Elena R. Alonso

Bio: Elena R. Alonso is an academic researcher from University of the Basque Country. The author has contributed to research in topics: Conformational isomerism & Rotational spectroscopy. The author has an hindex of 9, co-authored 49 publications receiving 276 citations. Previous affiliations of Elena R. Alonso include University of Valladolid.

Toward the RNA-World in the Interstellar Medium-Detection of Urea and Search of 2-Amino-oxazole and Simple Sugars.

Abstract: In the past decade, astrochemistry has witnessed an impressive increase in the number of detections of complex organic molecules. Some of these species are of prebiotic interest such as glycolaldeh...

The role of amino acid side chains in stabilizing dipeptides: the laser ablation Fourier transform microwave spectrum of Ac-Val-NH2.

Abstract: The steric effects imposed by the isopropyl group of valine in the conformational stabilization of the capped dipeptide N-acetyl-l-valinamide (Ac-Val-NH2) have been studied by laser ablation molecular beam Fourier transform microwave (LA-MB-FTMW) spectroscopy. The rotational and quadrupole coupling constants of the two 14N nuclei determined in this work show that this dipeptide exists as a mixture of C7 and C5 conformers in the supersonic expansion. The conformers are stabilized by a C[double bond, length as m-dash]OH-N intramolecular hydrogen bond closing a seven- or a five-membered ring, respectively. The observation of both conformers is in good agreement with previous results on the related dipeptides containing different residues, confirming that the polarity/non-polarity of the side chains of the amino acid is responsible for the conformational locking/unlocking. The voluminous isopropyl group is not able to prevent the less stable C5 conformer from forming but it destabilizes the C[double bond, length as m-dash]OH-N interaction.

Unveiling the n→π* interactions in dipeptides

Abstract: Numerous studies have suggested that the n→π* interactions between carbonyls could contribute significantly to the stability of proteins. Nevertheless, their evaluation is challenging because of the solvent environment or crystal packing forces in solids. Here we study the rotational spectrum of HGlyProOH dipeptide, a very common sequence found in collagen, the most abundant protein in vertebrates, in isolated conditions. Three different structures are unequivocally characterized in the gas phase. Interestingly, the most abundant structure is stabilized by an n→π* interaction and adopts the same conformation as is found in crystalline collagen. This observation serves to support the importance of the n→π* interactions between carbonyl groups. The n→π* interaction between carbonyls in peptide bonds has been proposed to contribute to protein conformational stability. Here the authors report gas-phase rotational spectroscopy of the glycine-proline dipeptide, revealing that the n→π* interaction stabilizes the trans conformation of the dipeptide with energetics comparable to those of hydrogen bonds.

Unveiling the Neutral Forms of Glutamine.

Abstract: Neutral glutamine has been evaporated by laser ablation of its solid sample to seed a rare gas carrier prior to a supersonic expansion and proved by Fourier transform microwave techniques. We report on three distinct neutral conformers that show a singular non-interacting and flexible amide sidechain in contrast with the other proteinogenic aliphatic amino acids. It could explain the essential biological role of glutamine as a nitrogen source, and its unique ability to form a variety of hydrogen bonds with peptide backbones. Common computational methods fail to predict the delicate balance of intramolecular interactions controlling the geometry of the most stable conformer. The spectroscopic data here reported can be used to benchmark novel computational methods in quantum chemistry.

The GUAPOS project - II. A comprehensive study of peptide-like bond molecules

Abstract: Context. Peptide-like bond molecules, which can take part in the formation of proteins in a primitive Earth environment, have been detected only towards a few hot cores and hot corinos up to now.Aims. We present a study of HNCO, HC(O)NH2 , CH3 NCO, CH3 C(O)NH2 , CH3 NHCHO, CH3 CH2 NCO, NH2 C(O)NH2 , NH2 C(O)CN, and HOCH2 C(O)NH2 towards the hot core G31.41+0.31. The aim of this work is to study these species together to allow a consistent study among them.Methods. We have used the spectrum obtained from the ALMA 3 mm spectral survey GUAPOS, with a spectral resolution of ~0.488 MHz (~1.3–1.7 km s−1 ) and an angular resolution of 1.′′2 × 1.′′2 (~4500 au), to derive column densities of all the molecular species presented in this work, together with 0.′′2 × 0.′′2 (~750 au) ALMA observations from another project to study the morphology of HNCO, HC(O)NH2 , and CH3 C(O)NH2 .Results. We have detected HNCO, HC(O)NH2 , CH3 NCO, CH3 C(O)NH2 , and CH3 NHCHO, but no CH3 CH2 NCO, NH2 C(O)NH2 , NH2 C(O)CN, or HOCH2 C(O)NH2 . This is the first time that these molecules have been detected all together outside the Galactic centre. We have obtained molecular fractional abundances with respect to H2 from 10−7 down to a few 10−9 and abundances with respect to CH3 OH from 10−3 to ~4 × 10−2 , and their emission is found to be compact (~2′′, i.e. ~7500 au). From the comparison with other sources, we find that regions in an earlier stage of evolution, such as pre-stellar cores, show abundances at least two orders of magnitude lower than those in hot cores, hot corinos, or shocked regions. Moreover, molecular abundance ratios towards different sources are found to be consistent between them within ~1 order of magnitude, regardless of the physical properties (e.g. different masses and luminosities), or the source position throughout the Galaxy. Correlations have also been found between HNCO and HC(O)NH2 as well as CH3 NCO and HNCO abundances, and for the first time between CH3 NCO and HC(O)NH2 , CH3 C(O)NH2 and HNCO, and CH3 C(O)NH2 and HC(O)NH2 abundances. These results suggest that all these species are formed on grain surfaces in early evolutionary stages of molecular clouds, and that they are subsequently released back to the gas phase through thermal desorption or shock-triggered desorption.

Molecular Evolution and Star Formation: From Prestellar Cores to Protostellar Cores

Abstract: We investigate molecular evolution in a star-forming core that is initially a hydrostatic starless core and collapses to form a low-mass protostar. The results of a one-dimensional radiation-hydrodynamics calculation are adopted as a physical model of the core. We first derive radii at which CO and large organic species sublimate. CO sublimation in the central region starts shortly before the formation of the first hydrostatic core. When the protostar is born, the CO sublimation radius extends to 100 AU, and the region inside $\lesssim 10$ AU is hotter than 100 K, at which some large organic species evaporate. We calculate the temporal variation of physical parameters in infalling shells, in which the molecular evolution is solved using an updated gas-grain chemical model to derive the spatial distribution of molecules in a protostellar core. The shells pass through the warm region of $10 -100$ K in several $\times$ $10^4$ yr, and fall into the central star $\sim 100$ yr after they enter the region where $T \gtrsim 100$ K. We find that large organic species are formed mainly via grain-surface reactions at temperatures of $20 -40$ K and then desorbed into the gas-phase at their sublimation temperatures. Carbon-chain species can be formed by a combination of gas-phase reactions and grain-surface reactions following the sublimation of CH$_4$. Our model also predicts that CO$_2$ is more abundant in isolated cores, while gas-phase large organic species are more abundant in cores embedded in ambient clouds.

Accuracy and Interpretability: The Devil and the Holy Grail. New Routes across Old Boundaries in Computational Spectroscopy.

Abstract: The past decade has witnessed an increasing interaction between experiment and theory in the field of molecular spectroscopy. On the computational side, ongoing developments of hardware and software have moved computational spectroscopy from a highly specialized research area to a general tool for researchers in different fields of chemical science. However, since its dawn, computational spectroscopy has been characterized by the dichotomies of qualitative and quantitative description, and of interpretation and accuracy. Indeed, the analysis of experiments is seldom straightforward because of the subtle interplay of several different effects, which are not easy to evaluate and isolate, and/or the complexity of the system under consideration. Often, the accuracy has to be set aside for a more qualitative analysis that will provide the means for a broad interpretation. In such a scenario, the most recent advances in theoretical treatments as well as computational tools have opened the way to the reconciliation of accuracy and interpretability, resulting in unequivocal analyses and assignments of experimental spectra and their unbiased interpretation. This Review aims at being a comprehensive, authoritative, critical, and readable account of general interest to the chemistry community because of the wealth of qualitative and quantitative information that can be obtained from spectroscopic investigations. Limiting ourselves to rotational and vibrational spectroscopy, emphasis will be put on accuracy and interpretability as well as on the routes toward their reconciliation and integration.

Origin of the Photoluminescence of Metal Nanoclusters: From Metal-Centered Emission to Ligand-Centered Emission

Abstract: Recently, metal nanoclusters (MNCs) emerged as a new class of luminescent materials and have attracted tremendous interest in the area of luminescence-related applications due to their excellent luminous properties (good photostability, large Stokes shift) and inherent good biocompatibility. However, the origin of photoluminescence (PL) of MNCs is still not fully understood, which has limited their practical application. In this mini-review, focusing on the origin of the photoemission emission of MNCs, we simply review the evolution of luminescent mechanism models of MNCs, from the pure metal-centered quantum confinement mechanics to ligand-centered p band intermediate state (PBIS) model via a transitional ligand-to-metal charge transfer (LMCT or LMMCT) mechanism as a compromise model.

A rigorous detection of interstellar CH3NCO: An important missing species in astrochemical networks

Abstract: The recent analysis of the composition of the frozen surface of comet 67P/Churyumov-Gerasimenko has revealed a significant number of complex organic molecules. Methyl isocyanate (CH3NCO) is one of the more abundant species detected on the comet surface. In this work we report extensive characterization of its rotational spectrum resulting in a list of 1269 confidently assigned laboratory lines and its detection in space towards the Orion clouds where 399 lines of the molecule have been unambiguously identified. We find that the limited mm-wave laboratory data reported prior to our work require some revision. The abundance of CH3NCO in Orion is only a factor of ten below those of HNCO and CH3CN. Unlike the molecular abundances in the coma of comets, which correlate with those of warm molecular clouds, molecular abundances in the gas phase in Orion are only weakly correlated with those measured on the comet surface. We also compare our abundances with those derived recently for this molecule towards Sgr B2 (Halfen et al. 2015, ApJ, 812, L5). A more accurate abundance of CH3NCO is provided for this cloud based on our extensive laboratory work.