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 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 Environmental parameters, and not phylogeny, determine the composition of extracellular polymeric substances in microbial mats from extreme environments(Elsevier, 2019-02-10) Blanco, Yolanda; Rivas, Luis Alfonso; González-Toril, Elena; Ruiz-Bermejo, Marta; Moreno Paz, Mercedes; Parro, Víctor; Palacín, Arantxa; Aguilera, Angeles; Puente Sánchez, Fernando; Ministerio de Economía y Competitividad (MINECO); Agencia Estatal de Investigación (AEI)The ability to establish biofilms is a key trait for microorganisms growing in extreme environments. The extracellular polymeric substances (EPS) present in biofilms provide not only surface attachment, but also protection against all kinds of environmental stressors, including desiccation, salinity, temperature or heavy metal pollution. The acquisition of suitable biofilm characteristics might thus be an important process mediating the adaptation of microorganisms to novel environmental conditions. In this work we have characterized the EPS of 20 phylogenetically diverse biofilms collected in situ from five contrasting extreme environments, including two geothermal areas (Copahue, Argentina; Seltun, Iceland), two cold areas (Pastoruri glacier, Peru; Byers Peninsula, Antarctica) and one extremely acidic river (Río Tinto, Spain). Biofilms were subjected to biochemical characterization, glycan profiling and immunoprofiling with an antibody microarray. Our results showed that environmental conditions strongly influence biofilm characteristics, with microorganisms from the same environment achieving similar EPS compositions regardless of the phylogeny of their main species. The concentration of some monosaccharides in the EPS could be related to environmental conditions such as temperature or heavy metal toxicity, suggesting that in some cases stress resistance can be mediated by specific sugars. Overall, our results highlight the existence of conserved EPS compositional patterns for each extreme environment, which could in turn be exploited to engineer ecological adaptations in genetically modified microorganisms.Publicación Acceso Abierto An XPS study of HCN-derived films on pyrite surfaces: a prebiotic chemistry standpoint towards the development of protective coatings(Royal Society of Chemistry, 2021-06-06) Pérez Fernández, Cristina; Ruiz-Bermejo, Marta; Gálvez Martínez, Santos; Mateo Marti, Eva; Agencia Estatal de Investigación (AEI); 0000-0002-8059-1335; 0000-0003-4709-4676; Unidad de Excelencia Científica María de Maeztu Centro de Astrobiología del Instituto Nacional de Técnica Aeroespacial y CSIC, MDM-2017-0737Traditionally, the effect of mineral surfaces on increasing molecular complexity has been considered a major issue in studies about the origin of life. In contrast, herein, the effects of organic films derived from cyanide over an important prebiotic mineral, pyrite, are considered. An XPS spectroscopy study was carried out to understand the surface chemistry of the HCN-derived polymer/pyrite system. As a result, the simulation of a plausible prebiotic alkaline hydrothermal environment led to the identification of an NH4CN-based film with protective corrosion properties that immediately prevented the oxidation of the highly reactive pyrite surface. In addition, the effect of coating with antioxidant properties was preserved over a relatively long time, and the polymeric film was very stable under ambient conditions. These results increase the great potential of HCN polymers for development as a cheap and easily produced new class of multifunctional polymeric materials that also show promising and attractive insights into prebiotic chemistry.Publicación Restringido Modelling the kinetics and structural property evolution of a versatile reaction: aqueous HCN polymerization(Royal Society of Chemistry (RSC), 2018-05-29) Fernández, Amparo; Ruiz-Bermejo, Marta; de la fuente, Jose Luis; Ministerio de Economía y Competitividad (MINECO); Instituto Nacional de Técnica Aeroespacial (INTA)The kinetics of the reaction of the synthesis of HCN polymers in aqueous medium at high temperatures have been analysed to ascertain a suitable model for this material, for which it was recently demonstrated that prebiotic chemistry may now be adapted in the development of a new generation of high performance coatings and adhesives with biomedical applications. These experimental conditions were chosen for the simplicity of the reagents, being particularly convenient in regard to potential industrial scale-up of coating technology, where these polymers have revealed an interesting field of application. The kinetics of the precipitation polymerization of HCN in water were studied under isothermal conditions at four different temperatures between 75 °C and 90 °C throughout gravimetric measurements. The use of the Kamal–Sourour autocatalytic kinetic model was proposed, properly describing the overall formation process of this insoluble HCN polymer. All of the kinetic parameters, including reaction orders, kinetic constants and activation energy, were determined for the cross-linking polymerization reaction under study, and a relevant autocatalysis effect was observed. An isoconversion method was also used to analyse the variation of the global activation energy with conversion; and characterization by means of elemental analysis, Fourier transform infrared (FTIR) spectroscopy, and scanning electron microscopy (SEM) was carried out. This study demonstrates the autocatalytic, robust and straightforward character of this heterogeneous aqueous HCN polymerization, and to the best of our knowledge, this report describes the first time that a systematic and extended kinetic analysis has been conducted to obtain a more comprehensive and deeper understanding of this complex reaction, which is of great interest to the origin of life and, currently, to materials science.Publicación Acceso Abierto Tuning the Morphology in the Nanoscale of NH4CN Polymers Synthesized by Microwave Radiation: A Comparative Study(Multidisciplinary Digital Publishing Institute (MDPI), 2021-12-24) Pérez Fernández, Cristina; Valles González, M. P.; González-Toril, Elena; Mateo Marti, Eva; de la fuente, Jose Luis; Ruiz-Bermejo, Marta; Instituto Nacional de Técnica Aeroespacial (INTA); Ministerio de Ciencia e Innovación (MICINN); Agencia Estatal de Investigación (AEI); Centro de Astrobiología del Instituto Nacional de Técnica Aeroespacial y CSIC, MDM-2017-0737A systematic study is presented to explore the NH4CN polymerization induced by microwave (MW) radiation, keeping in mind the recent growing interest in these polymers in material science. Thus, a first approach through two series, varying the reaction times and the temperatures between 130 and 205 °C, was conducted. As a relevant outcome, using particular reaction conditions, polymer conversions similar to those obtained by means of conventional thermal methods were achieved, with the advantage of a very significant reduction of the reaction times. The structural properties of the end products were evaluated using compositional data, spectroscopic measurements, simultaneous thermal analysis (STA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). As a result, based on the principal component analysis (PCA) from the main experimental results collected, practically only the crystallographic features and the morphologies in the nanoscale were affected by the MW-driven polymerization conditions with respect to those obtained by classical syntheses. Therefore, MW radiation allows us to tune the morphology, size and shape of the particles from the bidimensional C=N networks which are characteristic of the NH4CN polymers by an easy, fast, low-cost and green-solvent production. These new insights make these macromolecular systems attractive for exploration in current soft-matter science.Publicación Acceso Abierto Kinetic Study of the Effective Thermal Polymerization of a Prebiotic Monomer: Aminomalononitrile(Multidisciplinary Digital Publishing Institute, 2023-01-17) Hortelano, C.; Ruiz-Bermejo, Marta; de la fuente, Jose Luis; Agencia Estatal de Investigación (AEI); Ministerio de Ciencia e Innovación (MICINN)Publicación Restringido Air effect on both polymerization kinetics and thermal degradation properties of novel HCN polymers based on diaminomaleonitrile(Elsevier, 2022-12) Hortelano, C.; Ruiz-Bermejo, Marta; de la fuente, Jose Luis; Instituto Nacional de Técnica Aeroespacial (INTA); Ministerio de Ciencia, Innovación y Universidades (MICIN); Agencia Estatal de Investigación (AEI); Centro de Astrobiología del Instituto Nacional de Técnica Aeroespacial y CSIC, MDM-2017-0737The impact of air on the bulk polymerization kinetics of diaminomaleonitrile (DAMN), tetramer of HCN, and thermal degradation properties of this resulting conjugated C=N polymeric system is investigated under different temperature regimes and environments. This study shows the effect of exposure to air and oxygen, time, temperature, and evolved gases during DAMN polymerization reactions, which can be suitably monitored by differential scanning calorimetry (DSC) through both dynamic and isothermal measurements. Thus, low heating rates and isothermal scans at 150-170 °C allow us to describe the solid-state polymerization (SSP) of DAMN, and those experiments at 190, 195 and 200 °C and higher heating runs define its melt polymerization (MP) behaviour. Both processes are highly efficient, possibly due to the self-acceleration nature of their kinetics, which is consistent with a three-step Šesták-Berggren (SB) model. The oxygen effect was analysed to determine their tolerance to this variable and confirm the nonradical nature of the mechanism under study. In addition, a detailed thermal characterization by simultaneous DSC/thermogravimetry coupled to mass spectrometry (TG-MS) of these singular polymeric systems obtained under air atmosphere has been completed, and the improvement of the thermal stability of those samples prepared by an SSP at lower temperature was confirmed. The present work offers lower-cost and simpler synthetic methods to obtain this novel class of promising multifunctional polymeric materials through highly efficient and very fast processes.Publicación Acceso Abierto Strong parameter hierarchy in the interstellar phosphorus chemical network(Frontiers in Bioscience Publications, 2025-07-30) Marina, Fernández-Ruz; Jimenez-Serra, Izaskun; Castro, Mario; Ruiz-Bermejo, Marta; Aguirre, Jacobo; European Research Council (ERC); Ministerio de Ciencia e Innovación (MICINN); Consejo Superior de Investigaciones Científicas (CSIC)Phosphorus-bearing molecules are fundamental for life on Earth, yet their astrochemical origins remain poorly understood. Their formation in the interstellar medium has been challenging to elucidate due to limited spectroscopic detections and the reliance on theoretical models that depend on numerous kinetic parameters whose values are very uncertain. Multi-parameter models often suffer from “sloppiness”, where many parameter combinations exhibit negligible influence on model outcomes, while a few dominate system behavior. In this study, we introduce the Fisher Information Spectral Reduction (FISR) algorithm, a novel and computationally efficient method to reduce the complexity of such sloppy models. Our approach exposes the strong parameter hierarchy governing these systems by identifying and eliminating parameters associated with insensitive directions in the parameter space. Applying this methodology to the phosphorus astrochemistry network, we reduce the number of reaction rate coefficients from 14 to 3, pinpointing the key reactions and kinetic parameters responsible for forming PO and PN, the main phosphorus-bearing molecules typically detected in interstellar space. The simplified model retains its predictive accuracy, offering deeper insights into the mechanisms driving phosphorus chemistry in the interstellar medium. This methodology is applicable to multi-parameter models of any kind and, specifically in astrochemistry, facilitates the development of simpler, more realistic and interpretable models to effectively guide targeted observational efforts.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.
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