Estimation of comprehensive two-dimensional gas chromatographic response from one-dimensional gas chromatography data

Trabajo presentado a la XV Reunión Científica de la Sociedad Española de Cromatografía y Técnicas Afines (SECyTA) celebrada en Castellón de la Plana del 28 al 30 de octubre de 2015Optimization of a separation in comprehensive two-dimensional gas chromatography (GC×GC) requires the selection of an appropriate set column, and the optimisation of their respective dimensions, temperature programs and flow rates. Until not so long ago, a time consuming trial and error process was the only way to select the columns and chromatographic conditions for the two GC dimensions. During the last few years, several attempts have been proposed to estimate the chromatographic response in GC×GC [1-4]. Although most of these methods are helpful contributions, some of them focussed exclusively on the retention time estimation and do not consider the effect of peak width, also essential for a correct prediction of the chromatographic separation capability. Others are based on theoretical formulas not applicable to the extreme experimental conditions used in GC×GC, or are only valid for specific types of compounds or stationary phases: these models cannot be corrected for different separation problems. In this work, modelization of retention time and peak width has been carried out from experimental 1D GC data in order to estimate the response in GC×GC separation for different column sets operated under different flows and temperatures. Several theoretical and experimental models are proposed for estimation of 1D and 2D retention time and peak width; in experimental models, 1D GC data are required together with information on column characteristics and operation conditions. Models for hold-up time, retention factor and peak width were first validated in 1D GC from the fit between experimental and calculated data. Their validation in GC×GC was carried out by using n-alkanes and a mixture of disaccharides as their trimethylsilyl oxime derivatives. Comparison of experimental and estimated data showed good results for retention time in both first and second dimension. Peak widths presented, however, some errors, caused by the no consideration on estimation of the effect of the modulator or the rather unusual chromatographic conditions used. The developed programme is very versatile as it can be used for the calculation of the chromatographic response of compounds with different polarity and volatility, analysed under different pressures and temperature ramps, and with different sets of columns. [1] J.V. Seeley, E.M. Libby, K.A.H. Edwards, S.K. Seeley, J. Chromatogr. A 1216 (2009) 1650. [2] F.L. Dorman, P.D. Schettler, L.A. Vogt, J.W. Cochran, J. Chromatogr. A 1186 (2008) 196. [3] Y. Zhao, J. Zhang, B. Wang, S.H. Kim, A. Fang, B. Bogdanov, Z. Zhou, C. McClain, X. Zhang, J. Chromatogr. A 1218 (2011) 2577. [4] S. Zhu, S. He, D.R. Worton, A.H. Goldstein, J. Chromatogr. A 1233 (2012) 147. Acknowledgements: This work has been funded by Ministerio de Economía y Competitividad (project CTQ2012-32957), Comunidad Autónoma de Madrid (Spain) and European funding from FEDER program (AVANSECAL-CM S2013/ABI-3028) and Fundación Ramón Areces. ACS thanks Ministerio de Economía y Competitividad of Spain for a Ramón y Cajal contract.CTQ2012-32957Peer reviewe

Chemical modification of titanium precursor to obtain stable silica-titania sol: acetylacetone

[ES] La técnica Sol-Gel se ha utilizado para sintetizar una serie de sistemas multicomponentes, entre ellos SiO2 – TiO2. El mayor problema en la obtención de geles multicomponentes estables es la desigual velocidad de hidrólisis y condensación que presentan los alcóxidos precursores de los cationes de interés. En este trabajo se muestra cómo adicionando acetilacetona, acacH, al sistema TEOS – Ti(OBu)4 – H2O se puede obtener un sol estable. Se tomaron diferentes concentraciones de los precursores de silicio y titanio y una sola concentración de acacH. Se utilizó espectroscopia infrarroja, FTIR, para identificar los grupos funcionales presentes en el sistema y además se midió regularmente la viscosidad para determinar cualitativamente el avance de la policondensación del sistema.[EN] Sol-gel processing has become a well established technique for producing ceramic powders or glasses. This processing has been utilized to synthesize several interesting systems, e.g. the SiO2 – TiO2 system. A major concern in the stable multicomponent geles is that the hydrolysis and condensation velocities are diferent for each precursor, TEOS and Ti(OBu)4 in this work. The chemical control of these reactions is currently performed by adding complexing reagents that react with metal alkoxides at a molecular level, giving rise to new molecular precursors of different structure, reactivity and functionanality. This paper shows that stable TEOS – Ti(OBu)4 – H2O sol can be reproducibly prepared in the presence of acetylacetone. We shall then show that the acac behaves as a ligand, directly bonded to the titanium ion. Thus the formation of precipitate is avoided. Infra-red spectroscopy (FTIR) and viscosity measures were used to demostrated this behaviour of the system.Este trabajo fue financiado a través de los proyectos COLCIENCIAS N° 1103-05-605-93 y VRI-Universidad del Cauca N° 752. Agradecemos a Ecopetrol-ICP la colaboración prestada con los estudios de espectroscopia infrarroja y a la red CyTED VIII.E la ayuda económica y técnica gracias a la cual A. Mafla pudo realizar su pasantía en el ICVCSIC de Madrid-España.Peer reviewe

Lactonas sesquiterpénicas en el Género Centaurea

Se presenta una revisión de lactonas sesquiterpénicas procedentes de especies del género Centaurea (Compositae).A survey of sesquiterpene lactones from the species of Centaurea genus (Compositae) is presented

Lactonas sesquiterpénicas en el Género Centaurea

Se presenta una revisión de lactonas sesquiterpénicas procedentes de especies del género Centaurea (Compositae).Se presenta una revisión de lactonas sesquiterpénicas procedentes de especies del género Centaurea (Compositae)

Hydrolase–like catalysis and structural resolution of natural products by a metal–organic framework

The exact chemical structure of non–crystallising natural products is still one of the main challenges in Natural Sciences. Despite tremendous advances in total synthesis, the absolute structural determination of a myriad of natural products with very sensitive chemical functionalities remains undone. Here, we show that a metal–organic framework (MOF) with alcohol–containing arms and adsorbed water, enables selective hydrolysis of glycosyl bonds, supramolecular order with the so–formed chiral fragments and absolute determination of the organic structure by single–crystal X–ray crystallography in a single operation. This combined strategy based on a biomimetic, cheap, robust and multigram available solid catalyst opens the door to determine the absolute configuration of ketal compounds regardless degradation sensitiveness, and also to design extremely–mild metal–free solid–catalysed processes without formal acid protons.This work was supported by the Ministero dell’Istruzione, dell’Università e della Ricerca (Italy) and the MINECO (Spain) (Projects CTQ2016-75671-P, CTQ 2017-86735-P, RTC-2017-6331-5, Severo Ochoa program SEV-2016-0683 and Excellence Unit “Maria de Maeztu” MDM-2015-0538). R.B. thanks the MIUR (Project PON R&I FSE-FESR 2014–2020) for grant. L.B wishes to thank Italian MIUR for grant n. AIM1899391–1 in the framework of the project “Azione I.2, Mobilità dei Ricercatori, PON R&I 2014–2020”. Thanks are also extended to the “2019 Post-doctoral Junior Leader-Retaining Fellowship, la Caixa Foundation (ID100010434 and fellowship code LCF/BQ/PR19/11700011” (J. F.- S.). S. S.-N. thanks ITQ for the concession of a contract. D.A. acknowledges the financial support of the Fondazione CARIPLO/“Economia Circolare: ricerca per un futuro sostenibile” 2019, Project code: 2019–2090, MOCA. E.P. acknowledges the financial support of the European Research Council under the European Union’s Horizon 2020 research and innovation program/ERC Grant Agreement No. 814804, MOF-reactors

Impact of power ultrasound on chemical and physicochemical quality indicators of strawberries dried by convection

[EN] A study on the quality parameters of strawberries dehydrated by convection assisted by power ultrasound (US) at 40 70 C and 30 and 60W has been carried out for the first time. In general, the quality of US-treated samples was higher than that of commercial samples. Even under the most severe conditions used (US at 70 C and 60 W), high values of vitamin C retention (>65%) and scarce advance of Maillard reaction (2-furoylmethyl derivatives of Lys and Arg < 90 mg 100 g 1 protein) were observed. Rehydration ratio was not affected by the power applied and the obtained values were similar to those of convectively-treated samples. According to the results here presented, US is a suitable example of an emerging and environmentally friendly technology that accelerates convective drying, allowing the obtainment of dried strawberries with premium quality.This work has been funded by Ministry of Economy and Competitiveness of Spain and ERDF (FEDER) (Project DPI2012-37466-C03-03), Fun-c-Food (CSD2007-00063 Consolider-INGENIO 2010), CYTED IBEROFUN (P109AC0302) and Comunidad de Valencia, Project PROMETEO/2010/062. J.G.S. also thanks CSIC and the EU for a predoctoral JAE grant. A.C.S. thanks the Spanish Ministry of Economy and Competitiveness for a Ramon y Cajal contract.Gamboa-Santos, J.; Montilla, A.; Cortijo Soria, A.; Cárcel Carrión, JA.; García Pérez, JV.; Villamiel, M. (2014). Impact of power ultrasound on chemical and physicochemical quality indicators of strawberries dried by convection. Food Chemistry. 161:40-46. https://doi.org/10.1016/j.foodchem.2014.03.106S404616

<i>Gaia</i> Data Release 1. Summary of the astrometric, photometric, and survey properties

Context. At about 1000 days after the launch of Gaia we present the first Gaia data release, Gaia DR1, consisting of astrometry and photometry for over 1 billion sources brighter than magnitude 20.7. Aims. A summary of Gaia DR1 is presented along with illustrations of the scientific quality of the data, followed by a discussion of the limitations due to the preliminary nature of this release. Methods. The raw data collected by Gaia during the first 14 months of the mission have been processed by the Gaia Data Processing and Analysis Consortium (DPAC) and turned into an astrometric and photometric catalogue. Results. Gaia DR1 consists of three components: a primary astrometric data set which contains the positions, parallaxes, and mean proper motions for about 2 million of the brightest stars in common with the HIPPARCOS and Tycho-2 catalogues – a realisation of the Tycho-Gaia Astrometric Solution (TGAS) – and a secondary astrometric data set containing the positions for an additional 1.1 billion sources. The second component is the photometric data set, consisting of mean G-band magnitudes for all sources. The G-band light curves and the characteristics of ∼3000 Cepheid and RR-Lyrae stars, observed at high cadence around the south ecliptic pole, form the third component. For the primary astrometric data set the typical uncertainty is about 0.3 mas for the positions and parallaxes, and about 1 mas yr−1 for the proper motions. A systematic component of ∼0.3 mas should be added to the parallax uncertainties. For the subset of ∼94 000 HIPPARCOS stars in the primary data set, the proper motions are much more precise at about 0.06 mas yr−1. For the secondary astrometric data set, the typical uncertainty of the positions is ∼10 mas. The median uncertainties on the mean G-band magnitudes range from the mmag level to ∼0.03 mag over the magnitude range 5 to 20.7. Conclusions. Gaia DR1 is an important milestone ahead of the next Gaia data release, which will feature five-parameter astrometry for all sources. Extensive validation shows that Gaia DR1 represents a major advance in the mapping of the heavens and the availability of basic stellar data that underpin observational astrophysics. Nevertheless, the very preliminary nature of this first Gaia data release does lead to a number of important limitations to the data quality which should be carefully considered before drawing conclusions from the data

Regulation of Bestrophins by Ca2+: A Theoretical and Experimental Study

Bestrophins are a recently discovered family of Cl− channels, for which no structural information is available. Some family members are activated by increased intracellular Ca2+ concentration. Bestrophins feature a well conserved Asp-rich tract in their COOH terminus (Asp-rich domain), which is homologous to Ca2+-binding motifs in human thrombospondins and in human big-conductance Ca2+- and voltage-gated K+ channels (BKCa). Consequently, the Asp-rich domain is also a candidate for Ca2+ binding in bestrophins. Based on these considerations, we constructed homology models of human bestrophin-1 (Best1) Asp-rich domain using human thrombospondin-1 X-ray structure as a template. Molecular dynamics simulations were used to identify Asp and Glu residues binding Ca2+ and to predict the effects of their mutations to alanine. We then proceeded to test selected mutations in the Asp-rich domain of the highly homologous mouse bestrophin-2. The mutants expressed in HEK-293 cells were investigated by electrophysiological experiments using the whole-cell voltage-clamp technique. Based on our molecular modeling results, we predicted that Asp-rich domain has two defined binding sites and that D301A and D304A mutations may impact the binding of the metal ions. The experiments confirmed that these mutations do actually affect the function of the protein causing a large decrease in the Ca2+-activated Cl− current, fully consistent with our predictions. In addition, other studied mutations (E306A, D312A) did not decrease Ca2+-activated Cl− current in agreement with modeling results

Regulation of Bestrophins by Ca2+: A Theoretical and Experimental Study

Bestrophins are a recently discovered family of Cl− channels, for which no structural information is available. Some family members are activated by increased intracellular Ca2+ concentration. Bestrophins feature a well conserved Asp-rich tract in their COOH terminus (Asp-rich domain), which is homologous to Ca2+-binding motifs in human thrombospondins and in human big-conductance Ca2+- and voltage-gated K+ channels (BKCa). Consequently, the Asp-rich domain is also a candidate for Ca2+ binding in bestrophins. Based on these considerations, we constructed homology models of human bestrophin-1 (Best1) Asp-rich domain using human thrombospondin-1 X-ray structure as a template. Molecular dynamics simulations were used to identify Asp and Glu residues binding Ca2+ and to predict the effects of their mutations to alanine. We then proceeded to test selected mutations in the Asp-rich domain of the highly homologous mouse bestrophin-2. The mutants expressed in HEK-293 cells were investigated by electrophysiological experiments using the whole-cell voltage-clamp technique. Based on our molecular modeling results, we predicted that Asp-rich domain has two defined binding sites and that D301A and D304A mutations may impact the binding of the metal ions. The experiments confirmed that these mutations do actually affect the function of the protein causing a large decrease in the Ca2+-activated Cl− current, fully consistent with our predictions. In addition, other studied mutations (E306A, D312A) did not decrease Ca2+-activated Cl− current in agreement with modeling results

Characterization of Italian honeys (Marche Region) on the basis of their mineral content and some typical quality parameters

<p>Abstract</p> <p>Background</p> <p>The characterization of three types of Marche (Italy) honeys (Acacia, Multifloral, Honeydew) was carried out on the basis of the their quality parameters (pH, sugar content, humidity) and mineral content (Na, K, Ca, Mg, Cu, Fe, and Mn). Pattern recognition methods such as principal components analysis (PCA) and linear discriminant analysis (LDA) were performed in order to classify honey samples whose botanical origins were different, and identify the most discriminant parameters. Lastly, using ANOVA and correlations for all parameters, significant differences between diverse types of honey were examined.</p> <p>Results</p> <p>Most of the samples' water content showed good maturity (98%) whilst pH values were in the range 3.50 – 4.21 confirming the good quality of the honeys analysed. Potassium was quantitatively the most relevant mineral (mean = 643 ppm), accounting for 79% of the total mineral content. The Ca, Na and Mg contents account for 14, 3 and 3% of the total mineral content respectively, while other minerals (Cu, Mn, Fe) were present at very low levels. PCA explained 75% or more of the variance with the first two PC variables. The variables with higher discrimination power according to the multivariate statistical procedure were Mg and pH. On the other hand, all samples of acacia and honeydew, and more than 90% of samples of multifloral type have been correctly classified using the LDA. ANOVA shows significant differences between diverse floral origins for all variables except sugar, moisture and Fe.</p> <p>Conclusion</p> <p>In general, the analytical results obtained for the Marche honeys indicate the products' high quality. The determination of physicochemical parameters and mineral content in combination with modern statistical techniques can be a useful tool for honey classification.</p