrene (B[a]P), pentachlorophenol, and sulfone-containing aromatic compounds, respectively, the assay was validated in the SOLID instrument for the analysis of carbon-rich samples used as analogues of the organic material in carbonaceous chondrites or even Mars samples. Most of the antibodies enabled sensitivities at the 1–10 ppb level and some even at the part-per-trillion level. The multiplex immunoassay allowed the detection of B[a]P as well as aromatic sulfones in a water/methanol extract of an Early Cretaceous lignite sample (ca. 140 Ma) representing type IV kerogen. No L- or D-aromatic amino acids were detected, reflecting the advanced diagenetic stage and the fossil nature of the sample. The results demonstrate the ability of the liquid extraction by ultrasonication and the versatility of the multiplex inhibitory immunoassays in the SOLID instrument to discriminate between organic matter derived from life and nonlife processes, an essential step toward life detection outside Earth.Publicación Acceso Abierto Prebiotic chemistry in neutral/reduced-alkaline gas-liquid interfaces(Springer Nature, 2019-02-13) Mompeán, Cristina; Roig Marín-Yaseli, Margarita; Espigares, Patricia; González Toril, Elena; Zorzano, María-Paz; Ruiz-Bermejo, Marta; Ministerio de Economía y Competitividad (MINECO); Instituto Nacional de Técnica Aeroespacial (INTA)The conditions for the potential abiotic formation of organic compounds from inorganic precursors have great implications for our understanding of the origin of life on Earth and for its possible detection in other environments of the Solar System. It is known that aerosol-interfaces are effective at enhancing prebiotic chemical reactions, but the roles of salinity and pH have been poorly investigated to date. Here, we experimentally demonstrate the uniqueness of alkaline aerosols as prebiotic reactors that produce an undifferentiated accumulation of a variety of multi-carbon biomolecules resulting from high-energy processes (in our case, electrical discharges). Using simulation experiments, we demonstrate that the detection of important biomolecules in tholins increases when plausible and particular local planetary environmental conditions are simulated. A greater diversity in amino acids, carboxylic acids, N-heterocycles, and ketoacids, such as glyoxylic and pyruvic acid, was identified in tholins synthetized from reduced and neutral atmospheres in the presence of alkaline aqueous aerosols than that from the same atmospheres but using neutral or acidic aqueous aerosols.Publicación Acceso Abierto A Comprehensive Review of HCN-Derived Polymers(Multidisciplinary Digital Publishing Institute (MDPI), 2021-03-29) Ruiz-Bermejo, Marta; de la fuente, Jose Luis; Pérez Fernández, Cristina; Mateo Marti, Eva; Ruiz Bermejo, M. [0000-0002-8059-1335]; Mateo Martí, E. [0000-0003-4709-4676]; Unidad de Excelencia Científica María de Maeztu del Centro de Astrobiología del Instituto Nacional de Técnica Aeroespacial y CSIC, MDM-2017-0737HCN-derived polymers are a heterogeneous group of complex substances synthesized from pure HCN; from its salts; from its oligomers, specifically its trimer and tetramer, amino-nalono-nitrile (AMN) and diamino-maleo-nitrile (DAMN), respectively; or from its hydrolysis products, such as formamide, under a wide range of experimental conditions. The characteristics and properties of HCN-derived polymers depend directly on the synthetic conditions used for their production and, by extension, their potential applications. These puzzling systems have been known mainly in the fields of prebiotic chemistry and in studies on the origins of life and astrobiology since the first prebiotic production of adenine by Oró in the early years of the 1960s. However, the first reference regarding their possible role in prebiotic chemistry was mentioned in the 19th century by Pflüger. Currently, HCN-derived polymers are considered keys in the formation of the first and primeval protometabolic and informational systems, and they may be among the most readily formed organic macromolecules in the solar system. In addition, HCN-derived polymers have attracted a growing interest in materials science due to their potential biomedical applications as coatings and adhesives; they have also been proposed as valuable models for multifunctional materials with emergent properties such as semi-conductivity, ferroelectricity, catalysis and photocatalysis, and heterogeneous organo-synthesis. However, the real structures and the formation pathways of these fascinating substances have not yet been fully elucidated; several models based on either computational approaches or spectroscopic and analytical techniques have endeavored to shed light on their complete nature. In this review, a comprehensive perspective of HCN-derived polymers is presented, taking into account all the aspects indicated above.Publicación Restringido HCN-derived polymers from thermally induced polymerization of diaminomaleonitrile: A non-enzymatic peroxide sensor based on prebiotic chemistry(Elsevier, 2021-11-24) Ruiz-Bermejo, Marta; García Armada, Pilar; Mateo Marti, Eva; de la fuente, Jose Luis; Ministerio de Ciencia e Innovación (MICINN); Instituto Nacional de Técnica Aeroespacial (INTA); Centro de Astrobiología del Instituto Nacional de Técnica Aeroespacial y CSIC, MDM-2017-0737HCN-derived polymers have recently attracted considerable attention due to their promising applications as multifunctional materials. This study, inspired by plausible early Earth geochemical conditions, describes a strategy to synthesize them from the self-initiated thermal bulk polymerization of the HCN tetramer, diaminomaleonitrile (DAMN), with outstanding sensing properties. These conjugated polymers were obtained through noncatalysed and simple isothermal reactions at 170 °C in the solid-state, and experiments at 190 °C permitted polymerization in the melt. Both processes are highly efficient, allowing quantitative yields of the end products. The conductivity properties of both polymers have been explored to show their high potential, especially DAMN polymers synthesized in melt, as nonenzymatic peroxide sensors. To better understand the differences found between the two series, structural characterisation was carried out using compositional data, Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR) and X-ray photoelectron (XPS) spectroscopies, and X-ray diffraction (XRD) measurements. The interpretation of the structural data suggests that a two-dimensional (2-D) macrostructure based on N-heterocyclics is predominant regardless of the state of monomer aggregation during the course of polymerization, but preferably formed in the melt. The morphological and thermal stability properties of the polymers based on DAMN were also evaluated. Finally, the most likely mechanisms based on the dehydrocyanation and deamination reactions that take place during the polymerization reaction are proposed. This study demonstrates the robust and straightforward character of these thermally activated polymerizations, which are of interest to chemical evolution research and to current materials and surface science.Publicación Restringido Solid-state polymerization of diaminomaleonitrile: Toward a new generation of conjugated functional materials(Elsevier BV, 2021-05-03) Hortelano, C.; Ruiz-Bermejo, Marta; de la fuente, Jose Luis; Unidad de Excelencia Científica María de Maeztu Centro de Astrobiología del Instituto Nacional de Técnica Aeroespacial y CSIC, MDM-2017-0737The solid-state polymerization (SSP) of organic molecules to form two-dimensional (2D) materials remains a challenge, especially when these reactions are performed in one pot using a single reagent. As will be shown, the SSP of the HCN tetramer diaminomaleonitrile (DAMN) may be an excellent example of these reactions. Dynamic experiments by differential scanning calorimetry (DSC) allow the analysis of the thermally initiated bulk polymerization of DAMN. Under nonisothermal measurements at low heating rates, a multiple-step polymerization reaction takes place. The SSP of DAMN is highly efficient, possibly due to the autocatalytic nature of its kinetics, which are consistent with the two-parameter Šesták-Berggren (SB) model and describe the three stages found in its complicated mechanism, confirmed also from an analysis of the variation in the apparent activation energy with the conversion degree. Relevant mechanistic aspects, such as the dehydrocyanation and deamination processes during SSP, are extracted by thermogravimetry-mass spectrometry (TG-MS). Moreover, some structural and morphological properties of these materials are characterized by Fourier-transform infrared (FTIR) spectroscopy and microscopy. All this information allows us to propose hypothetical pathways for the production of a complex conjugated system, predominantly constituted by a 2D macrostructure based on imidazole rings. This work opens up new possibilities for the synthesis of functional poly(heterocycle) systems, expanding our view of a plausible prebiotic chemical reaction space and providing the foundation for systematic studies of the structure-property relationships of novel HCN-derived polymers, which are currently of great interest in the fields of materials and surface science.
