Infrared spectral investigations of UV irradiated nucleobases adsorbed on mineral surfaces

Fornaro, Teresa; Brucato, J. R.; Pace, E.; Guidi, M. Cestelli; Branciamore, Sergio; Pucci, Amaranta

doi:10.1016/j.icarus.2013.07.024

Cited by 32 publications

(55 citation statements)

References 65 publications

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“…As a consequence, when considering nucleobases in condensed-phases or adsorbed onto surfaces, assignments of spectroscopic features based on gas-phase data could be misleading 30 , bringing to an incorrect interpretation of the spectra and thus of the actual groups involved in the interactions. Therefore, for a correct assignment of vibrational frequencies it is fundamental to carry out computational spectroscopy studies not only for isolated molecules but especially for the complexes.…”

Section: Discussionmentioning

confidence: 99%

“…However, due to the great variety of interactions between the adsorbate and the interface and to complex environmental factors, the results of experimental spectroscopic studies on these kinds of systems are difficult to interpret 30 . Even though some hints can be obtained through the comparison with available gas-phase spectroscopic data, these are not sufficient for a complete characterization of their properties.…”

Section: Introductionmentioning

confidence: 99%

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Dispersion corrected DFT approaches for anharmonic vibrational frequency calculations: nucleobases and their dimers

Fornaro

Biczysko

Monti

et al. 2014

Phys. Chem. Chem. Phys.

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101

113

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Computational spectroscopy techniques have become in the last years effective means to analyze and assign infrared (IR) spectra for molecular systems of increasing dimensions and in different environments. However, transition from compilations of harmonic data to full anharmonic simulations of spectra is still under way. The most promising results for large systems have been obtained, in our opinion, by perturbative vibrational approaches based on potential energy surfaces computed by hybrid (especially B3LYP) density functionals and medium size (e.g. SNSD) basis sets. In this framework, we are actively developing a comprehensive and robust computational protocol aimed to a quantitative reproduction of the spectra of nucleic acid bases complexes and their adsorption on solid supports (organic/inorganic). In this contribution we report the essential results of the first step devoted to isolated monomers and dimers. It is well known that in order to model the vibrational spectra of weakly bound molecular complexes dispersion interactions should be taken into proper account. In this work, we have chosen two popular and inexpensive approaches to model dispersion interaction, namely the semi-empirical dispersion correction (D3) and pseudopotential based (DCP) methodologies both in conjunction with the B3LYP functional. These have been used for simulating fully anharmonic IR spectra of nucleobases and their dimers through generalized second order vibrational perturbation theory (GVPT2). We have studied, in particular, isolated adenine, hypoxanthine, uracil, thymine and cytosine, the hydrogen-bonded and stacked adenine and uracil dimers, and the stacked adenine-naphthalene heterodimer. Anharmonic frequencies are compared with standard B3LYP results and experimental findings, while the computed interaction energies and structures of complexes are compared to the best available theoretical estimates.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Dispersion corrected DFT approaches for anharmonic vibrational frequency calculations: nucleobases and their dimers

Fornaro

Biczysko

Monti

et al. 2014

Phys. Chem. Chem. Phys.

Self Cite

101

113

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“…Minerals may play a fundamental role in processes that lead to the emergence of complex molecules because they can act as catalysts, promoting chemical reactions and the synthesis of new molecular species on their surface or protecting molecules against UV degradation. Moreover, they can adsorb molecules allowing their concentration in the ice mantles (Fornaro et al 2013). Among these latter complex molecules, formamide (HCONH 2 ) is of crucial importance.…”

Section: Introductionmentioning

confidence: 99%

Photoprocessing of formamide ice: route towards prebiotic chemistry in space

Corazzi

Fedele

Poggiali

et al. 2020

A&A

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Aims. Formamide (HCONH 2 ) is the simplest molecule containing the peptide bond first detected in the gas phase in Orion-KL and SgrB 2 . In recent years, it has been observed in high temperature regions such as hot corinos, where thermal desorption is responsible for the sublimation of frozen mantles into the gas phase. The interpretation of observations can benefit from information gathered in the laboratory, where it is possible to simulate the thermal desorption process and to study formamide under simulated space conditions such as UV irradiation. Methods. Here, two laboratory analyses are reported: we studied formamide photo-stability under UV irradiation when it is adsorbed by space relevant minerals at 63 K and in the vacuum regime. We also investigated temperature programmed desorption of pure formamide ice in the presence of TiO 2 dust before and after UV irradiation. Results. Through these analyses, the effects of UV degradation and the interaction between formamide and different minerals are compared. We find that silicates, both hydrates and anhydrates, offer molecules a higher level of protection from UV degradation than mineral oxides. The desorption temperature found for pure formamide is 220 K. The desorption temperature increases to 250 K when the formamide desorbs from the surface of TiO 2 grains. Conclusions. Through the experiments outlined here, it is possible to follow the desorption of formamide and its fragments, simulate the desorption process in star forming regions and hot corinos, and constrain parameters such as the thermal desorption temperature of formamide and its fragments and the binding energies involved. Our results offer support to observational data and improve our understanding of the role of the grain surface in enriching the chemistry in space.

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“…), magnesium oxide, and forsterite (Fornaro et al. ) lead to reduced half‐lives for biologically relevant organic compounds in UV irradiation experiments.…”

Section: Objective 2: Assess and Interpret The Potential Biological Hmentioning

confidence: 99%

The potential science and engineering value of samples delivered to Earth by Mars sample return

Beaty¹,

Grady²,

McSween³

et al. 2019

Meteorit & Planetary Scien

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Executive Summary Return of samples from the surface of Mars has been a goal of the international Mars science community for many years. Affirmation by NASA and ESA of the importance of Mars exploration led the agencies to establish the international MSR Objectives and Samples Team (iMOST). The purpose of the team is to re‐evaluate and update the sample‐related science and engineering objectives of a Mars Sample Return (MSR) campaign. The iMOST team has also undertaken to define the measurements and the types of samples that can best address the objectives. Seven objectives have been defined for MSR, traceable through two decades of previously published international priorities. The first two objectives are further divided into sub‐objectives. Within the main part of the report, the importance to science and/or engineering of each objective is described, critical measurements that would address the objectives are specified, and the kinds of samples that would be most likely to carry key information are identified. These seven objectives provide a framework for demonstrating how the first set of returned Martian samples would impact future Martian science and exploration. They also have implications for how analogous investigations might be conducted for samples returned by future missions from other solar system bodies, especially those that may harbor biologically relevant or sensitive material, such as Ocean Worlds (Europa, Enceladus, Titan) and others. Summary of Objectives and Sub‐Objectives for MSR Identified by iMOST This objective is divided into five sub‐objectives that would apply at different landing sites. 1.1 Characterize the essential stratigraphic, sedimentologic, and facies variations of a sequence of Martian sedimentary rocks. 1.2 Understand an ancient Martian hydrothermal system through study of its mineralization products and morphological expression. 1.3 Understand the rocks and minerals representative of a deep subsurface groundwater environment. 1.4 Understand water/rock/atmosphere interactions at the Martian surface and how they have changed with time. 1.5 Determine the petrogenesis of Martian igneous rocks in time and space. This objective has three sub‐objectives: 2.1 Assess and characterize carbon, including possible organic and pre‐biotic chemistry. 2.2 Assay for the presence of biosignatures of past life at sites that hosted habitable environments and could have preserved any biosignatures. 2.3 Assess the possibility that any life forms detected are alive, or were recently alive. Summary of iMOST Findings Several specific findings were identified during the iMOST study. While they are not explicit recommendations, we suggest that they should serve as guidelines for future decision making regarding planning of potential future MSR missions. The samples to be collected by the Mars 2020 (M‐2020) rover will be of sufficient size and quality to address and solve a wide variety of scientific questions. Samples, by definition, are a statistical representation of a larger entity...

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Infrared spectral investigations of UV irradiated nucleobases adsorbed on mineral surfaces

Cited by 32 publications

References 65 publications

Dispersion corrected DFT approaches for anharmonic vibrational frequency calculations: nucleobases and their dimers

Dispersion corrected DFT approaches for anharmonic vibrational frequency calculations: nucleobases and their dimers

Photoprocessing of formamide ice: route towards prebiotic chemistry in space

The potential science and engineering value of samples delivered to Earth by Mars sample return

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