Adenine as a Halogen Bond Acceptor: A Combined Experimental and DFT Study

In this work, we report the cocrystallization of N9-ethyladenine with 1,2,4,5-tetrafluoro-3,6-diiodobenzene (TFDIB), a classical XB donor. As far as our knowledge extends, this is the first cocrystal reported to date where an adenine derivative acts as a halogen bond acceptor. In the solid state, each adenine ring forms two centrosymmetric H-bonded dimers: one using N1···HA6–N6 and the other N7···HB6–N6. Therefore, only N3 is available as a halogen bond acceptor that, indeed, establishes an N···I halogen bonding interaction with TFDIB. The H-bonded dimers and halogen bonds have been investigated via DFT (Density Functional Theory) calculations and the Bader’s Quantum Theory of Atoms In Molecules (QTAIM) method at the B3LYP/6-311+G* level of theory. The influence of H-bonding interactions on the lone pair donor ability of N3 has also been analyzed using the molecular electrostatic potential (MEP) surface calculations.This research was funded by MINECO/AEI from Spain, project numbers ENE2015-63969, CTQ2017-85821-R FEDER and SEV2015-0496We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI)Peer reviewe

Fusing actigraphy signals for outpatient monitoring

[EN] Actigraphy devices have been successfully used as effective tools in the treatment of diseases such as sleep disorders or major depression. Although several efforts have been made in recent years to develop smaller and more portable devices, the features necessary for the continuous monitoring of outpatients require a less intrusive, obstructive and stigmatizing acquisition system. A useful strategy to overcome these limitations is based on adapting the monitoring system to the patient lifestyle and behavior by providing sets of different sensors that can be worn simultaneously or alternatively. This strategy offers to the patient the option of using one device or other according to his/her particular preferences. However this strategy requires a robust multi-sensor fusion methodology capable of taking maximum profit from all of the recorded information. With this aim, this study proposes two actigraphy fusion models including centralized and distributed architectures based on artificial neural networks. These novel fusion methods were tested both on synthetic datasets and real datasets, providing a parametric characterization of the models' behavior, and yielding results based on real case applications. The results obtained using both proposed fusion models exhibit good performance in terms of robustness to signal degradation, as well as a good behavior in terms of the dependence of signal quality on the number of signals fused. The distributed and centralized fusion methods reduce the mean averaged error of the original signals to 44% and 46% respectively when using simulated datasets. The proposed methods may therefore facilitate a less intrusive and more dependable way of acquiring valuable monitoring information from outpatients.This work was partially funded by the European Commission: Help4Mood (Contract No. FP7-ICT-2009-4: 248765). E. FusterGarcia acknowledges Programa Torres Quevedo from Ministerio de Educacion y Ciencia, co-founded by the European Social Fund (PTQ-12-05693).Fuster García, E.; Bresó Guardado, A.; Martínez Miranda, JC.; Rosell-Ferrer, J.; Matheson, C.; García Gómez, JM. (2015). Fusing actigraphy signals for outpatient monitoring. Information Fusion. 23:69-80. https://doi.org/10.1016/j.inffus.2014.08.003S69802

Oxalic Acid, a Versatile Coformer for Multicomponent Forms with 9-Ethyladenine

Six new multicomponent solids of 9-ethyladenine and oxalic acid have been detected and characterized. The salt screening has been performed by mechanochemical and solvent crystallization processes. Single crystals of the anhydrous salts in 1:1 and 2:1 nucleobase:coformer molar ratio were obtained by solution crystallization and elucidated by single-crystal X-ray analysis. The supramolecular interactions observed in these solids have been studied using density functional theory (DFT) calculations and characterized by the quantum theory of “atoms in molecules” (QTAIM) and the noncovalent interaction plot (NCIPlot) index methods. The energies of the H-bonding networks observed in the solid state of the anhydrous salts in 1:1 and 2:1 nucleobase:coformer are reported, disclosing the strong nature of the charge assisted NH···O hydrogen bonds and also the relative importance of ancillary C–H··O H-bonds.M.B. and E.M. are grateful to the Severo Ochoa FunFuture project (MICINN, CEX2019- 917S) and Generalitat de Catalunya (2017SGR1687). M.B.-O. thanks the Vice-Rector for Research and International Relations of the University of the Balearic Islands for the financial support in setting up the single-crystal X-ray diffraction facility. A.F. thanks the MICIU/AEI from Spain for financial support (Projects CTQ2017-85821-R and PID2020-115637GB-I00, Feder funds).Peer reviewe

Adenine as a Halogen Bond Acceptor: A Combined Experimental and DFT Study

In this work, we report the cocrystallization of N9-ethyladenine with 1,2,4,5-tetrafluoro-3,6-diiodobenzene (TFDIB), a classical XB donor. As far as our knowledge extends, this is the first cocrystal reported to date where an adenine derivative acts as a halogen bond acceptor. In the solid state, each adenine ring forms two centrosymmetric H-bonded dimers: one using N1···HA6–N6 and the other N7···HB6–N6. Therefore, only N3 is available as a halogen bond acceptor that, indeed, establishes an N···I halogen bonding interaction with TFDIB. The H-bonded dimers and halogen bonds have been investigated via DFT (Density Functional Theory) calculations and the Bader’s Quantum Theory of Atoms In Molecules (QTAIM) method at the B3LYP/6-311+G* level of theory. The influence of H-bonding interactions on the lone pair donor ability of N3 has also been analyzed using the molecular electrostatic potential (MEP) surface calculations.This research was funded by MINECO/AEI from Spain, project numbers ENE2015-63969, CTQ2017-85821-R FEDER and SEV2015-0496We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI)Peer reviewe

1-Ethyluracil, a New Scaffold for Preparing Multicomponent Forms: Synthesis, Characterization, and Computational Studies

In this work, we describe the successful preparation of a series of cocrystals of the modified nucleobase 1-ethyluracil with different coformers in a 1:1 or 2:1 (nucleobase:coformer) ratio including urea (URE) or some compounds containing carboxylic and hydroxyl groups such as l-malic acid (MAL), l-tartaric acid (TAR), 2-hydroxybenzoic acid (SAL), 4-hydroxybenzoic acid (4HB), and 2,4-dihydroxybenzoic acid (DHB). The influence of the hydroxyl substituent on the alkyl chain for 1·TAR and 1·SAL cocrystals or the phenyl ring for 1·SAL, 1·4HB, and 1·DHB multicomponent solids was studied. All of the compounds were characterized by powder X-ray diffraction, FT-IR, and thermal methods. Moreover, for those whose single-crystal structures could be determined, computational studies were also performed to investigate the factors that may affect the cocrystal formation, the recurrent motifs, and the energies associated with the H-bonding interactions using DFT calculations and a combination of the quantum theory of atoms in molecules (QTAIM) and the noncovalent interaction index (NCIplot) computational tools.This work has been carried out through MINECO/FEDER grant ENE2015-63969. M.B. and E.M. are grateful to the Severo Ochoa FunFuture project (MICINN, CEX2019-917S) and the Generalitat de Catalunya (2017SGR1687). M.B.-O. thanks the Vice-Rector for Research and International Relations of the University of the Balearic Islands for financial support in setting up the single-crystal X-ray diffraction facility. A.F. thanks the MICIU/AEI from Spain for financial support (Project CTQ2017-85821-R, Feder funds).Peer reviewe

Síntesis y utilización del complejo ternario Cu-fenantrolina-ácido iodohipúrico y compuestos relacionados como fármacos antitumorales

Solicitud de patente (concesión en curso).-- Referencia OEPM: P200601111.-- Fecha de presentación: 03/05/2006.-- Solicitantes: Universitat de les Illes Balears (UIB).La presente invención se refiere a complejos ternarios formados por Cu (II), 1,10-fenantrolina o 2,2-bipiridilo y diferentes ácidos hipúricos de fórmula general: [Cu A B2]+C · nH2O, donde A se selecciona de entre: I-hip, Hip, BGG y B^IGG; B se selecciona de entre: phen y bpy; C se selecciona de entre I-hip^-, Hip^-, B^IGG^-; BGG^- y I^-; y n, si existe, son las aguas de cristalización que pueden variar entre 1 y 7. Dichos compuestos en disolución presentan una gran estabilidad en forma de complejos de Cu (I), que actúan a nivel de ADN y, por tanto, son útiles como agentes antitumorales, en particular en cáncer humano y especialmente cáncer de pulmón.Peer reviewe

Adenine as a Halogen Bond Acceptor: A combined experimental and DFT study

[eng] In this work, we report the cocrystallization of N9-ethyladenine with 1,2,4,5-tetrafluoro-3,6- diiodobenzene (TFDIB), a classical XB donor. As far as our knowledge extends, this is the first cocrystal reported to date where an adenine derivative acts as a halogen bond acceptor. In the solid state, each adenine ring forms two centrosymmetric H-bonded dimers: one using N1···HA6-N6 and the other N7···HB6-N6. Therefore, only N3 is available as a halogen bond acceptor that, indeed, establishes an N···I halogen bonding interaction with TFDIB. The H-bonded dimers and halogen bonds have been investigated via DFT (Density Functional Theory) calculations and the Bader's Quantum Theory of Atoms In Molecules (QTAIM) method at the B3LYP/6-311+G* level of theory. The influence of H-bonding interactions on the lone pair donor ability of N3 has also been analyzed using the molecular electrostatic potential (MEP) surface calculations

Endkonturnahes selektives Lasersintern von keramischen Pulvern

In der aktuellen Forschung werden die Eigenschaften und Anwendungen von ultrakurzgepulster Laserstrahlung im selektiven Lasersintern von keramischen Pulvern untersucht. Die hohe Verschleißfestigkeit und Biokompatibilität prädestinieren Keramiken für vielfältige technische und medizinische Anwendungen. Hohe Rissneigung durch Temperaturgradienten im Sinterprozess, sowie die hohen Schmelztemperaturen sind dabei Herausforderungen und stehen im Fokus der Technologieentwicklung. Die Nutzung einer inversen Schichterzeugungskinematik ermöglicht einen effizienten Pulverauftrag. Kerninnovation ist die Anwendung des Ultrakurzpulslasers. Mit diesem gelingt es, sowohl Zirkonoxid als auch Aluminiumoxid in verschiedenen stofflichen Konfigurationen zu sintern, wobei stabile und teilweise glasierte Oberflächen sowie stapelbare Sinterschichten erfolgreich erzeugt werden.In current research, the properties and applications of ultra-short pulsed laser radiation in the selective laser sintering of ceramic powders are explored. The high wear resistance and biocompatibility of ceramics make them usable for a wide range of technical and medical applications. Challenges, such as a high propensity for cracking due to temperature gradients during the sintering process and the elevated melting temperatures, are central to technology development. The use of an inverse layer generation kinematics enables efficient powder application. The core innovation is the application of the ultrashort pulse laser. With this, it is possible to sinter both zirconia and alumina in various material configurations, successfully producing stable and partially glazed surfaces as well as stackable sintered layers

9-Ethyladenine: Mechanochemical Synthesis, Characterization and DFT Calculations of Novel Cocrystals and Salts

Liquid-assisted grinding and solvent crystallizations have been undertaken to prepare salts and cocrystals of the modified nucleobase 9-ethyladenine with several carboxylic acids. The new solid forms have been characterized by X-ray powder and single-crystal diffraction, attenuated total reflectance Fourier transformed infrared spectroscopy, and thermal methods. From single-crystal structures we have observed that the length of the alkyl chain in the carboxylic acid prevents a canonical self-assembly for the longest coformer. Moreover, density functional theory (DFT) calculations combined with the quantum theory of “Atoms-in-Molecules” QTAIM have been performed to analyze the different binding modes of adenine and the energetic features of the complexes. In particular, the interaction energies of several adenine dimers and trimers, and also the hydrogen bonds with carboxylic acids interacting with Watson–Crick and Hoogsten faces of adenine, have been computed and compared.This research was funded by MINECO/AEI from Spain, project numbers ENE2015-63969, CTQ2017-85821-R FEDER, and SEV2015-0496 and by the DireccióGeneral de Recerca i Innovaciódel Govern Balear (AAEE039/2017).Peer reviewe