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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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 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 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.Publicación Restringido Temperature effect on aqueous NH4CN polymerization: Relationship between kinetic behaviour and structural properties(Elsevier BV, 2020-06-05) Mas, I.; de la fuente, Jose Luis; Ruiz-Bermejo, Marta; Agencia Estatal de Investigación (AEI); De la Fuente, J. L. [https://orcid.org/0000-0002-1855-0153]; Unidad de Excelencia Científica María de Maeztu Centro de Astrobiología del Instituto Nacional de Técnica Aeroespacial y CSIC, MDM-2017-0737Herein, a kinetic analysis for aqueous NH4CN polymerizations is presented, which is consistent with an autocatalytic model when polymerizations are performed at relatively high temperatures, 80–90 °C. Further experiments at lower polymerization temperatures, approximately 50 °C, have demonstrated that this relevant prebiotic reaction follows nth-order kinetics rather than an autocatalytic mechanism. In addition, the sol fractions of these precipitation polymerizations have been evaluated by UV–Vis measurements, which also show a mechanistic shift with the reaction temperature. This change in the kinetic behaviour led to the proposal of a simple empirical methodology to describe both chemical- and diffusion-controlled regions. Despite the simplicity of the approach based on the Hill equation, fundamental kinetic parameters, such as the activation energy, can be determined in the diffusion-free zone. These results motivated a systematic structural characterization study of the respective insoluble polymers by means of elemental analysis, FT-IR and NMR spectroscopies and XRD. All these kinetic and structural analyses confirmed that the temperature has a significant effect on the polymerization kinetic of the system, on the macrostructural features and properties of the HCN-based polymers, and presumably also on the polymerization pathways. These data increase our knowledge about the chemistry of this particular family of HCN polymers, which is currently of interest both in the field of materials science and in prebiotic chemistry and astrobiology.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 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.
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